Scientific Output
Over 10.000 scientific papers have been published by members of the Materials Chain since the foundation of the University Alliance Ruhr in 2010. This tremendous output is proof of the excellent environment the Ruhr Area provides for research in the field of materials science and technology.
Below, you can either scroll through the complete list of our annually published material, or search for a specific author or term via the free text search to get to know our research strengths. You can also review the publication record of every Materials Chain member via his or her personal member’s page.
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2022 • 808 Active Buffer Matrix in Nanoparticle-Based Silicon-Rich Silicon Nitride Anodes Enables High Stability and Fast Charging of Lithium-Ion Batteries
Kilian, S.O. and Wankmiller, B. and Sybrecht, A.M. and Twellmann, J. and Hansen, M.R. and Wiggers, H.
Advanced Materials Interfaces 9 (2022)A very promising way to improve the stability of silicon in lithium-ion battery (LIB) anodes is the use of nanostructured silicon-rich silicon nitride (SiNx), known as a conversion-type anode material. To investigate the conversion mechanism in this material in detail, SiN0.5 nanoparticles are synthesized and examined as LIB anodes using a combination of ex situ X-ray photoelectron spectroscopy and solid-state 7Li MAS NMR measurements. During the initial cycle, the conversion of SiN0.5 nanoparticles results in the formation of lithium silicides and a buffer matrix consisting of different lithium nitridosilicates and lithium nitride. These phases can be reversibly lithiated and contribute to the total reversible capacity of the silicon nitride active material. The structure of the material after conversion is best described by an amorphous solid solution. Further, it is shown that silicon-rich silicon nitrides possess improved rate capability because of the higher ionic conductivity of the buffer matrix compared to pure silicon, and very fine dispersion of silicon clusters throughout the buffer matrix. Thus, unlike most conversion materials, the silicon-rich silicon nitride exhibits an additional intrinsic active functionality of the buffer matrix that goes far beyond the mere reduction of electrolyte contact area and volume expansion. © 2022 The Authors. Advanced Materials Interfaces published by Wiley-VCH GmbH.view abstract doi: 10.1002/admi.202201389 2022 • 807 Conductivity enhancement of Al- and Ta-substituted Li7La3Zr2O7 solid electrolytes by nanoparticles
Bauer, A. and Ali, M.Y. and Orthner, H. and Uhlenbruck, S. and Wiggers, H. and Fattakhova-Rohlfing, D. and Guillon, O.
Journal of the European Ceramic Society 42 1033-1041 (2022)A nanopowder consisting of La2Zr2O7 particles with lithium containing species on their surface was prepared by spray flame synthesis and subsequently added to Li7La3Zr2O12 powder obtained by a conventional solid-state reaction. The spray flame synthesis method utilized in this work yields nanoparticles with a small size of approximately 5 nm, which is unprecedented within the scope of oxide-based ionic conductors for solid-state batteries. Remarkably, the addition of nanoparticles for sintering at a relatively low temperature of 1000 °C significantly improved the ionic conductivity by 50 %. In contrast, there was no influence of incorporating nanoparticles on the conductivity at sintering temperatures at or above 1100 °C, which is the typical temperature range applied for conventional sintering of Li7La3Zr2O12. Compared to prior published work with analogous materials, a more than twofold improvement in conductivity was demonstrated while the sintering temperature was decreased by 100 °C. © 2021 Elsevier Ltdview abstract doi: 10.1016/j.jeurceramsoc.2021.11.029 2022 • 806 Determining the sintering kinetics of Fe and FexOy-Nanoparticles in a well-defined model flow reactor
Rosenberger, T. and Skenderović, I. and Sellmann, J. and Wollny, P. and Levish, A. and Wlokas, I. and Kempf, A. and Winterer, M. and Kruis, F.E.
Aerosol Science and Technology 56 833-846 (2022)A model flow reactor provides a narrow particle temperature-residence time distribution with well-defined conditions and is mandatory to measure changes of the particle structure precisely. The experimental data of iron and iron oxide agglomerates are used to determine the sintering kinetics considering the temperature-time history of the particles. Thousand particle trajectories are tracked in a validated CFD model at three different furnace temperatures each. Strongly agglomerated particles with a small primary particle size (∼4 nm) are synthesized by spark discharge and are size-selected (25–250 nm) before sintering. The structure development is measured simultaneously with different online instrumentations and the structure calculated by means of structure models. A simple sintering model, based on the reduction of surface energy, is numerically quantified with the experimental results. The surface of the particles is strongly dependent on the primary particle size and the agglomerate structure. The chemical phase is analyzed using the offline techniques XANES, XRD, and EELS. It is observed that the addition of hydrogen led to a reduction of iron oxide to iron nanoparticles and to changes of the sintering kinetics. The sintering exponent (Formula presented.) = 1 was found to be optimal. For Fe, an activation energy (Formula presented.) of 59.15 kJ/mol and a pre-exponential factor (Formula presented.) of 1.57 104 s/m were found, for Fe3O4 an activation energy (Formula presented.) of 55.22 kJ/mol and a pre-exponential factor (Formula presented.) of 2.54 104 s/m. Copyright © 2022 American Association for Aerosol Research. © 2022 American Association for Aerosol Research.view abstract doi: 10.1080/02786826.2022.2089011 2022 • 805 Efficient Synthesis of Macromolecular DO3A@Gn Derivatives for Potential Application in MRI Diagnostics: From Polymer Conjugates to Polymer Nanoparticles
Kampmann, A.-L. and Hiller, W. and Weberskirch, R.
Macromolecular Chemistry and Physics (2022)Here, the synthesis of three different macromolecular DO3A@Gn conjugates based on poly(2-oxazoline)s is presented. Therefore, poly(2-methyl-2-oxazoline) is synthesized by a ring-opening, cationic polymerization and the polymerization is terminated with DO3A(tBu)3. The best results are obtained after 48 h at 120 °C with degree of termination of 86%. After deprotection of the DO3A ligand and complexation with Gn3+, relaxivity as measured with a magnetic field strength of 9.4 T (400 MHz) reveals values for r1 of up to 2.32 mm−1 s−1. The concept is extended to a block copolymer based on 2-heptyl-2-oxazoline and 2-methyl-2-oxazoline that is again terminated with DO3A(tBu)3 to form micelles with a size of 12.6 ± 0.7 nm after DO3A(tBu)3 termination and deprotection of the 1,4,7,10-tetraazacyclododecane-N,N,N,N-tetraacetic acid ligand. After complexation with Gn3+, relaxivity r1 is 10.1 mm−1 s−1 as determined from the slope of the plot of 1/T1 against the gadolinium(III) concentration at 9.4 T. Finally, crosslinked nanoparticles are prepared from amphiphilic macro-monomers that form micelles in water and are crosslinked throughout the core in the presence of azoisobutyronitrile (AIBN). The nanoparticle is 32.9 ± 7.8 nm in size after Gn3+ complexation and reveals a relaxivity r1 of 6.77 mm−1 s−1. © 2022 The Authors. Macromolecular Chemistry and Physics published by Wiley-VCH GmbH.view abstract doi: 10.1002/macp.202200211 2022 • 804 Electrophoretic Deposition of Platinum Nanoparticles using Ethanol-Water Mixtures Significantly Reduces Neural Electrode Impedance
Ramesh, V. and Giera, B. and Karnes, J.J. and Stratmann, N. and Schaufler, V. and Li, Y. and Rehbock, C. and Barcikowski, S.
Journal of the Electrochemical Society 169 (2022)Platinum electrodes are critical components in many biomedical devices, an important example being implantable neural stimulation or recording electrodes. However, upon implantation, scar tissue forms around the electrode surface, causing unwanted deterioration of the electrical contact. We demonstrate that sub-monolayer coatings of platinum nanoparticles (PtNPs) applied to 3D neural electrodes by electrophoretic deposition (EPD) can enhance the electrode?s active surface area and significantly lower its impedance. In this work we use ethanol-water mixtures as the EPD solvent, in contrast to our previous studies carried out in water. We show that EPD coating in 30 vol.% ethanol improves the device?s electrochemical performance. Computational mesoscale multiparticle simulations were for the first time applied to PtNP-on-Pt EPD, revealing correlations between ethanol concentration, electrochemical properties, and coating homogeneity. Thereto, this optimum ethanol concentration (30 vol.%) balances two opposing trends: (i) the addition of ethanol reduces water splitting and gas bubble formation, which benefits surface coverage, and (ii) increased viscosity and reduced permittivity occur at high ethanol concentrations, which impair the coating quality and favoring clustering. A seven-fold increase in active surface area and significantly reduced in vitro impedance of the nano-modified neural stimulation electrode surfaces highlight the influence of ethanol-water mixtures in PtNP EPD. © 2022 The Electrochemical Society ("ECS"). Published on behalf of ECS by IOP Publishing Limited.view abstract doi: 10.1149/1945-7111/ac51f8 2022 • 803 Engineering mesoporous silica nanoparticles for drug delivery: where are we after two decades?
Vallet-Regí, M. and Schüth, F. and Lozano, D. and Colilla, M. and Manzano, M.
Chemical Society Reviews 51 5365-5451 (2022)The present review details a chronological description of the events that took place during the development of mesoporous materials, their different synthetic routes and their use as drug delivery systems. The outstanding textural properties of these materials quickly inspired their translation to the nanoscale dimension leading to mesoporous silica nanoparticles (MSNs). The different aspects of introducing pharmaceutical agents into the pores of these nanocarriers, together with their possible biodistribution and clearance routes, would be described here. The development of smart nanocarriers that are able to release a high local concentration of the therapeutic cargo on-demand after the application of certain stimuli would be reviewed here, together with their ability to deliver the therapeutic cargo to precise locations in the body. The huge progress in the design and development of MSNs for biomedical applications, including the potential treatment of different diseases, during the last 20 years will be collated here, together with the required work that still needs to be done to achieve the clinical translation of these materials. This review was conceived to stand out from past reports since it aims to tell the story of the development of mesoporous materials and their use as drug delivery systems by some of the story makers, who could be considered to be among the pioneers in this area. © 2022 The Royal Society of Chemistryview abstract doi: 10.1039/d1cs00659b 2022 • 802 Enhanced heterogeneous activation of peroxymonosulfate by Ruddlesden-Popper-type La2CoO4+δ nanoparticles for bisphenol A degradation
Hammad, M. and Alkan, B. and Al-kamal, A.K. and Kim, C. and Ali, M.Y. and Angel, S. and Wiedemann, H.T.A. and Klippert, D. and Schmidt, T.C. and Kay, C.W.M. and Wiggers, H.
Chemical Engineering Journal 429 (2022)The scalable synthesis of stable catalysts for environmental remediation applications remains challenging. Nonetheless, metal leaching is a serious environmental issue hindering the practical application of transition-metal based catalysts including Co-based catalysts. Herein, for the first time, we describe a facile one-step and scalable spray-flame synthesis of high surface area La2CoO4+δ nanoparticles containing excess oxygen interstitials (+δ) and use them as a stable and efficient catalyst for activating peroxymonosulfate (PMS) towards the degradation of bisphenol A. Importantly, the La2CoO4+δ catalyst exhibits higher catalytic degradation of bisphenol A (95% in 20 min) and stability than LaCoO3–x nanoparticles (60%) in the peroxymonosulfate activation system. The high content of Co2+ in the structure showed a strong impact on the catalytic performance of the La2CoO4+δ + PMS system. Despite its high specific surface area, our results showed a very low amount of leached cobalt (less than 0.04 mg/L in 30 min), distinguishing it as a material with high chemical stability. According to the radical quenching experiments and the electron paramagnetic resonance technology, SO4[rad]–, [rad]OH, and 1O2 were generated and SO4[rad]– played a dominant role in bisphenol A degradation. Moreover, the La2CoO4+δ + PMS system maintained conspicuous catalytic performance for the degradation of other organic pollutants including methyl orange, rhodamine B, and methylene blue. Overall, our results showed that we developed a new synthesis method for stable La2CoO4+δ nanoparticles that can be used as a highly active heterogeneous catalyst for PMS-assisted oxidation of organic pollutants. © 2021 Elsevier B.V.view abstract doi: 10.1016/j.cej.2021.131447 2022 • 801 Identification of the main mixing process in the synthesis of alloy nanoparticles by laser ablation of compacted micropowder mixtures
Waag, F. and Fares, W.I.M.A. and Li, Y. and Andronescu, C. and Gökce, B. and Barcikowski, S.
Journal of Materials Science 57 3041-3056 (2022)Alloy nanoparticles offer the possibility to tune functional properties of nanoscale structures. Prominent examples of tuned properties are the local surface plasmon resonance for sensing applications and adsorption energies for applications in catalysis. Laser synthesis of colloidal nanoparticles is well suited for generating alloy nanoparticles of desired compositions. Not only bulk alloys but also compacted mixtures of single-metal micropowders can serve as ablation targets. However, it is still unknown how mixing of the individual metals transfers from the micro- to the nanoscale. This work experimentally contributes to the elucidation of the mixing processes during the laser-based synthesis of alloy nanoparticles. Key parameters, such as the initial state of mixing in the ablation target, the laser pulse duration, the laser spot size, and the ablation time, are varied. Experiments are performed on a cobalt-iron alloy, relevant for application in oxidation catalysis, in ethanol. The extent of mixing in the targets after ablation and in individual nanoparticles are studied by energy-dispersive X-ray spectroscopy and by cyclic voltammetry at relevant conditions for the oxygen evolution reaction, as model reaction. The results point at the benefits of well pre-mixed ablation targets and longer laser pulse durations for the laser-based synthesis of alloy nanoparticles. Graphical abstract: [Figure not available: see fulltext.] © 2021, The Author(s).view abstract doi: 10.1007/s10853-021-06731-2 2022 • 800 LES of nanoparticle synthesis in the spraysyn burner: A comparison against experiments
Sellmann, J. and Wollny, P. and Baik, S.-J. and Suleiman, S. and Schneider, F. and Schulz, C. and Wiggers, H. and Wlokas, I. and Kempf, A.M.
Powder Technology 404 (2022)The synthesis of iron oxide nanoparticles from iron nitrate in the SpraySyn spray flame reactor was investigated by experiment and simulation. The focus was on the spray and flame structure, the particle growth by nucleation and coagulation, and the unresolved effects and their impact on the dispersed phase. The reacting flow was modeled in large eddy simulations with the premixed flamelet generated manifolds technique, including modifications for aerosol nucleation. Particle dynamics were described with a sectional model and a subgrid scale coagulation kernel. The particle size distributions at different distances from the burner surface were obtained using a particle mass spectrometer. The experiments and simulations are in good agreement for the flame centreline velocity and both size distribution and mean size of the particles (for particles larger 1 nm - the approximate detection limit of the experiment). Furthermore, simulations enabled to interpret the temporal evolution of the particle size distribution. © 2022 Elsevier B.V.view abstract doi: 10.1016/j.powtec.2022.117466 2022 • 799 Mono-, Di-, and Tri-Valent Cation Doped BiFe0.95Mn0.05O3 Nanoparticles: Ferroelectric Photocatalysts
Dubey, A. and Keat, C.H. and Shvartsman, V.V. and Yusenko, K.V. and Castillo, M.E. and Buzanich, A.G. and Hagemann, U. and Kovalenko, S.A. and Stähler, J. and Lupascu, D.C.
Advanced Functional Materials 32 (2022)The ferroelectricity of multivalent codoped Bismuth ferrite (BiFeO3; BFO) nanoparticles (NPs) is revealed and utilized for photocatalysis, exploiting their narrow electronic bandgap. The photocatalytic activity of ferroelectric photocatalysts BiFe0.95Mn0.05O3 (BFM) NPs and mono-, di-, or tri-valent cations (Ag+, Ca2+, Dy3+; MDT) coincorporated BFM NPs are studied under ultrasonication and in acidic conditions. It is found that such doping enhances the photocatalytic activity of the ferroelectric NPs approximately three times. The correlation of the photocatalytic activity with structural, optical, and electrical properties of the doped NPs is established. The increase of spontaneous polarization by the mono- and tri-valent doping is one of the major factors in enhancing the photocatalytic performance along with other factors such as stronger light absorption in the visible range, low recombination rate of charge carriers, and larger surface area of NPs. A-site doping of BFO NPs by divalent elements suppresses the polarization, whereas trivalent (Dy3+) and monovalent (Ag+) cations provide an increase of polarization. The depolarization field in these single domain NPs acts as a driving force to mitigate recombination of the photoinduced charge carriers. © 2022 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH.view abstract doi: 10.1002/adfm.202207105 2022 • 798 Rare-earth doped BiFe0.95Mn0.05O3 nanoparticles for potential hyperthermia applications
Dubey, A. and Salamon, S. and Attanayake, S.B. and Ibrahim, S. and Landers, J. and Castillo, M.E. and Wende, H. and Srikanth, H. and Shvartsman, V.V. and Lupascu, D.C.
Frontiers in Bioengineering and Biotechnology 10 (2022)Ionic engineering is exploited to substitute Bi cations in BiFe0.95Mn0.05O3 NPs (BFM) with rare-earth (RE) elements (Nd, Gd, and Dy). The sol-gel synthesized RE-NPs are tested for their magnetic hyperthermia potential. RE-dopants alter the morphology of BFM NPs from elliptical to rectangular to irregular hexagonal for Nd, Gd, and Dy doping, respectively. The RE-BFM NPs are ferroelectric and show larger piezoresponse than the pristine BFO NPs. There is an increase of the maximum magnetization at 300 K of BFM up to 550% by introducing Gd. In hyperthermia tests, 3 mg/ml dispersion of NPs in water and agar could increase the temperature of the dispersion up to ∼39°C under an applied AC magnetic field of 80 mT. Although Gd doping generates the highest increment in magnetization of BFM NPs, the Dy-BFM NPs show the best hyperthermia results. These findings show that RE-doped BFO NPs are promising for hyperthermia and other biomedical applications. Copyright © 2022 Dubey, Salamon, Attanayake, Ibrahim, Landers, Castillo, Wende, Srikanth, Shvartsman and Lupascu.view abstract doi: 10.3389/fbioe.2022.965146 2022 • 797 Recrystallization in non-conventional microstructures of 316L stainless steel produced via laser powder-bed fusion: effect of particle coarsening kinetics
Pinto, F.C. and Aota, L.S. and Souza Filho, I.R. and Raabe, D. and Sandim, H.R.Z.
Journal of Materials Science (2022)Abstract: Alloys processed by laser powder-bed fusion show distinct microstructures composed of dislocation cells, dispersed nanoparticles, and columnar grains. Upon post-build annealing, such alloys show sluggish recrystallization kinetics compared to the conventionally processed counterpart. To understand this behavior, AISI 316L stainless steel samples were constructed using the island scan strategy. Rhodonite-like (MnSiO3) nanoparticles and dislocation cells are found within weakly-textured grains in the as-built condition. Upon isothermal annealing at 1150 °C (up to 2880 min), the nucleation of recrystallization occurs along the center of the melt pool, where nuclei sites, high stored elastic energy, and local large misorientation are found in the as-built condition. The low value of the Avrami coefficient (n = 1.16) can be explained based on the non-random distribution of nucleation sites. The local interaction of the recrystallization front with nanoparticles speeds up their coarsening causing the decrease of the Zener-Smith pinning force. This allows the progression of recrystallization in LPBF alloys, although sluggish. These results allow us to understand the progress of recrystallization in LPBF 316L stainless steel, shedding light on the nucleation mechanisms and on the competition between driving and dragging pressures in non-conventional microstructures. They also help to understand the most relevant microstructural aspects applicable for tuning microstructures and designing new LPBF alloys. Graphical abstract: [Figure not available: see fulltext.] © 2022, The Author(s).view abstract doi: 10.1007/s10853-021-06859-1 2022 • 796 The Influence of Nanoconfinement on Electrocatalysis
Wordsworth, J. and Benedetti, T.M. and Somerville, S.V. and Schuhmann, W. and Tilley, R.D. and Gooding, J.J.
Angewandte Chemie - International Edition 61 (2022)The use of nanoparticles and nanostructured electrodes are abundant in electrocatalysis. These nanometric systems contain elements of nanoconfinement in different degrees, depending on the geometry, which can have a much greater effect on the activity and selectivity than often considered. In this Review, we firstly identify the systems containing different degrees of nanoconfinement and how they can affect the activity and selectivity of electrocatalytic reactions. Then we follow with a fundamental understanding of how electrochemistry and electrocatalysis are affected by nanoconfinement, which is beginning to be uncovered, thanks to the development of new, atomically precise manufacturing and fabrication techniques as well as advances in theoretical modeling. The aim of this Review is to help us look beyond using nanostructuring as just a way to increase surface area, but also as a way to break the scaling relations imposed on electrocatalysis by thermodynamics. © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.view abstract doi: 10.1002/anie.202200755 2021 • 795 A new water-soluble thermosensitive star-like copolymer as a promising carrier of the chemotherapeutic drug doxorubicin
Chernykh, M. and Zavalny, D. and Sokolova, V. and Ponomarenko, S. and Prylutska, S. and Kuziv, Y. and Chumachenko, V. and Marynin, A. and Kutsevol, N. and Epple, M. and Ritter, U. and Piosik, J. and Prylutskyy, Y.
Materials 14 (2021)A new water-soluble thermosensitive star-like copolymer, dextran-graft-poly-N-iso-propilacrylamide (D-g-PNIPAM), was created and characterized by various techniques (size-exclusion chromatography, differential scanning calorimetry, Fourier-transform infrared (FTIR) spectroscopy, and dynamic light scattering (DLS) spectroscopy). The viability of cancer cell lines (human transformed cervix epithelial cells, HeLa) as a model for cancer cells was studied using MTT and Live/Dead assays after incubation with a D-g-PNIPAM copolymer as a carrier for the drug doxorubicin (Dox) as well as a D-g-PNIPAM + Dox mixture as a function of the concentration. FTIR spectroscopy clearly indicated the complex formation of Dox with the D-g-PNIPAM copolymer. The size distribution of particles in Hank’s solution was determined by the DLS technique at different temperatures. The in vitro uptake of the studied D-g-PNIPAM + Dox nanoparticles into cancer cells was demonstrated by confocal laser scanning microscopy. It was found that D-g-PNIPAM + Dox nanoparticles in contrast to Dox alone showed higher toxicity toward cancer cells. All of the aforementioned facts indicate a possibility of further preclinical studies of the water-soluble D-g-PNIPAM particles’ behavior in animal tumor models in vivo as promising carriers of anticancer agents. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.view abstract doi: 10.3390/ma14133517 2021 • 794 Biological and Medical Applications of Calcium Phosphate Nanoparticles
Sokolova, V. and Epple, M.
Chemistry - A European Journal 27 7471-7488 (2021)Calcium phosphate nanoparticles have a high biocompatibility and biodegradability due to their chemical similarity to human hard tissue, for example, bone and teeth. They can be used as efficient carriers for different kinds of biomolecules such as nucleic acids, proteins, peptides, antibodies, or drugs, which alone are not able to enter cells where their biological effect is required. They can be loaded with cargo molecules by incorporating them, unlike solid nanoparticles, and also by surface functionalization. This offers protection, for example, against nucleases, and the possibility for cell targeting. If such nanoparticles are functionalized with fluorescing dyes, they can be applied for imaging in vitro and in vivo. Synthesis, functionalization and cell uptake mechanisms of calcium phosphate nanoparticles are discussed together with applications in transfection, gene silencing, imaging, immunization, and bone substitution. Biodistribution data of calcium phosphate nanoparticles in vivo are reviewed. © 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbHview abstract doi: 10.1002/chem.202005257 2021 • 793 Calibrating SECCM measurements by means of a nanoelectrode ruler. The intrinsic oxygen reduction activity of PtNi catalyst nanoparticles
Tetteh, E.B. and Löffler, T. and Tarnev, T. and Quast, T. and Wilde, P. and Aiyappa, H.B. and Schumacher, S. and Andronescu, C. and Tilley, R.D. and Chen, X. and Schuhmann, W.
Nano Research (2021)Scanning electrochemical cell microscopy (SECCM) is increasingly applied to determine the intrinsic catalytic activity of single electrocatalyst particle. This is especially feasible if the catalyst nanoparticles are large enough that they can be found and counted in post-SECCM scanning electron microscopy images. Evidently, this becomes impossible for very small nanoparticles and hence, a catalytic current measured in one landing zone of the SECCM droplet cannot be correlated to the exact number of catalyst particles. We show, that by introducing a ruler method employing a carbon nanoelectrode decorated with a countable number of the same catalyst particles from which the catalytic activity can be determined, the activity determined using SECCM from many spots can be converted in the intrinsic catalytic activity of a certain number of catalyst nanoparticles.[Figure not available: see fulltext.] © 2021, The Author(s).view abstract doi: 10.1007/s12274-021-3702-7 2021 • 792 Characterization and Optimization of AZO Nanoparticles as Coatings for Flexible Substrates toward High IR Reflectivity
Etemad-Parishanzadeh, O. and Ali, W. and Linders, J. and Straube, T. and Lutz, H. and Aggarwal, V. and Mayer, C. and Textor, T. and Gutmann, J.S. and Mayer-Gall, T.
ACS Applied Materials and Interfaces 13 61707-61722 (2021)Energy consumption by air-conditioning is expansive and leads to the emission of millions of tons of CO2 every year. A promising approach to circumvent this problem is the reflection of solar radiation: Rooms that would not heat up by irradiation will not need to be cooled down. Especially, transparent conductive metal oxides exhibit high infrared (IR) reflectivity and are commonly applied as low-emissivity coatings (low-e coatings). Indium tin oxide (ITO) coatings are the state-of-the-art application, though indium is a rare and expensive resource. This work demonstrates that aluminum-doped zinc oxide (AZO) can be a suitable alternative to ITO for IR-reflection applications. AZO synthesized here exhibits better emissivity to be used as roofing membrane coatings for buildings in comparison to commercially available ITO coatings. AZO particles forming the reflective coating are generated via solvothermal synthesis routes and obtain high conductivity and IR reflectivity without the need of any further post-thermal treatment. Different synthesis parameters were studied, and their effects on both conductive and optical properties of the AZO nanoparticles were evaluated. To this end, a series of characterization methods, especially 27Al-nuclear magnetic resonance spectroscopy (27Al-NMR) analysis, have been conducted for a deeper insight into the particles' structure to understand the differences in conductivity and optical properties. The optimized AZO nanoparticles were coated on flexible transparent textile-based roofing membranes and tested as low-e coatings. The membranes demonstrated higher thermal reflectance compared with commercial ITO materials with an emissivity value lowered by 16%. © 2021 The Authors. Published by American Chemical Society.view abstract doi: 10.1021/acsami.1c22151 2021 • 791 Coating of cochlear implant electrodes with bioactive DNA-loaded calcium phosphate nanoparticles for the local transfection of stimulatory proteins
Wey, K. and Schirrmann, R. and Diesing, D. and Lang, S. and Brandau, S. and Hansen, S. and Epple, M.
Biomaterials 276 (2021)Calcium phosphate nanoparticles were loaded with nucleic acids to enhance the on-growth of tissue to a cochlear implant electrode. The nanoparticle deposition on a metallic electrode surface is possible by electrophoretic deposition (EPD) or layer-by-layer deposition (LbL). Impedance spectroscopy showed that the coating layer did not interrupt the electrical conductance at physiological frequencies and beyond (1–40,000 Hz). The transfection was demonstrated with the model cell lines HeLa and 3T3 as well as with primary explanted spiral ganglion neurons (rat) with the model protein enhanced green fluorescent protein (EGFP). The expression of the functional protein brain-derived neurotrophic factor (BDNF) was also shown. Thus, a coating of inner-ear cochlear implant electrodes with nanoparticles that carry nucleic acids will enhance the ongrowth of spiral ganglion cell axons for an improved transmission of electrical pulses. © 2021 Elsevier Ltdview abstract doi: 10.1016/j.biomaterials.2021.121009 2021 • 790 CrOx-Mediated Performance Enhancement of Ni/NiO-Mg:SrTiO3in Photocatalytic Water Splitting
Han, K. and Haiber, D.M. and Knöppel, J. and Lievens, C. and Cherevko, S. and Crozier, P. and Mul, G. and Mei, B.
ACS Catalysis 11 11049-11058 (2021)By photodeposition of CrOxon SrTiO3-based semiconductors doped with aliovalent Mg(II) and functionalized with Ni/NiOxcatalytic nanoparticles (economically significantly more viable than commonly used Rh catalysts), an increase in apparent quantum yield (AQYs) from ∼10 to 26% in overall water splitting was obtained. More importantly, deposition of CrOxalso significantly enhances the stability of Ni/NiO nanoparticles in the production of hydrogen, allowing sustained operation, even in intermittent cycles of illumination.In situelemental analysis of the water constituents during or after photocatalysis by inductively coupled plasma mass spectrometry/optical emission spectrometry shows that after CrOxdeposition, dissolution of Ni ions from Ni/NiOx-Mg:SrTiO3is significantly suppressed, in agreement with the stabilizing effect observed, when both Mg dopant and CrOxare present. State-of-the-art electron microscopy and energy-dispersive X-ray spectroscopy (EDX) and electron energy-loss spectroscopy (EELS) analyses demonstrate that upon preparation, CrOxis photodeposited in the vicinity of several, but not all, Ni/NiOxparticles. This implies the formation of a Ni-Cr mixed metal oxide, which is highly effective in water reduction. Inhomogeneities in the interfacial contact, evident from differences in contact angles between Ni/NiOxparticles and the Mg:SrTiO3semiconductor, likely affect the probability of reduction of Cr(VI) species during synthesis by photodeposition, explaining the observed inhomogeneity in the spatial CrOxdistribution. Furthermore, by comparison with undoped SrTiO3, Mg-doping appears essential to provide such favorable interfacial contact and to establish the beneficial effect of CrOx. This study suggests that the performance of semiconductors can be significantly improved if inhomogeneities in interfacial contact between semiconductors and highly effective catalytic nanoparticles can be resolved by (surface) doping and improved synthesis protocols. © 2021 The Authors. Published by American Chemical Societyview abstract doi: 10.1021/acscatal.1c03104 2021 • 789 Determination of Particle Size, Core and Shell Size Distributions of Core–Shell Particles by Analytical Ultracentrifugation
Schmidt, T. and Linders, J. and Mayer, C. and Cölfen, H.
Particle and Particle Systems Characterization 38 (2021)In core–shell nanoparticle analysis, the determination of size distributions of the different particle parts is often complicated, especially in liquid media. Density matching is introduced as a method for analyzing core–shell nanoparticles using Analytical Ultracentrifugation (AUC), making it possible to obtain the core size distribution in liquid dispersions. For this approach, the density of the dispersion is adjusted to the density of the shell. Oil filled nanocapsules are utilized with component densities of around 1 g mL−1 to demonstrate this technique. The shell size distribution is calculated supposing the particle size distribution as a convolution of the shell- and core size distributions. Finally, the distributions of core size, shell thickness, particle size, and particle density and thus particle composition are obtained. To clarify the effect of swelling, AUC measurements are combined with further size characterization methods like Particle Tracking Microscopy and Dynamic Light Scattering. © 2021 The Authors. Particle & Particle Systems Characterization published by Wiley-VCH GmbH.view abstract doi: 10.1002/ppsc.202100079 2021 • 788 Directly Measured Electrocaloric Effect in Relaxor Polymer Nanocomposites
Hambal, Y. and Menze, K.-H. and Shvartsman, V.V. and Lupascu, D.C.
IEEE International Symposium on Applications of Feeroelectric, ISAF 2021, International Symposium on Integrated Functionalities, ISIF 2021 and Piezoresponse Force Microscopy Workshop, PFM 2021 - Proceedings (2021)Composites of electroactive polymers and ferroelectric nanoparticles are promising for energy storage and electrocaloric applications. In this paper we report on synthesis and electrocaloric properties of P(VDF-TrFE-CFE)/ BaZr0.20Ti0.80O3 nanocomposites. BaZr0.20Ti0.80O3 (BZT) nanoparticles were synthesized via the hydrothermal route. The P(VDF-TrFE-CFE)/BZT composite films with varying amount (1.25 vol.% to 5 vol.%) of the nanoparticles were prepared by the solution casting method. The nanocomposite films showed a significant increase in the dielectric permittivity with the amount of nanoparticles. An increase in the polarization as well as in hysteresis losses with the amount of nanoparticles was observed. The direct electrocaloric effect was measured using a custom built quasi-Adiabatic calorimeter. The P(VDF-TrFE-CFE)/BZT nanocomposite film with 5 vol.% BZT showed an electrocaloric temperature change of ~ 1.8 K at room temperature and an electric field of 50 MV/m, which is comparable to literature values. © 2021 IEEE.view abstract doi: 10.1109/ISAF51943.2021.9477327 2021 • 787 From volatility to solubility: Thermodynamics of imidazolium-based ionic liquids containing chloride and bromide anions
Zaitsau, D.H. and Siewert, R. and Pimerzin, A.A. and Bülow, M. and Held, C. and Loor, M. and Schulz, S. and Verevkin, S.P.
Journal of Molecular Liquids 323 (2021)Ionic liquids (ILs) are effectively used for tuning the composition and the morphology of nanoparticles or stabilizing agents for nanoparticles for catalytic dehydrogenation. Thermodynamic properties of ionic liquids, e.g. vapor pressures and vaporization enthalpies help optimise these processes. Vapor pressures and vaporization enthalpies of the series of 1-alkyl-3-methylimidazolium ionic liquids with chloride and bromide anions have been measured by using quartz-crystal microbalance (QCM). Possible thermal decomposition pathways of [C2C1Im][Br] during vaporization were analyzed by using high-level quantum-chemical methods. These theoretical results explained and supported the absence of decomposition in QCM experimental conditions. According to the measured vapor pressures the [CnC1Im][Cl] and [CnC1Im][Br] series are very suitable for catalytic applications, taking also into account their sufficient thermal stability at the level of 523–543 K. Solubility parameters of ILs and practically relevant solutes were assessed with help of experimental vaporization enthalpies. © 2020 Elsevier B.V.view abstract doi: 10.1016/j.molliq.2020.114998 2021 • 786 Gas-Phase Synthesis of Silicon-Rich Silicon Nitride Nanoparticles for High Performance Lithium–Ion Batteries
Kilian, S.O. and Wiggers, H.
Particle and Particle Systems Characterization 38 (2021)The practical application of silicon-based anodes is severely hindered by continuous capacity fade during cycling. A very promising way to stabilize silicon in lithium–ion battery (LIB) anodes is the utilization of nanostructured silicon-rich silicon nitride (SiNx), a conversion-type anode material. Here, SiNx with structure sizes in the sub-micrometer range have been synthesized in a hot-wall reactor by pyrolysis of monosilane and ammonia. This work focusses on understanding process parameter–particle property correlations. Further, a model for the growth of SiNx nanoparticles in this hot–wall–reactor design is proposed. This synthesis concept is of specific interest regarding simplicity, flexibility, and scalability: A way utilizing any mixtures of precursor gases to build multi-functional nanoparticles that can be directly used for LIBs instead of focusing on modification of nanostructures after they have been formed. Lab-scale production rates as high as 30 g h−1 can be easily achieved and further scaled. SiN0.7 nanoparticles provide a first cycle coulombic efficiency of 54%, a specific discharge capacity of 1367 mAh g−1, and a capacity retention over 80% after 300 cycles at 0.5 C (j = 0.68 mA cm−2). These results imply that silicon-rich silicon nitrides are promising candidates for high-performance LIBs with very high durability. © 2021 The Authors. Particle & Particle Systems Characterization published by Wiley-VCH GmbHview abstract doi: 10.1002/ppsc.202100007 2021 • 785 Highly conductive titania supported iridium oxide nanoparticles with low overall iridium density as OER catalyst for large-scale PEM electrolysis
Böhm, D. and Beetz, M. and Gebauer, C. and Bernt, M. and Schröter, J. and Kornherr, M. and Zoller, F. and Bein, T. and Fattakhova-Rohlfing, D.
Applied Materials Today 24 (2021)To enable future large-scale generation of hydrogen via proton exchange membrane (PEM) electrolysis, utilization of scarce iridium-based catalysts required for the oxygen evolution reaction (OER) has to be significantly lowered. To address this question, the facile synthesis of a highly active TiO2 supported iridium oxide based OER catalyst with reduced noble metal content and an Ir-density of the catalyst powder as low as 0.05–0.08 gIr cm-3 is described in this work. A high surface area corrosion-resistant titania catalyst support homogeneously coated with a 1-2 nm thin layer of amorphous IrOOHx is oxidized in molten NaNO3 between 350-375°C. This procedure allows for a controllable phase transformation and crystallization to form a layer of interconnected IrO2 nanoparticles of ≈2 nm on the surface of the TiO2 support. The increase in crystallinity is thereby accompanied by a significant increase in conductivity of up to 11 S cm-1 for a 30 wt% Ir loaded catalyst. Oxidized samples further display a significantly increased stability with less detectable Ir dissolution under OER conditions. With a mass-based activity of 59 A g-1 at an overpotential of 300 mV, the electrocatalytic activity is maintained at the level of the highly active amorphous IrOOHx phase used as precursor and outperforms it at higher current densities through the increased conductivity. MEA measurements with catalyst loadings of 0.2-0.3 mg cm-2 further confirm the high catalytic activity and initial stability at industrially relevant current densities. The introduced synthesis approach therefore shows a path for the fabrication of novel highly active and atom-efficient oxide supported catalysts with complex nanostructures and thin homogenous nanoparticle coatings that allows a future large-scale application of PEM electrolysis technology without restrictions by the natural abundance of iridium. © 2021 Elsevier Ltdview abstract doi: 10.1016/j.apmt.2021.101134 2021 • 784 How the Physicochemical Properties of the Bulk Material Affect the Ablation Crater Profile, Mass Balance, and Bubble Dynamics During Single-Pulse, Nanosecond Laser Ablation in Water
Kalus, M.-R. and Barcikowski, S. and Gökce, B.
Chemistry - A European Journal 27 5978-5991 (2021)Understanding the key steps that drive the laser-based synthesis of colloids is a prerequisite for learning how to optimize the ablation process in terms of nanoparticle output and functional design of the nanomaterials. Even though many studies focus on cavitation bubble formation using single-pulse ablation conditions, the ablation efficiency and nanoparticle properties are typically investigated under prolonged ablation conditions with repetition rate lasers. Linking single-pulse and multiple-pulse ablation is difficult due to limitations induced by gas formation cross-effects, which occur on longer timescales and depend on the target materials’ oxidation-sensitivity. Therefore, this study investigates the ablation and cavitation bubble dynamics under nanosecond, single laser pulse conditions for six different bulk materials (Au, Ag, Cu, Fe, Ti, and Al). Also, the effective threshold fluences, ablation volumes, and penetration depths are quantified for these materials. The thermal and chemical properties of the corresponding bulk materials not only favor the formation of larger spot sizes but also lead to the highest molar ablation efficiencies for low melting materials such as aluminum. Furthermore, the concept of the cavitation bubble growth linked with the oxidation sensitivity of the ablated material is discussed. With this, evidence is provided that intensive chemical reactions occurring during the very early timescale of ablation are significantly enhanced by the bubble collapse. © 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbHview abstract doi: 10.1002/chem.202005087 2021 • 783 Improved process efficiency in laser-based powder bed fusion of nanoparticle coated maraging tool steel powder
Pannitz, O. and Großwendt, F. and Lüddecke, A. and Kwade, A. and Röttger, A. and Sehrt, J.T.
Materials 14 (2021)Research and development in the field of metal-based additive manufacturing are advancing steadily every year. In order to increase the efficiency of powder bed fusion of metals using a laser beam system (PBF LB/M), machine manufacturers have implemented extensive optimizations with regard to the laser systems and build volumes. However, the optimization of metallic powder materials using nanoparticle additives enables an additional improvement of the laser–material interaction. In this work, tool steel 1.2709 powder was coated with silicon carbide (SiC), few-layer graphene (FLG), and iron oxide black (IOB) on a nanometer scale. Subsequently, the feedstock material and the modified powder materials were analyzed concerning the reflectance of the laser radiation and processed by PBF-LB/M in a systematic and consistent procedure to evaluate the impact of the nano-additivation on the process efficiency and mechanical properties. As a result, an increased build rate is achieved, exhibiting a relative density of 99.9% for FLG/1.2709 due to a decreased reflectance of this modified powder material. Furthermore, FLG/1.2709 provides hardness values after precipitation hardening with only aging comparable to the original 1.2709 material and is higher than the SiC- and IOB-coated material. Additionally, the IOB coating tends to promote oxide‐formation and lack‐of‐fusion defects. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.view abstract doi: 10.3390/ma14133465 2021 • 782 In situ photothermal response of single gold nanoparticles through hyperspectral imaging anti-stokes thermometry
Gargiulo, J. and Cortes, E. and Stefani, F.D. and Barella, M. and Violi, I.L. and Martinez, L.P. and Goschin, F. and Guglielmotti, V. and Pallarola, D. and Schlücker, S. and Pilo-Pais, M. and Acuna, G.P. and Maier, S.A.
ACS Nano 15 2458-2467 (2021)Several fields of applications require a reliable characterization of the photothermal response and heat dissipation of nanoscopic systems, which remains a challenging task for both modeling and experimental measurements. Here, we present an implementation of anti-Stokes thermometry that enables the in situ photothermal characterization of individual nanoparticles (NPs) from a single hyperspectral photoluminescence confocal image. The method is label-free, potentially applicable to any NP with detectable anti-Stokes emission, and does not require any prior information about the NP itself or the surrounding media. With it, we first studied the photothermal response of spherical gold NPs of different sizes on glass substrates, immersed in water, and found that heat dissipation is mainly dominated by the water for NPs larger than 50 nm. Then, the role of the substrate was studied by comparing the photothermal response of 80 nm gold NPs on glass with sapphire and graphene, two materials with high thermal conductivity. For a given irradiance level, the NPs reach temperatures 18% lower on sapphire and 24% higher on graphene than on bare glass. The fact that the presence of a highly conductive material such as graphene leads to a poorer thermal dissipation demonstrates that interfacial thermal resistances play a very significant role in nanoscopic systems and emphasize the need for in situ experimental thermometry techniques. The developed method will allow addressing several open questions about the role of temperature in plasmon-assisted applications, especially ones where NPs of arbitrary shapes are present in complex matrixes and environments. © 2021 American Chemical Society. All rights reserved.view abstract doi: 10.1021/acsnano.0c06185 2021 • 781 Influence of sub-monolayer quantities of carbon nanoparticles on the melting and crystallization behavior of polyamide 12 powders for additive manufacturing
Sommereyns, A. and Hupfeld, T. and Gann, S. and Wang, T. and Wu, C. and Zhuravlev, E. and Lüddecke, A. and Baumann, S. and Rudloff, J. and Lang, M. and Gökce, B. and Barcikowski, S. and Schmidt, M.
Materials and Design 201 (2021)In this paper, the influence of 0.005 vol% and 0.05 vol% of carbon nanoparticles on the surface of polyamide 12 powder particles by dry coating and colloidal additivation is evaluated in great detail concerning thermal and microstructural properties. The dispersion of the nanoparticles on the polymer surface influences the flowability of the feedstock powder already during the additivation process. When analyzing the composite powders dynamically and isothermally with fast scanning and differential scanning calorimetry, carbon nanoparticles influence the crystallization behavior of the feedstock material significantly by acting as nucleation seeds, already at a few percent of a monolayer coating, while showing no effect on the fast heating process. The difference in calorimetric properties and crystallization behavior between the additivation methods of different abrasive forces is discussed. The surface-additivated carbon nanoparticles significantly increase the crystalline area by up to a threefold and the crystallization rate by up to a hundredfold. Furthermore, they change the crystal growth from a typical two- to three-dimensional growth of spherulites to a one- to two-dimensional growth of ellipsoidal impinged lamellar structures. Between 0.005 vol% and 0.05 vol% of well-dispersed carbon nanoparticles should be added to polyamide 12 to trigger an anisotropic heterogeneous nucleation while avoiding agglomerates. © 2021 The Authorsview abstract doi: 10.1016/j.matdes.2021.109487 2021 • 780 Influence of the PVD process conditions on the incorporation of TiN nanoparticles into magnetron sputtered CrN thin films
Tillmann, W. and Kokalj, D. and Stangier, D. and Fu, Q. and Kruis, F.E.
Surface and Coatings Technology 409 (2021)CrTiN thin films are known to form a solid solution independent from the Ti content. Using a novel spatially separated synthesis approach, consisting of magnetron sputtering and atmospheric-pressure arc evaporation, artificial CrTiN nanocomposites were deposited. For the nanocomposite formation, TiN nanoparticles were synthesized using a transferred arc reactor and directly injected into growing CrN thin films using an aerodynamic lens system. The CrN and CrTiN thin films were deposited using various deposition conditions, such as heating power, substrate rotation velocity, nanoparticle injection distance, and cathode setup. The deposited thin films were analyzed regarding their physical structure, microstructure and mechanical properties. Based on the investigations, between 0.02 and 0.11 at.-% of TiN nanoparticles are embedded in the CrN matrix dependent on the deposition parameters. 2D GI-XRD experiments using synchrotron radiation confirm the nanocomposite structure for the two thin films with the highest TiN nanoparticle content. The crystallite size of the CrN thin film decreases from 9.4 ± 2.3 nm to 5.3 ± 1.2 nm due to the embedding of the nanoparticles. Concerning the physical structure, the nanoparticle injection leads to a change of the texture, as shown by the Debbye-Scherrer rings. Based on TEM-investigations, TiN nanoparticle agglomerates lead to a coarser microstructure of the CrN matrix. The hardness of the thin films is not significantly affected by the nanoparticle embedment. The nanoparticle injection distance and cathode setup reveal the highest impact on the film properties. © 2021 Elsevier B.V.view abstract doi: 10.1016/j.surfcoat.2021.126935 2021 • 779 Interface-Dominated Topological Transport in Nanograined Bulk Bi2Te3
Izadi, S. and Han, J.W. and Salloum, S. and Wolff, U. and Schnatmann, L. and Asaithambi, A. and Matschy, S. and Schlörb, H. and Reith, H. and Perez, N. and Nielsch, K. and Schulz, S. and Mittendorff, M. and Schierning, G.
Small 17 (2021)3D topological insulators (TI) host surface carriers with extremely high mobility. However, their transport properties are typically dominated by bulk carriers that outnumber the surface carriers by orders of magnitude. A strategy is herein presented to overcome the problem of bulk carrier domination by using 3D TI nanoparticles, which are compacted by hot pressing to macroscopic nanograined bulk samples. Bi2Te3 nanoparticles well known for their excellent thermoelectric and 3D TI properties serve as the model system. As key enabler for this approach, a specific synthesis is applied that creates nanoparticles with a low level of impurities and surface contamination. The compacted nanograined bulk contains a high number of interfaces and grain boundaries. Here it is shown that these samples exhibit metallic-like electrical transport properties and a distinct weak antilocalization. A downward trend in the electrical resistivity at temperatures below 5 K is attributed to an increase in the coherence length by applying the Hikami–Larkin–Nagaoka model. THz time-domain spectroscopy reveals a dominance of the surface transport at low frequencies with a mobility of above 103 cm2 V−1 s−1 even at room temperature. These findings clearly demonstrate that nanograined bulk Bi2Te3 features surface carrier properties that are of importance for technical applications. © 2021 The Authors. Small published by Wiley-VCH GmbHview abstract doi: 10.1002/smll.202103281 2021 • 778 Interrogating Gas-Borne Nanoparticles Using Laser-Based Diagnostics and Bayesian Data Fusion
Menser, J. and Daun, K. and Schulz, C.
Journal of Physical Chemistry C 125 8382-8390 (2021)We demonstrate how the evaporation properties of gas-borne nanoscale materials, here liquid silicon and germanium nanoparticles, can be obtained through a novel combination of in situ time-resolved laser-induced incandescence (TiRe-LII) and phase-selective laser-induced breakdown spectroscopy (PS-LIBS) based on Bayesian data fusion. This approach reduces the uncertainty in the parameters describing evaporation and condensation by more than a factor of 2 compared to the conventional path and has the capability to provide much needed particle-size-dependent information on nanomaterial phase transitions at high temperature. The inferred parameters are generally consistent with those repeated in the literature but with reduced uncertainty and an extended temperature range. © 2021 American Chemical Society.view abstract doi: 10.1021/acs.jpcc.0c10026 2021 • 777 Large-Scale Production of Carbon-Supported Cobalt-Based Functional Nanoparticles for Oxygen Evolution Reaction
Bähr, A. and Petersen, H. and Tüysüz, H.
ChemCatChem (2021)A series of Co-based nanoparticles supported on activated carbon was synthesized by using waste tea leaves as a template as well as a sustainable carbon source. The crystal structure of the Co particles was adjusted by post-treatments with H2O2, ethanol vapor, and H2, which result in Co3O4, CoO, and metallic Co phases, respectively. After these different treatments, the composite materials consist of small Co-based nanoparticles with an average crystallite size of 6–14 nm supported on activated carbon with apparent specific surface areas up to 1065 m2 g−1. Correlations between the structure of the materials and their activity for the oxygen evolution reaction (OER) were established, whereby the post-treatment with ethanol vapor was found to yield the most effective electrocatalyst. The material shows good stability at 10 mA cm−2 over 10 h and reaches a mass activity of 2.9 A mgCo−1, which is even higher than pristine ordered mesoporous Co3O4. The superior electrocatalytic performance is ascribed to a high dispersion of Co-based nanoparticles and the conductivity of the activated carbon that facilitate the charge transport. © 2021 The Authors. ChemCatChem published by Wiley-VCH GmbH.view abstract doi: 10.1002/cctc.202100594 2021 • 776 Laser-generated high entropy metallic glass nanoparticles as bifunctional electrocatalysts
Johny, J. and Li, Y. and Kamp, M. and Prymak, O. and Liang, S.-X. and Krekeler, T. and Ritter, M. and Kienle, L. and Rehbock, C. and Barcikowski, S. and Reichenberger, S.
Nano Research (2021)High entropy metallic glass nanoparticles (HEMG NPs) are very promising materials for energy conversion due to the wide tuning possibilities of electrochemical potentials offered by their multimetallic character combined with an amorphous structure. Up until now, the generation of these HEMG NPs involved tedious synthesis procedures where the generated particles were only available on highly specialized supports, which limited their widespread use. Hence, more flexible synthetic approaches to obtain colloidal HEMG NPs for applications in energy conversion and storage are highly desirable. We utilized pulsed laser ablation of bulk high entropy alloy targets in acetonitrile to generate colloidal carbon-coated CrCoFeNiMn and CrCoFeNiMnMo HEMG NPs. An in-depth analysis of the structure and elemental distribution of the obtained nanoparticles down to single-particle levels using advanced transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) methods revealed amorphous quinary and senary alloy phases with slight manganese oxide/hydroxide surface segregation, which were stabilized within graphitic shells. Studies on the catalytic activity of the corresponding carbon-HEMG NPs during oxygen evolution and oxygen reduction reactions revealed an elevated activity upon the incorporation of moderate amounts of Mo into the amorphous alloy, probably due to the defect generation by atomic size mismatch. Furthermore, we demonstrate the superiority of these carbon-HEMG NPs over their crystalline analogies and highlight the suitability of these amorphous multi-elemental NPs in electrocatalytic energy conversion. [Figure not available: see fulltext.] © 2021, The Author(s).view abstract doi: 10.1007/s12274-021-3804-2 2021 • 775 Link between Structural and Optical Properties of CoxFe3- xO4Nanoparticles and Thin Films with Different Co/Fe Ratios
Kampermann, L. and Klein, J. and Korte, J. and Kowollik, O. and Pfingsten, O. and Smola, T. and Saddeler, S. and Piotrowiak, T.H. and Salamon, S. and Landers, J. and Wende, H. and Ludwig, A. and Schulz, S. and Bacher, G.
Journal of Physical Chemistry C (2021)CoxFe3-xO4 nanoparticles (x = 0.4 to x = 2.5) and thin films (x = 0.9 to x = 2.2) are analyzed by Raman, absorption, and photoluminescence spectroscopy to link structural and optical properties to different cobalt to iron (Co/Fe) ratios. Raman spectroscopy shows that with decreasing Co content, the crystal structure changes from a predominantly normal cubic spinel phase to a mixed inverse spinel phase. This finding is supported by absorption spectroscopy that points out that inter valence charge transfer (IVCT) processes between octahedrally coordinated Co2+ and Fe3+ cations become more prominent with increasing Fe content. Independent of the Co/Fe ratio, CoxFe3-xO4 nanoparticles show a broad photoluminescence (PL) band with a maximum at around 510 nm. Time-resolved photoluminescence spectroscopy shows subnanosecond lifetimes and temperature-resolved photoluminescence experiments reveal that the green PL increases with decreasing temperature (300 to 10 K) while showing no temperature-dependent shift in energy. It is proposed that this green PL originates from OH-groups on the particles' surface. © 2021 The Authors. Published by American Chemical Society.view abstract doi: 10.1021/acs.jpcc.0c11277 2021 • 774 Link between Structural and Optical Properties of CoxFe3-xO4Nanoparticles and Thin Films with Different Co/Fe Ratios
Kampermann, L. and Klein, J. and Korte, J. and Kowollik, O. and Pfingsten, O. and Smola, T. and Saddeler, S. and Piotrowiak, T.H. and Salamon, S. and Landers, J. and Wende, H. and Ludwig, A. and Schulz, S. and Bacher, G.
Journal of Physical Chemistry C 125 14356-14365 (2021)CoxFe3-xO4nanoparticles (x= 0.4 tox= 2.5) and thin films (x= 0.9 tox= 2.2) are analyzed by Raman, absorption, and photoluminescence spectroscopy to link structural and optical properties to different cobalt to iron (Co/Fe) ratios. Raman spectroscopy shows that with decreasing Co content, the crystal structure changes from a predominantly normal cubic spinel phase to a mixed inverse spinel phase. This finding is supported by absorption spectroscopy that points out that inter valence charge transfer (IVCT) processes between octahedrally coordinated Co2+and Fe3+cations become more prominent with increasing Fe content. Independent of the Co/Fe ratio, CoxFe3-xO4nanoparticles show a broad photoluminescence (PL) band with a maximum at around 510 nm. Time-resolved photoluminescence spectroscopy shows subnanosecond lifetimes and temperature-resolved photoluminescence experiments reveal that the green PL increases with decreasing temperature (300 to 10 K) while showing no temperature-dependent shift in energy. It is proposed that this green PL originates from OH-groups on the particles’ surface. © 2021 The Authors. Published by American Chemical Societyview abstract doi: 10.1021/acs.jpcc.0c11277 2021 • 773 Maximize mixing in highly polyelemental solid solution alloy nanoparticles
Ludwig, Al.
Matter 4 2100-2101 (2021)In this issue of Matter, Yao et al. report on advanced non-equilibrium high-temperature entropy-controlled synthesis of polyelemental nanoparticles. They achieve extreme mixing of 15 metals, some of them previously immiscible, in the form of a single phase solid solution. The compositionally tunable properties of such atomic scale mixtures within a simple crystal structure makes them highly interesting for the design of new materials, e.g., electrocatalysts. © 2021 Elsevier Inc.view abstract doi: 10.1016/j.matt.2021.06.015 2021 • 772 Method to Construct Volcano Relations by Multiscale Modeling: Building Bridges between the Catalysis and Biosimulation Communities
Exner, K.S. and Ivanova, A.
Journal of Physical Chemistry B 125 2098-2104 (2021)Understanding the complex interactions of different building blocks within a sophisticated drug-delivery system (DDS), aimed at targeted transport of the drug to malignant cells, requires modeling techniques on different time and length scales. On the example of the anthracycline antibiotic doxorubicin (DOX), we investigate a potential DDS component, consisting of a gold nanoparticle and a short peptide sequence as carriers of DOX. The combination of atomistic molecular dynamics simulations and density functional theory calculations facilitates compiling a volcano plot, which allows deriving general conclusions on DDS constituents for chemotherapeutic agents within the class of anthracycline antibiotics: the nanoparticle and peptide carrier moieties need to be chosen in such a way that the anthracycline body of the drug is able to intercalate between both entities or between two (π-stacking) residues of the peptide. Using the popular volcano framework as a guideline, the present article connects the catalysis and biosimulation communities, thereby identifying a strategy to overcome the limiting volcano relation by tuning the coordination number of the drug in the DDS component. ©view abstract doi: 10.1021/acs.jpcb.1c00836 2021 • 771 Microstructure formation and mechanical properties of ODS steels built by laser additive manufacturing of nanoparticle coated iron-chromium powders
Doñate-Buendia, C. and Kürnsteiner, P. and Stern, F. and Wilms, M.B. and Streubel, R. and Kusoglu, I.M. and Tenkamp, J. and Bruder, E. and Pirch, N. and Barcikowski, S. and Durst, K. and Schleifenbaum, J.H. and Walther, F. and G...
Acta Materialia 206 (2021)Oxide dispersion strengthened (ODS) steels are known for their enhanced mechanical performance at high temperatures or under radiation exposure. Their microstructure depends on the manufacturing process, from the nanoparticle addition to the base steel powder, to the processing of the nanoparticle enriched powder. The optimization and control of the processing steps still represent a challenge to establish a clear methodology for the additive manufacturing of ODS steels. Here, we evaluate the microstructure, nanoparticle evolution, and mechanical properties of ODS steels prepared by dielectrophoretic controlled adsorption of 0.08 wt% laser-synthesized yttrium oxide (Y2O3) on an iron-chromium ferritic steel powder (PM2000). The influence of the ODS steel fabrication technique is studied for two standard additive manufacturing techniques, directed energy deposition (DED) and laser powder bed fusion (LPBF). The compressive strength of the ODS steels at 600 °C is increased by 21% and 29% for the DED and LPBF samples, respectively, compared to the DED and LPBF steels manufactured without Y2O3 nanoparticle addition. The Martens hardness is enhanced by 9% for the LPBF ODS steel while no significant change is observed in the DED ODS steel. The microstructure and nanoparticle composition and distribution are evaluated by electron backscatter diffraction, scanning electron microscopy–energy-dispersive X-ray spectroscopy, and atom probe tomography, to compare the microstructural features of DED and LPBF manufactured parts. Smaller grain size and more homogeneous distribution with lower agglomeration of Y-O nanoparticles in the LPBF sample are found to be key factors for enhanced mechanical response at 600 °C. The enhanced mechanical properties of the LPBF-processed sample and the more homogeneous nanoparticle dispersion can be linked to results obtained by finite element methods simulations of the melt pool that show two orders of magnitude faster cooling rates for LPBF than for DED. Therefore, this work presents and validates a complete laser-based methodology for the preparation and processing of an ODS steel, proving the modification of the microstructure and enhancement of the high-temperature strength of the as-built parts. © 2020view abstract doi: 10.1016/j.actamat.2020.116566 2021 • 770 Multidimensional thermally-induced transformation of nest-structured complex Au-Fe nanoalloys towards equilibrium
Johny, J. and Prymak, O. and Kamp, M. and Calvo, F. and Kim, S.-H. and Tymoczko, A. and El-Zoka, A. and Rehbock, C. and Schürmann, U. and Gault, B. and Kienle, L. and Barcikowski, S.
Nano Research (2021)Bimetallic nanoparticles are often superior candidates for a wide range of technological and biomedical applications owing to their enhanced catalytic, optical, and magnetic properties, which are often better than their monometallic counterparts. Most of their properties strongly depend on their chemical composition, crystallographic structure, and phase distribution. However, little is known of how their crystal structure, on the nanoscale, transforms over time at elevated temperatures, even though this knowledge is highly relevant in case nanoparticles are used in, e.g., high-temperature catalysis. Au-Fe is a promising bimetallic system where the low-cost and magnetic Fe is combined with catalytically active and plasmonic Au. Here, we report on the in situ temporal evolution of the crystalline ordering in Au-Fe nanoparticles, obtained from a modern laser ablation in liquids synthesis. Our in-depth analysis, complemented by dedicated atomistic simulations, includes a detailed structural characterization by X-ray diffraction and transmission electron microscopy as well as atom probe tomography to reveal elemental distributions down to a single atom resolution. We show that the Au-Fe nanoparticles initially exhibit highly complex internal nested nanostructures with a wide range of compositions, phase distributions, and size-depended microstrains. The elevated temperature induces a diffusion-controlled recrystallization and phase merging, resulting in the formation of a single face-centered-cubic ultrastructure in contact with a body-centered cubic phase, which demonstrates the metastability of these structures. Uncovering these unique nanostructures with nested features could be highly attractive from a fundamental viewpoint as they could give further insights into the nanoparticle formation mechanism under non-equilibrium conditions. Furthermore, the in situ evaluation of the crystal structure changes upon heating is potentially relevant for high-temperature process utilization of bimetallic nanoparticles, e.g., during catalysis. © 2021, The Author(s).view abstract doi: 10.1007/s12274-021-3524-7 2021 • 769 Nickel nanoparticles supported on nitrogen–doped carbon nanotubes are a highly active, selective and stable CO2 methanation catalyst
Gödde, J. and Merko, M. and Xia, W. and Muhler, M.
Journal of Energy Chemistry 54 323-331 (2021)CO2 methanation using nickel-based catalysts has attracted large interest as a promising power-to-gas route. Ni nanoparticles supported on nitrogen-doped CNTs with Ni loadings in the range from 10 wt% to 50 wt% were synthesized by impregnation, calcination and reduction and characterized by elemental analysis, X-ray powder diffraction, H2 temperature-programmed reduction, CO pulse chemisorption and transmission electron microscopy. The Ni/NCNT catalysts were highly active in CO2 methanation at atmospheric pressure, reaching over 50% CO2 conversion and over 95% CH4 selectivity at 340 °C and a GHSV of 50,000 mL g−1 h−1 under kinetically controlled conditions. The small Ni particle sizes below 10 nm despite the high Ni loading is ascribed to the efficient anchoring on the N-doped CNTs. The optimum loading of 30 wt%–40 wt% Ni was found to result in the highest Ni surface area, the highest degree of conversion and the highest selectivity to methane. A constant TOF of 0.3 s−1 was obtained indicating similar catalytic properties of the Ni nanoparticles in the range from 10 wt% to 50 wt% Ni loading. Long-term experiments showed that the Ni/NCNT catalyst with 30 wt% Ni was highly stable for 100 h time on stream. © 2020 Science Pressview abstract doi: 10.1016/j.jechem.2020.06.007 2021 • 768 Nitrogen and Oxygen Functionalization of Multi-walled Carbon Nanotubes for Tuning the Bifunctional Oxygen Reduction/Oxygen Evolution Performance of Supported FeCo Oxide Nanoparticles
Kazakova, M.A. and Koul, A. and Golubtsov, G.V. and Selyutin, A.G. and Ishchenko, A.V. and Kvon, R.I. and Kolesov, B.A. and Schuhmann, W. and Morales, D.M.
ChemElectroChem (2021)The combination of nanostructured transition metal oxides and carbon materials is a promising approach to obtain inexpensive, highly efficient, and stable bifunctional electrocatalysts for the oxygen reduction (ORR) and the oxygen evolution (OER) reactions. We present a strategy for improving the bifunctional ORR/OER activity of supported FeCoOx nanoparticles by tuning the properties of multi-walled carbon nanotubes (MWCNT) via nitrogen doping during their synthesis in the presence of ammonia and subsequent oxidative functionalization. In-depth structural characterization indicates that oxidative treatment provides fine control of the dispersion and localization of FeCoOx nanoparticles in MWCNT, while the optimal degree of nitrogen doping leads to increased bifunctional activity due to enhanced electrical conductivity as well as improved catalyst stability, in both OER and ORR conditions, for nanoparticles formed by two different synthesis routes. The findings reported can be strategically considered for the design of high-performance reversible ORR/OER electrocatalysts. © 2021 The Authors. ChemElectroChem published by Wiley-VCH GmbHview abstract doi: 10.1002/celc.202100556 2021 • 767 On the synthesis and structural evolution of artificial CrN/TiN nanocomposites
Tillmann, W. and Kokalj, D. and Stangier, D. and Fu, Q. and Kruis, F.E. and Kesper, L. and Berges, U. and Westphal, C.
Applied Surface Science 535 (2021)The synthesis of nanocomposites is limited to thermodynamically immiscible phases or to phase separation by exceeding the limits of solution. Hence, the formation of nanocomposites based on transition metals, revealing a nanocrystalline Metal-Nitride/nanocrystalline Metal-Nitride structure, is restricted. These restrictions can be overruled by a spatially separated synthesis of the two phases and a recombination during the deposition. With this approach, the limits of current systems can be expanded, enabling the synthesis of artificial nanocomposites based on a variety of materials. We demonstrate the synthesis of a composite of two nanocrystalline phases of the miscible transition metal-nitrides CrN and TiN. TiN nanoparticles were synthesized using an atmospheric-pressure arc reactor and in-situ injected into a growing CrN thin film. The thin films are analyzed regarding their physical- and microstructure using two-dimensional GIXRD, XPS based on synchrotron radiation and TEM. The CrTiN thin film reveals a two-phase structure consisting of nanocrystalline CrN and TiN phases with crystallite sizes of 9 nm and 4 nm according to GIXRD. XPS indicates bonding of Cr-N, Cr-Cr, and Ti-N. No hint for Cr-Ti bonding was found, excluding (Cr,Ti)N solid solution formation. Based on the TEM-investigations, TiN nanoparticles are embedded as agglomerates in the CrN matrix. © 2020 Elsevier B.V.view abstract doi: 10.1016/j.apsusc.2020.147736 2021 • 766 Phase-sensitive detection of gas-borne Si nanoparticles via line-of-sight UV/VIS attenuation
Asif, M. and Menser, J. and Endres, T. and Dreier, T. and Daun, K. and Schulz, C.
Optics Express 29 21795-21809 (2021)The distinct optical properties of solid and liquid silicon nanoparticles are exploited to determine the distribution of gas-borne solid and liquid particles in situ using line-of-sight attenuation measurements carried out across a microwave plasma reactor operated at 100 mbar. The ratio between liquid and solid particles detected downstream of the plasma varied with measurement location, microwave power, and flow rate. Temperatures of the liquid particles were pyrometrically-inferred using a spectroscopic model based on Drude theory. The phase-sensitive measurement supports the understanding of nanoparticle formation and interaction and thus the overall gas-phase synthesis process. © 2021 Optical Society of America under the terms of the OSA Open Access Publishing Agreementview abstract doi: 10.1364/OE.426528 2021 • 765 Pore penetration of porous catalyst supports by in-situ-adsorbed, agglomeration-quenched nanoparticles from pulsed laser ablation in supercritical CO2
Labusch, M. and Puthenkalam, S. and Cleve, E. and Barcikowski, S. and Reichenberger, S.
Journal of Supercritical Fluids 169 (2021)To synthesize nanoparticles for catalytic applications, pulsed laser ablation (PLA) in liquids has been established as a cost-effective method complementary to wet-chemical synthesis routes. Due to mass transport limitations in water, recent studies conducted PLA in supercritical CO2 (scCO2) to use the superior transport properties. Unfortunately, PLA in scCO2 so far led to the formation of bigger particles and agglomerates, which are unfavorable for the application as catalytically active material. As will be shown in this paper, the former are being avoided by means of an in-situ deposition approach of gold and platinum in scCO2 in presence of mesoporous γ-Al2O3 support. Transmission electron microscopy reveals that the resulting nanoparticle size is quenched while careful adjustment of the mixing conditions during PLA is shown to significantly reduce the agglomeration tendency. Cross-sections of the heterogeneous catalyst prove, that the nanoparticles penetrate the mesoporous support up to 109 nm deep. © 2020 Elsevier B.V.view abstract doi: 10.1016/j.supflu.2020.105100 2021 • 764 Properties of α-Brass Nanoparticles II: Structure and Composition
Weinreich, J. and Paleico, M.L. and Behler, J.
Journal of Physical Chemistry C 125 14897-14909 (2021)Nanoparticles have become increasingly interesting for a wide range of applications because in principle it is possible to tailor their properties by controlling size, shape, and composition. One of these applications is heterogeneous catalysis, and a fundamental understanding of the structural details of the nanoparticles is essential for any knowledge-based improvement of reactivity and selectivity. In this work, we investigate the atomic structure of brass nanoparticles containing up to 5000 atoms as a typical example for a binary alloy consisting of Cu and Zn. As systems of this size are too large for electronic structure calculations, in our simulations, we use a recently parameterized machine learning potential providing close to density functional theory accuracy. This potential is employed for a structural characterization as a function of chemical composition by various types of simulations such as Monte Carlo in the semigrand canonical ensemble and simulated annealing molecular dynamics. Our analysis reveals that the distribution of both elements in the nanoparticles is inhomogeneous, and zinc accumulates in the outermost layer, while the first subsurface layer shows an enrichment of copper. Only for high zinc concentrations, alloying can be found in the interior of the nanoparticles, and regular patterns corresponding to crystalline bulk phases of α-brass can then be observed. The surfaces of the investigated clusters exhibit well-ordered single-crystal facets, which can give rise to grain boundaries inside the clusters. The melting temperature of the nanoparticles is found to decrease with increasing zinc-atom fraction, a trend which is well known also for the bulk phase diagram of brass. © 2021 The Authors. Published by American Chemical Society.view abstract doi: 10.1021/acs.jpcc.1c02314 2021 • 763 Quality over quantity: How different dispersion qualities of minute amounts of nano-additives affect material properties in powder bed fusion of polyamide 12
Sommereyns, A. and Gann, S. and Schmidt, J. and Chehreh, A.B. and Lüddecke, A. and Walther, F. and Gökce, B. and Barcikowski, S. and Schmidt, M.
Materials 14 (2021)The great interest, within the fields of research and industry, in enhancing the range and functionality of polymer powders for laser powder bed fusion (LB-PBF-P) increases the need for material modifications. To exploit the full potential of the additivation method of feedstock powders with nanoparticles, the influence of nanoparticles on the LB-PBF process and the material behavior must be understood. In this study, the impact of the quantity and dispersion quality of carbon nanoparticles deposited on polyamide 12 particles is investigated using tensile and cubic specimens manufactured under the same process conditions. The nano-additives are added through dry coating and colloidal deposition. The specimens are analyzed by tensile testing, differential scanning calorimetry, polarized light and electron microscopy, X-ray diffraction, infrared spectroscopy, and micro-computed tomography. The results show that minute amounts (0.005 vol%) of highly dispersed carbon nanoparticles shift the mechanical properties to higher ductility at the expense of tensile strength. Despite changes in crystallinity due to nano-additives, the crystalline phases of polyamide 12 are retained. Layer bonding and part densities strongly depend on the quantity and dispersion quality of the nanoparticles. Nanoparticle loadings for CO2 laser-operated PBF show only minor changes in material properties, while the potential is greater at lower laser wavelengths. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.view abstract doi: 10.3390/ma14185322 2021 • 762 Reversible Self-Assembly of Gold Nanoparticles Based on Co-Functionalization with Zwitterionic and Cationic Binding Motifs**
He, H. and Rudolph, K. and Ostwaldt, J.-E. and Voskuhl, J. and Hirschhäuser, C. and Niemeyer, J.
Chemistry - A European Journal 27 13539-13543 (2021)We report a pH- and temperature-controlled reversible self-assembly of Au-nanoparticles (AuNPs) in water, based on their surface modification with cationic guanidiniocarbonyl pyrrole (GCP) and zwitterionic guanidiniocarbonyl pyrrole carboxylate (GCPZ) binding motifs. When both binding motifs are installed in a carefully balanced ratio, the resulting functionalized AuNPs self-assemble at pH 1, pH 7 and pH 13, whereas they disassemble at pH 3 and pH 11. Further disassembly can be achieved at elevated temperatures at pH 1 and pH 13. Thus, we were able to prepare functionalized nanoparticles that can be assembled/disassembled in seven alternating regimes, simply controlled by pH and temperature. © 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbHview abstract doi: 10.1002/chem.202102457 2021 • 761 Room temperature synthesized solid solution AuFe nanoparticles and their transformation into Au/Fe Janus nanocrystals
Efremova, M.V. and Spasova, M. and Heidelmann, M. and Grebennikov, I.S. and Li, Z.-A. and Garanina, A.S. and Tcareva, I.O. and Savchenko, A.G. and Farle, M. and Klyachko, N.L. and Majouga, A.G. and Wiedwald, U.
Nanoscale 13 10402-10413 (2021)Solid solution AuFe nanoparticles were synthesized for the first time under ambient conditions by an adapted method previously established for the Fe3O4-Au core-shell morphology. These AuFe particles preserved the fcc structure of Au incorporated with paramagnetic Fe atoms. The metastable AuFe can be segregated by transformation into Janus Au/Fe particles with bcc Fe and fcc Au upon annealing. The ferromagnetic Fe was epitaxially grown on low index fcc Au planes. This preparation route delivers new perspective materials for magnetoplasmonics and biomedical applications and suggests the reconsideration of existing protocols for magnetite-gold core-shell synthesis. © The Royal Society of Chemistry.view abstract doi: 10.1039/d1nr00383f 2021 • 760 Single co3o4 nanocubes electrocatalyzing the oxygen evolution reaction: Nano-impact insights into intrinsic activity and support effects
Liu, Z. and Corva, M. and Amin, H.M.A. and Blanc, N. and Linnemann, J. and Tschulik, K.
International Journal of Molecular Sciences 22 (2021)Single-entity electrochemistry allows for assessing electrocatalytic activities of individual material entities such as nanoparticles (NPs). Thus, it becomes possible to consider intrinsic electrochemical properties of nanocatalysts when researching how activity relates to physical and structural material properties. Conversely, conventional electrochemical techniques provide a normal-ized sum current referring to a huge ensemble of NPs constituting, along with additives (e.g., bind-ers), a complete catalyst-coated electrode. Accordingly, recording electrocatalytic responses of single NPs avoids interferences of ensemble effects and reduces the complexity of electrocatalytic pro-cesses, thus enabling detailed description and modelling. Herein, we present insights into the oxygen evolution catalysis at individual cubic Co3O4 NPs impacting microelectrodes of different support materials. Simulating diffusion at supported nanocubes, measured step current signals can be analyzed, providing edge lengths, corresponding size distributions, and interference-free turnover frequencies. The provided nano-impact investigation of (electro-)catalyst-support effects contra-dicts assumptions on a low number of highly active sites. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.view abstract doi: 10.3390/ijms222313137 2021 • 759 Single Particle Nanoelectrochemistry Reveals the Catalytic Oxygen Evolution Reaction Activity of Co3O4 Nanocubes
Quast, T. and Varhade, S. and Saddeler, S. and Chen, Y.-T. and Andronescu, C. and Schulz, S. and Schuhmann, W.
Angewandte Chemie - International Edition 60 23444-23450 (2021)Co3O4 nanocubes are evaluated concerning their intrinsic electrocatalytic activity towards the oxygen evolution reaction (OER) by means of single-entity electrochemistry. Scanning electrochemical cell microscopy (SECCM) provides data on the electrocatalytic OER activity from several individual measurement areas covering one Co3O4 nanocube of a comparatively high number of individual particles with sufficient statistical reproducibility. Single-particle-on-nanoelectrode measurements of Co3O4 nanocubes provide an accelerated stress test at highly alkaline conditions with current densities of up to 5.5 A cm−2, and allows to derive TOF values of up to 2.8×104 s−1 at 1.92 V vs. RHE for surface Co atoms of a single cubic nanoparticle. Obtaining such high current densities combined with identical-location transmission electron microscopy allows monitoring the formation of an oxy(hydroxide) surface layer during electrocatalysis. Combining two independent single-entity electrochemistry techniques provides the basis for elucidating structure–activity relations of single electrocatalyst nanoparticles with well-defined surface structure. © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbHview abstract doi: 10.1002/anie.202109201 2021 • 758 Single-Entity Electrocatalysis of Individual “Picked-and-Dropped” Co3O4 Nanoparticles on the Tip of a Carbon Nanoelectrode
Quast, T. and Aiyappa, H.B. and Saddeler, S. and Wilde, P. and Chen, Y.-T. and Schulz, S. and Schuhmann, W.
Angewandte Chemie - International Edition 60 3576-3580 (2021)Nano-electrochemical tools to assess individual catalyst entities are critical to comprehend single-entity measurements. The intrinsic electrocatalytic activity of an individual well-defined Co3O4 nanoparticle supported on a carbon-based nanoelectrode is determined by employing an efficient SEM-controlled robotic technique for picking and placing a single catalyst particle onto a modified carbon nanoelectrode surface. The stable nanoassembly is microscopically investigated and subsequently electrochemically characterized. The hexagonal-shaped Co3O4 nanoparticles demonstrate size-dependent electrochemical activity and exhibit very high catalytic activity with a current density of up to 11.5 A cm−2 at 1.92 V (vs. RHE), and a turnover frequency of 532±100 s−1 at 1.92 V (vs. RHE) towards catalyzing the oxygen evolution reaction. © 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbHview abstract doi: 10.1002/anie.202014384 2021 • 757 Single-Particle Hyperspectral Imaging Reveals Kinetics of Silver Ion Leaching from Alloy Nanoparticles
Al-Zubeidi, A. and Stein, F. and Flatebo, C. and Rehbock, C. and Hosseini Jebeli, S.A. and Landes, C.F. and Barcikowski, S. and Link, S.
ACS Nano 15 8363-8375 (2021)Gold-silver alloy nanoparticles are interesting for multiple applications, including heterogeneous catalysis, optical sensing, and antimicrobial properties. The inert element gold acts as a stabilizer for silver to prevent particle corrosion, or conversely, to control the release kinetics of antimicrobial silver ions for long-term efficiency at minimum cytotoxicity. However, little is known about the kinetics of silver ion leaching from bimetallic nanoparticles and how it is correlated with silver content, especially not on a single-particle level. To characterize the kinetics of silver ion release from gold-silver alloy nanoparticles, we employed a combination of electron microscopy and single-particle hyperspectral imaging with an acquisition speed fast enough to capture the irreversible silver ion leaching. Single-particle leaching profiles revealed a reduction in silver ion leaching rate due to the alloying with gold as well as two leaching stages, with a large heterogeneity in rate constants. We modeled the initial leaching stage as a shrinking-particle with a rate constant that exponentially depends on the silver content. The second, slower leaching stage is controlled by the electrochemical oxidation potential of the alloy being steadily increased by the change in relative gold content and diffusion of silver atoms through the lattice. Interestingly, individual nanoparticles with similar sizes and compositions exhibited completely different silver ion leaching yields. Most nanoparticles released silver completely, but 25% of them appeared to arrest leaching. Additionally, nanoparticles became slightly porous. Alloy nanoparticles, produced by scalable laser ablation in liquid, together with kinetic studies of silver ion leaching, provide an approach to design the durability or bioactivity of alloy nanoparticles. ©view abstract doi: 10.1021/acsnano.0c10150 2021 • 756 Spatial distribution of gas-phase synthesized germanium nanoparticle volume-fraction and temperature using combined in situ line-of-sight emission and extinction spectroscopy
Liu, G. and Asif, M. and Menser, J. and Dreier, T. and Mohri, K. and Schulz, C. and Endres, T.
Optics Express 29 8387-8406 (2021)In this study, emission and extinction spectroscopy were combined to in situ measure temperature and volume fraction distributions of liquid germanium nanoparticle gas-phase synthesized in an argon/hydrogen/germane flow through a microwave plasma. Emission of the hot particles and extinction against a continuous background were recorded by a spectrometer in the 380-703 nm and 230-556 nm ranges, respectively, selected based on the specific optical properties of the material. Absorption coefficients were deconvoluted from line-of-sight attenuation (LOSA) measurements by a least-square algorithm and then used to determine the local volume fraction distribution. The temperature field was derived from the line-of-sight emission (LOSE) spectra with the prior knowledge of absorption coefficients. A multi-wavelength reconstruction model was developed for the determination of the spatially-resolved distribution of the measured quantities assuming a stationary axisymmetric flow. Advantages of the method include experimental simplicity, low cost, and adaptability to up-scaled reactor sizes. © 2021 Optical Society of America under the terms of the OSA Open Access Publishing Agreement.view abstract doi: 10.1364/OE.418922 2021 • 755 Superparamagnetic nanoparticles with LC polymer brush shell as efficient dopants for ferronematic phases
Koch, K. and Kundt, M. and Barkane, A. and Nadasi, H. and Webers, S. and Landers, J. and Wende, H. and Eremin, A. and Schmidt, A.M.
Physical Chemistry Chemical Physics 23 24557-24569 (2021)Liquid crystal (LC) based magnetic materials consisting of LC hosts doped with functional magnetic nanoparticles enable optical switching of the mesogens at moderate magnetic field strengths and thereby open the pathway for the design of novel smart devices. A promising route for the fabrication of stable ferronematic phases is the attachment of a covalently bound LC polymer shell onto the surface of nanoparticles. With this approach, ferronematic phases based on magnetically blocked particles and the commercial LC 4-cyano-4′-pentylbiphenyl (5CB) liquid crystal were shown to have a sufficient magnetic sensitivity, but the mechanism of the magneto-nematic coupling is unidentified. To get deeper insight into the coupling modes present in these systems, we prepared ferronematic materials based on superparamagnetic particles, which respond to external fields with internal magnetic realignment instead of mechanical rotation. This aims at clarifying whether the hard coupling of the magnetization to the particle's orientation (magnetic blocking) is a necessary component of the magnetization-nematic director coupling mechanism. We herein report the fabrication of a ferronematic phase consisting of surface-functionalized superparamagnetic Fe3O4 particles and 5CB. We characterize the phase behavior and investigate the magneto-optical properties of the new ferronematic phase and compare it to the ferronematic system containing magnetically blocked CoFe2O4 particles to get information about the origin of the magneto-nematic coupling. © the Owner Societies.view abstract doi: 10.1039/d1cp03005a 2021 • 754 The Impact of Antimony on the Performance of Antimony Doped Tin Oxide Supported Platinum for the Oxygen Reduction Reaction
Jalalpoor, D. and Göhl, D. and Paciok, P. and Heggen, M. and Knossalla, J. and Radev, I. and Peinecke, V. and Weidenthaler, C. and Mayrhofer, K.J.J. and Ledendecker, M. and Schüth, F.
Journal of the Electrochemical Society 168 (2021)Antimony doped tin oxide (ATO) supported platinum nanoparticles are considered a more stable replacement for conventional carbon supported platinum materials for the oxygen reduction reaction. However, the interplay of antimony, tin and platinum and its impact on the catalytic activity and durability has only received minor attention. This is partly due to difficulties in the preparation of morphology- and surface-area-controlled antimony-doped tin oxide materials. The presented study sheds light onto catalyst-support interaction on a fundamental level, specifically between platinum as a catalyst and ATO as a support material. By using a previously described hard-templating method, a series of morphology controlled ATO support materials for platinum nanoparticles with different antimony doping concentrations were prepared. Compositional and morphological changes before and during accelerated stress tests are monitored, and underlying principles of deactivation, dissolution and catalytic performance are elaborated. We demonstrate that mobilized antimony species and strong metal support interactions lead to Pt/Sb alloy formation as well as partially blocking of active sites. This has adverse consequences on the accessible platinum surface area, and affects negatively the catalytic performance of platinum. Operando time-resolved dissolution experiments uncover the potential boundary conditions at which antimony dissolution can be effectively suppressed and how platinum influences the dissolution behavior of the support. © 2021 The Author(s). Published on behalf of The Electrochemical Society by IOP Publishing Limited.view abstract doi: 10.1149/1945-7111/abd830 2021 • 753 Towards synthetic L10-FeNi: Detecting the absence of cubic symmetry in Laser-Ablated Fe-Ni nanoparticles
Lin, Q. and Nadarajah, R. and Hoglund, E. and Semisalova, A. and Howe, J.M. and Gökce, B. and Zangari, G.
Applied Surface Science 567 (2021)The L10 crystal structure underlines an important class of chemically ordered alloys that exhibits uniaxial magnetocrystalline anisotropy. The near-equiatomic L10-FeNi extracted from meteorites has demonstrated intriguing magnetic properties for permanent magnet applications. However, the synthesis of this chemically ordered non-cubic structure has been a longstanding challenge. Here, we demonstrate the absence of cubic symmetry in near-equiatomic Fe-Ni nanoparticles synthesized by picosecond-pulsed laser ablation in liquids. The non-cubic phase detected in these particles can only be L10-FeNi or hexagonal close-packed (HCP) FeNi, and the absence of cubic symmetry was unequivocal. The orientation relationship between the non-cubic phase and the adjacent cubic phase was characterized by a series of transmission electron microscopy (TEM) techniques, which consistently suggests that the formation of the non-cubic phase involves a martensitic transformation process. © 2021 Elsevier B.V.view abstract doi: 10.1016/j.apsusc.2021.150664 2021 • 752 Triple Modification of Alginate Hydrogels by Fibrin Blending, Iron Nanoparticle Embedding, and Serum Protein-Coating Synergistically Promotes Strong Endothelialization
Richter, A. and Li, Y. and Rehbock, C. and Barcikowski, S. and Haverich, A. and Wilhelmi, M. and Böer, U.
Advanced Materials Interfaces 8 (2021)Stent therapy can reduce both morbidity and mortality of chronic coronary stenosis and acute myocardial infarction. However, delayed re-endothelialization, endothelial dysfunction, and chronic inflammation are still unsolved problems. Alginate hydrogels can be used as a coating for stent surfaces; however, complete and fast endothelialization cannot be achieved. In this study, alginate hydrogels are modified by fibrin blending, iron nanoparticle (Fe-NP) embedding, and serum protein coating (SPC) while surface properties and endothelialization capacity are monitored. Only a triple, synergetic modification of the alginate coating by simultaneous I) fibrin blending, II) Fe-NP addition complemented by III) SPC is found to significantly improve endothelial cell viability (live–dead-staining) and proliferation (WST-8 assay). These conditions yield formation of closed endothelial cell monolayers and an up to threefold increase (p < 0.01) in viability, while, interestingly, no effect is found when the modifications (I)–(III) are conducted individually. This synergetic effect is attributed to an accumulation of agglomerated Fe-NP and serum proteins along fibrin fibers, observed via laser scanning microscopy tracking nanoparticle scattering and tetramethylrhodamine (TRITC)-albumin fluorescence. These synergetic effects can pave the way toward a novel strategy for the modification of various hydrogel-based biomaterials and biomaterial coatings. © 2021 The Authors. Advanced Materials Interfaces published by Wiley-VCH GmbHview abstract doi: 10.1002/admi.202002015 2021 • 751 Unraveling the Formation Mechanism of Nanoparticles Sputtered in Ionic Liquid
Meischein, M. and Wang, X. and Ludwig, Al.
Journal of Physical Chemistry C (2021)The formation of nanoparticles by sputtering on ionic liquids could occur at the surface or in the volume of the liquid. To clarify which process occurs, Cu was sputtered in inert and oxidative plasma onto two different ionic liquids. 1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [Bmim][(Tf)2N] and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [Emim][(Tf)2N] were selected for their low solubility of oxygen and their different surface tensions to differentiate the influence of the ionic liquid characteristics on the formation process and characteristics of nanoparticles. The chemical state of nanoparticles in the ionic liquids, metallic or oxidized, was analyzed by X-ray photoelectron spectroscopy. Transmission electron microscopy was performed to acquire nanoparticle size distributions and shapes. The results indicate that nanoparticle formation occurs within the ionic liquid volume, contradicting the prevailing assumption that nanoparticle formation begins at the ionic liquid surface. Nanoparticle size distributions indicate that a higher viscosity of the ionic liquid results in higher nanoparticle diameters. © 2021 The Authors. Published by American Chemical Society.view abstract doi: 10.1021/acs.jpcc.1c07621 2021 • 750 Upscaling nanoparticle synthesis by sputter deposition in ionic liquids
Meischein, M. and Ludwig, Al.
Journal of Nanoparticle Research 23 (2021)Upscaling of nanoparticle fabrication by sputtering into an ionic liquid is shown for the example of Cu. Long-time sputtering (24 h) into a large amount (50 mL) of the ionic liquid 1-butyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)imide [Bmim][(Tf)2 N] yields an amount of approximately 1 g Cu nanoparticles (mean spherical diameter (2.6 ± 1.1) nm), stabilized in ionic liquid without agglomerations. Extraction of Cu nanoparticles from the stabilizing ionic liquid was performed with the capping agent hexadecylamine. Extracted particles could be redispersed in other solvents, thus enabling applications of sputtered nanoparticles beyond ionic liquids. © 2021, The Author(s).view abstract doi: 10.1007/s11051-021-05248-8 2021 • 749 Wavelet neural network modeling for the retention efficiency of sub-15 nm nanoparticles in ultrafiltration under small particle to pore diameter ratio
Fan, Z. and Ji, P.-P. and Zhang, J. and Segets, D. and Chen, D.-R. and Chen, S.-C.
Journal of Membrane Science 635 (2021)Ultrafiltration (UF) using membranes with a small ratio of particle to pore diameter (PPD) would be very desirable for energy saving. The nanoparticle (NP) retention efficiency of membranes with a small PPD ratio depends on various physical and chemical properties of NPs, membranes and solutions as well as the filtration conditions. Until now, no simple model is available for the calculation of NP retention efficiency in UF membranes, besides, it is unlikely to conduct experiments covering all conditions for obtaining the efficiency. The artificial neural network (ANN) has been attracting much attention for studying the performance of a highly nonlinear system. In this study, a wavelet ANN model was developed to predict the NP retentions in membranes for the dead-ended UFs under different conditions. A total of 13 parameters, including the membrane features, particle properties, water solution characteristics, operating conditions, etc., are considered as ANN inputs and the NP retention efficiency as the output. A total of 200 datasets with high quality from literature were selected, in which 50% were for the model training, 30% for the model validation and the remaining 20% for the model testing. A high correlation between the output and inputs was obtained and the significance of the 13 parameters on the NP retention was ranked. A case study was performed to further validate the trained ANN model in the prediction of the retention efficiency of 10 nm gold NPs in a 50 nm pore sized polycarbonate track etched (PCTE) membrane at different pH conditions (5–9). Focusing on the variation of pH, an excellent agreement between the model prediction and the calculation by the modified extended Derjaguin Landau Verwey Overbeek-Maxwell (MEDLVO-Maxwell) model originating from classical and extended DLVO theory was obtained. The interaction energy in the MEDLVO-Maxwell model was based on the separation distance calculated by a quench molecular dynamics (MD) simulation. This study illustrates and validates the application of ANN modeling on the NP retention efficiency prediction in the UF with small PPD ratios. © 2021 Elsevier B.V.view abstract doi: 10.1016/j.memsci.2021.119503 2021 • 748 X-ray-Based Techniques to Study the Nano-Bio Interface
Sanchez-Cano, C. and Alvarez-Puebla, R.A. and Abendroth, J.M. and Beck, T. and Blick, R. and Cao, Y. and Caruso, F. and Chakraborty, I. and Chapman, H.N. and Chen, C. and Cohen, B.E. and Conceição, A.L.C. and Cormode, D.P. and C...
ACS Nano 15 3754-3807 (2021)X-ray-based analytics are routinely applied in many fields, including physics, chemistry, materials science, and engineering. The full potential of such techniques in the life sciences and medicine, however, has not yet been fully exploited. We highlight current and upcoming advances in this direction. We describe different X-ray-based methodologies (including those performed at synchrotron light sources and X-ray free-electron lasers) and their potentials for application to investigate the nano-bio interface. The discussion is predominantly guided by asking how such methods could better help to understand and to improve nanoparticle-based drug delivery, though the concepts also apply to nano-bio interactions in general. We discuss current limitations and how they might be overcome, particularly for future use in vivo. ©view abstract doi: 10.1021/acsnano.0c09563 2020 • 747 A model flow reactor design for the study of nanoparticle structure formation under well-defined conditions
Rosenberger, T. and Sellmann, J. and Wlokas, I. and Kruis, F.E.
Review of Scientific Instruments 91 (2020)Structure formation models describe the change of the particle structure, e.g., by sintering or coating, as a function of the residence time and temperature. For the validation of these models, precise experimental data are required. The precise determination of the required data is difficult due to simultaneously acting mechanisms leading to particle structure formation as well as their dependency on various particle properties and process conditions in the reactor. In this work, a model flow reactor (MFR) is designed and optimized, supported by a validated computational fluid dynamic simulation, to determine the structure formation of nanoparticles under well-defined conditions. Online instrumentation is used to measure the particle mass and different equivalent diameter to detect changes of the particle shape and to calculate the particle structure, defined by the primary particle size, the number of primary particles per agglomerate, coating thickness, effective density, and fractal dimension, by means of structural models. High precision is achieved by examining size-selected particles in a low number concentration and a laminar flow field. Coagulation can be neglected due to the low particle number concentration. Structure formation is restricted to a defined region by direct particle trajectories from the water-cooled aerosol inlet to the water-cooled outlet. A preheated sheath gas is used to concentrate the aerosol on the centerline. The simulated particle trajectories exhibit a well-defined and narrow temperature residence time distribution. Residence times of at least 1 s in the temperature range from 500 K to 1400 K are achieved. The operation of the MFR is demonstrated by the sintering of size-selected FexOy agglomerates with measurements of the particle size and mass distribution as a function of the temperature. An increase of the effective density, resulting from the decreasing particle size at constant particle mass, is observed. © 2020 Author(s).view abstract doi: 10.1063/5.0018880 2020 • 746 A Supported Bismuth Halide Perovskite Photocatalyst for Selective Aliphatic and Aromatic C–H Bond Activation
Dai, Y. and Poidevin, C. and Ochoa-Hernández, C. and Auer, A.A. and Tüysüz, H.
Angewandte Chemie - International Edition 59 5788-5796 (2020)Direct selective oxidation of hydrocarbons to oxygenates by O2 is challenging. Catalysts are limited by the low activity and narrow application scope, and the main focus is on active C−H bonds at benzylic positions. In this work, stable, lead-free, Cs3Bi2Br9 halide perovskites are integrated within the pore channels of mesoporous SBA-15 silica and demonstrate their photocatalytic potentials for C−H bond activation. The composite photocatalysts can effectively oxidize hydrocarbons (C5 to C16 including aromatic and aliphatic alkanes) with a conversion rate up to 32900 μmol gcat−1 h−1 and excellent selectivity (>99 %) towards aldehydes and ketones under visible-light irradiation. Isotopic labeling, in situ spectroscopic studies, and DFT calculations reveal that well-dispersed small perovskite nanoparticles (2–5 nm) possess enhanced electron–hole separation and a close contact with hydrocarbons that facilitates C(sp3)−H bond activation by photoinduced charges. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.view abstract doi: 10.1002/anie.201915034 2020 • 745 Aerosol synthesis of titanium nitride nanoparticles by direct current arc discharge method
Fu, Q. and Kokalj, D. and Stangier, D. and Kruis, F.E. and Tillmann, W.
Advanced Powder Technology 31 4119-4128 (2020)Arc discharge synthesis has industrial relevance due to its low cost and scale-up potential. The production of titanium nitride nanoparticles was achieved by direct current arc discharge in an atmospheric-pressured ambient composed of N2 and Ar. We systematically investigated the effect of the synthesis parameters, including quench gas velocity, quench gas composition, and applied arc current, on the particle quality, yield, and size. It is found that increasing quench gas velocity enables to produce particles with a primary size of 10–15 nm, while titanium nitride particles of 20–50 nm are produced at low quench gas velocity based on scanning electron microscope (SEM) analysis. X-ray diffraction (XRD) results indicated that titanium nitride particles produced at various nitrogen compositions are almost stoichiometric, while the crystallite size increases almost 20 nm when increasing nitrogen contents in the quench gas. Quench gas composition also has a significant impact on the arc voltage as well as particle production rate. When increasing the nitrogen concentration from 20% to 100%, the production rate can be enhanced by a factor of three. Besides, raising the applied arc current from 12 A to 50 A leads to a yield enhancement of factor 10. According to the Brunauer-Emmett-Teller (BET) measurement, the increase of applied arc current has a limited impact on primary particle size. The enhancement in particle production rate is mainly reflected by the larger agglomerate sizes and agglomerate number concentration. Additionally, based on experimental observations and previous studies, a mechanism is presented to explain the growth of deposits on the cathode tip. © 2020 The Society of Powder Technology Japanview abstract doi: 10.1016/j.apt.2020.08.012 2020 • 744 Analysis of the nanoparticle dispersion and its effect on the crystalline microstructure in carbon-additivated PA12 feedstock material for laser powder bed fusion
Hupfeld, T. and Sommereyns, A. and Riahi, F. and Doñate-Buendía, C. and Gann, S. and Schmidt, M. and Gökce, B. and Barcikowski, S.
Materials 13 (2020)Driven by the rapid development of additive manufacturing technologies and the trend towards mass customization, the development of new feedstock materials has become a key aspect. Additivation of the feedstock with nanoparticles is a possible route for tailoring the feedstock material to the printing process and to modify the properties of the printed parts. This study demonstrates the colloidal additivation of PA12 powder with laser-synthesized carbon nanoparticles at >95% yield, focusing on the dispersion of the nanoparticles on the polymer microparticle surface at nanoparticle loadings below 0.05 vol%. In addition to the descriptors "wt%" and "vol%", the descriptor "surf%" is discussed for characterizing the quantity and quality of nanoparticle loading based on scanning electron microscopy. The functionalized powders are further characterized by confocal dark field scattering, differential scanning calorimetry, powder rheology measurements (avalanche angle and Hausner ratio), and regarding their processability in laser powder bed fusion (PBF-LB). We find that heterogeneous nucleation is induced even at a nanoparticle loading of just 0.005 vol%. Finally, analysis of the effect of low nanoparticle loadings on the final parts' microstructure by polarization microscopy shows a nanoparticle loading-dependent change of the dimensions of the lamellar microstructures within the printed part. © 2020 by the authors.view abstract doi: 10.3390/ma13153312 2020 • 743 Anchoring of palladium nanoparticles on N-doped mesoporous carbon
Warczinski, L. and Hu, B. and Eckhard, T. and Peng, B. and Muhler, M. and Hättig, C.
Physical Chemistry Chemical Physics 22 21317-21325 (2020)Pd nanoparticles deposited on nitrogen-doped mesoporous carbon are promising catalysts for highly selective and effective catalytic hydrogenation reactions. To design and utilize these novel catalysts, it is essential to understand the effect of N doping on the metal-support interactions. A combined experimental (X-ray photoelectron spectroscopy) and computational (density functional theory) approach is used to identify preferential adsorption sites and to give detailed explanations of the corresponding metal-support interactions. Pyridinic N atoms turned out to be the preferential adsorption sites for Pd nanoparticles on nitrogen-doped mesoporous carbon, interacting through their lone pairs (LPs) with the Pd atoms via N-LP-Pd dσ and N-LP-Pd s and Pd dπ-π∗ charge transfer, which leads to a change in the Pd oxidation state. Our results evidence the existence of bifunctional palladium nanoparticles containing Pd0 and Pd2+ centers. © the Owner Societies.view abstract doi: 10.1039/d0cp03234d 2020 • 742 Assembly, Stability, and Electrical Properties of Sparse Crystalline Silicon Nanoparticle Networks Applied to Solution-Processed Field-Effect Transistors
Chryssikos, D. and Wiesinger, M. and Bienek, O. and Wiggers, H. and Stutzmann, M. and Cattani-Scholz, A. and Pereira, R.N.
ACS Applied Electronic Materials 2 692-700 (2020)Thin films of crystalline silicon nanoparticles (Si NPs) processed from liquid dispersions of NPs (NP inks) using printing-type deposition methods are currently being intensively investigated for the development of electronic and optoelectronic nanotechnologies. Various (opto)electronic applications have already been demonstrated based on these materials, but so far, devices exhibit modest performance because of relatively low electrical conductivity and charge carrier mobility. In this work, we aim at unveiling the major factors affecting the long-range transport of charges in Si NP thin films. For this, we monitor the electrical properties of thin-film field effect transistors (FETs) as the active channel of the devices is gradually filled with Si NPs. To produce these FET devices featuring stable, sparse Si NP networks within the active channel, we developed a fabrication protocol based on NP deposition by device substrate immersion in a NP ink, made of Si NPs and chlorobenzene, followed by annealing and ultrasonication. We found that both the electrical conductivity and the charge carrier mobility of the FETs increase extremely rapidly as the device channel coverage with NPs increases. Thus, the NP network corresponds effectively to an inhomogeneous blend of conducting and insulating Si NPs, with the most efficient charge percolation paths involving only a fraction of the NPs. We discuss the factors that may lead to this behavior, in view of developing Si NP thin films with competitive charge transport characteristics. Copyright © 2020 American Chemical Society.view abstract doi: 10.1021/acsaelm.9b00786 2020 • 741 Assessing the Influence of Supercritical Carbon Dioxide on the Electrochemical Reduction to Formic Acid Using Carbon-Supported Copper Catalysts
Junge Puring, K. and Evers, O. and Prokein, M. and Siegmund, D. and Scholten, F. and Mölders, N. and Renner, M. and Roldan Cuenya, B. and Petermann, M. and Weidner, E. and Apfel, U.-P.
ACS Catalysis 10 12783-12789 (2020)The electrocatalytic reduction of carbon dioxide (CO2) by means of renewable energies is widely recognized as a promising approach to establish a sustainable closed carbon cycle economy. However, widespread application is hampered by the inherent difficulty in suppressing the hydrogen evolution reaction and controlling the overall process selectivity. Further critical parameters are the limited solubility of CO2 in many electrolytes and its hindered mass transport to the electrodes. Herein we report on a series of nanoparticle Cu electrocatalysts on different carbon supports and their potential to perform the electrochemical CO2 reduction under supercritical conditions (scCO2). Herein, CO2 serves as the reaction medium and reactant alike. By a detailed comparison to ambient conditions we show that scCO2 conditions largely suppress the undesirable hydrogen evolution and favor the production of formic acid by the Cu electrodes. Furthermore, we show that scCO2 conditions significantly prevent Cu nanoparticle agglomeration during electrocatalysis. © 2020 American Chemical Society.view abstract doi: 10.1021/acscatal.0c02983 2020 • 740 Characterization of few-layer graphene aerosols by laser-induced incandescence
Musikhin, S. and Fortugno, P. and Corbin, J.C. and Smallwood, G.J. and Dreier, T. and Daun, K.J. and Schulz, C.
Carbon 167 870-880 (2020)Gas-phase synthesis is a promising route for producing large amounts of high quality few-layer graphene (FLG) nanoparticles economically, but optimizing these processes requires a detailed understanding of the formation kinetics, which in turn demands diagnostics for characterizing this material in situ. This work reports the first laser-induced incandescence measurements on FLG aerosols. Temporally- and spectrally-resolved incandescence signals from FLG particles are measured and used to calculate pyrometric temperatures. Differences between incandescence signals and pyrometric temperatures obtained from FLG and aerosolized soot nanoaggregates are attributed to the larger absorption cross-section and specific surface area of FLG compared to soot. LII signal intensity is found to vary linearly with particle number concentration measured independently by a condensation particle counter. Overall, these results demonstrate the potential for laser-induced incandescence to measure FLG nanoparticle mass (volume) fraction and active surface area in situ, as well as to differentiate graphene from other types of carbonaceous nanomaterials online. © 2020 Elsevier Ltdview abstract doi: 10.1016/j.carbon.2020.05.052 2020 • 739 Continuous-Flow Flat Jet Setup for Uniform Pulsed Laser Postprocessing of Colloids
Zerebecki, S. and Reichenberger, S. and Barcikowski, S.
Journal of Physical Chemistry A 124 11125-11132 (2020)Pulsed laser postprocessing (PLPP) of colloidal nanoparticles and related laser fragmentation in liquid (LFL) using a liquid jet setup have become an acknowledged tool to reduce the nanoparticle diameter down to a few nanometers, alter the crystal phase, or increase the defect density under high-purity and continuous-flow conditions. In recent studies on LFL that were conducted with a cylindrical liquid jet, intensity gradients and related incomplete illumination of the volume element passing through the laser beam path were reported to cause a broadening of the product particle size distribution, melting, and phase segregation. In this paper, we present a new flat jet design, which reduces the deviation of the laser intensity up to 10 times compared to the conventional cylindrical liquid jet. The experimental threshold intensity for gold nanoparticle fragmentation found with the cylindrical setup strongly deviates from the theoretical prediction, while they are in very good agreement for the flat jet setup. Additionally, a narrow product size fraction of 3 ± 2 nm was found for the flat jet, while the main product fraction gained from the cylindrical jet was 10 ± 8 nm in size under the same conditions. Consequently, the flat jet setup allows us not only to study laser fragmentation mechanisms with higher precision but also to gain product particles with narrow particle size distribution at single pulse per particle conditions even at elevated mass concentrations (>50 mg L-1). In future studies, these promising results also render the flat jet setup relevant for the other disciplines of PLPP such as laser melting and defect engineering. © 2020 American Chemical Society.view abstract doi: 10.1021/acs.jpca.0c08787 2020 • 738 Controlling the Number of Branches and Surface Facets of Pd-Core Ru-Branched Nanoparticles to Make Highly Active Oxygen Evolution Reaction Electrocatalysts
Myekhlai, M. and Benedetti, T.M. and Gloag, L. and Poerwoprajitno, A.R. and Cheong, S. and Schuhmann, W. and Gooding, J.J. and Tilley, R.D.
Chemistry - A European Journal 26 15501-15504 (2020)Producing stable but active materials is one of the enduring challenges in electrocatalysis and other types of catalysis. Producing branched nanoparticles is one potential solution. Controlling the number of branches and branch size of faceted branched nanoparticles is one of the major synthetic challenges to achieve highly active and stable nanocatalysts. Herein, we use a cubic-core hexagonal-branch mechanism to synthesize branched Ru nanoparticles with control over the size and number of branches. This structural control is the key to achieving high exposure of active {10–11} facets and optimum number of Ru branches that enables improved catalytic activity for oxygen evolution reaction while maintaining high stability. © 2020 Wiley-VCH GmbHview abstract doi: 10.1002/chem.202003561 2020 • 737 Dual pH-Induced Reversible Self-Assembly of Gold Nanoparticles by Surface Functionalization with Zwitterionic Ligands
He, H. and Ostwaldt, J.-E. and Hirschhäuser, C. and Schmuck, C. and Niemeyer, J.
Small 16 (2020)The dual pH-induced reversible self-assembly (PIRSA) of Au-nanoparticles (Au NPs) is reported, based on their decoration with the self-complementary guanidiniocarbonyl pyrrole carboxylate zwitterion (GCPZ). The assembly of such functionalized Au NPs is found at neutral pH, based on supramolecular pairing of the GCPZ groups. The resulting self-assembled system can be switched back to the disassembled state by addition of base or acid. Two predominant effects that contribute to the dual-PIRSA of Au NPs are identified, namely the ionic hydrogen bonding between the GCPZ groups, but also a strong hydrophobic effect. The contribution of each interaction is depending on the concentration of GCPZ on NPs, which allows to control the self-assembly state over a wide range of different water/solvent ratios. © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/smll.202001044 2020 • 736 Effect of nanoparticle additivation on the microstructure and microhardness of oxide dispersion strengthened steels produced by laser powder bed fusion and directed energy deposition
Doñate-Buendia, C. and Streubel, R. and Kürnsteiner, P. and Wilms, M.B. and Stern, F. and Tenkamp, J. and Bruder, E. and Barcikowski, S. and Gault, B. and Durst, K. and Schleifenbaum, J.H. and Walther, F. and Gökce, B.
Procedia CIRP 94 41-45 (2020)In this contribution, the effect of nanoparticle additivation on the microstructure and microhardness of oxide dispersion strengthened steels (ODS) manufactured by laser powder bed fusion (L-PBF) and directed energy deposition (DED) additive manufacturing (AM) is studied. The powder composites are made of micrometer-sized iron-chromium-alloy based powder which are homogenously decorated with Y2O3 nanoparticles synthesized by pulsed laser fragmentation in water. Consolidated by L-PBF and DED, an enhanced microhardness of the AM-built ODS sample is found. This increase is related to the significant microstructural differences found between the differently processed samples. © 2020 The Authors. Published by Elsevier B.V.view abstract doi: 10.1016/j.procir.2020.09.009 2020 • 735 Effective size separation of laser-generated, surfactant-free nanoparticles by continuous centrifugation
Kohsakowski, S. and Seiser, F. and Wiederrecht, J.-P. and Reichenberger, S. and Vinnay, T. and Barcikowski, S. and Marzun, G.
Nanotechnology 31 (2020)High-power, nanosecond, pulsed-laser ablation in liquids enables the continuous synthesis of highly pure colloidal nanoparticles (NPs) at an application-relevant scale. The gained mass-weighted particle size distribution is however often reported to be broad, requiring post treatment like centrifugation to remove undesired particle size fractions. To date, available centrifugation techniques are generally discontinuous, limiting the throughput and hindering economic upscaling. Hence, throughout this paper, a scalable, continuously operating centrifugation of laser-generated platinum NPs in a tubular bowl centrifuge is reported for the first time. To that end, using a 121 W ns-laser, the continuous production of a colloidal suspension of NPs, yet with broad particle size distribution has been employed, yielding productivities of 1-2 g h-1 for gold, silver, and platinum. The power-specific productivities (Au: 18 mg h-1 W-1, Pt: 13 mg h-1 W-1, Ag: 8 mg h-1 W-1, Ni: 6 mg h-1 W-1) are far higher than reported before. Subsequent downstream integration of a continuously operating tubular bowl centrifuge was successfully achieved for Pt NPs allowing the removal of undesired particle size with high throughput. By means of a systematic study of relevant centrifugation parameters involved, effective size optimization and respective size sharpness parameters for a maximum Pt NP diameter of 10 nm are reported. The results of the experimental centrifugation of laser-generated Pt NPs were in excellent agreement with the theoretically calculated cut-off diameter. After centrifugation with optimized parameters (residence time of 5 min; g-force of 38,454 g), the polydispersity indices of the Pt NPs size distributions were reduced by a factor of six, and high monodispersity was observed. © 2019 IOP Publishing Ltd.view abstract doi: 10.1088/1361-6528/ab55bd 2020 • 734 Effects of filter structure, flow velocity, particle concentration and fouling on the retention efficiency of ultrafiltration for sub-20 nm gold nanoparticles
Lee, H. and Segets, D. and Süß, S. and Peukert, W. and Chen, S.-C. and Pui, D.Y.H.
Separation and Purification Technology 241 (2020)Ultrafiltration techniques with membranes of pore sizes under 100 nm have been widely applied in drinking water, wastewater, semiconductor and pharmaceutical process water treatments for nanoparticle (NP) and pathogen removal. The most direct way to evaluate the membrane performance is to experimentally obtain the size fractional retention efficiency. However, the real-life performance of the membrane in terms of fouling (or loading) characteristics and the effects of the concentration of challenging particles and rate of flux (or filtration velocities) on the filtration efficiency during fouling have not been well understood. In this study, systematic filtration experiments for filtration efficiency at clean and loaded conditions were conducted for three different 50 nm rated membrane filters, including PTFE (Polytetrafluoroethylene), PCTE (Polycarbonate Track-Etched) and MCE (Mixed Cellulose Ester) membranes, against 5, 10 and 20 nm Au NPs at different feed concentrations and fluxes. The results showed that the effects of feed concentration and flux are significant. This study provides important insights of retention mechanisms and efficiency for different ultrafiltration membrane structures at varied filtration velocities and fouling characteristics giving clear directions of future NP ultrafiltration research. © 2020 Elsevier B.V.view abstract doi: 10.1016/j.seppur.2020.116689 2020 • 733 Efficient OER Catalyst with Low Ir Volume Density Obtained by Homogeneous Deposition of Iridium Oxide Nanoparticles on Macroporous Antimony-Doped Tin Oxide Support
Böhm, D. and Beetz, M. and Schuster, M. and Peters, K. and Hufnagel, A.G. and Döblinger, M. and Böller, B. and Bein, T. and Fattakhova-Rohlfing, D.
Advanced Functional Materials 30 (2020)A multistep synthesis procedure for the homogeneous coating of a complex porous conductive oxide with small Ir nanoparticles is introduced to obtain a highly active electrocatalyst for water oxidation. At first, inverse opal macroporous Sb doped SnO2 (ATO) microparticles with defined pore size, composition, and open-porous morphology are synthesized that reach a conductivity of ≈3.6 S cm−1 and are further used as catalyst support. ATO-supported iridium catalysts with a controlled amount of active material are prepared by solvothermal reduction of an IrOx colloid in the presence of the porous ATO particles, whereby homogeneous coating of the complete outer and inner surface of the particles with nanodispersed metallic Ir is achieved. Thermal oxidation leads to the formation of ATO-supported IrO2 nanoparticles with a void volume fraction of ≈89% calculated for catalyst thin films based on scanning transmission electron microscope tomography data and microparticle size distribution. A remarkably low Ir bulk density of ≈0.08 g cm−3 for this supported oxide catalyst architecture with 25 wt% Ir is determined. This highly efficient oxygen evolution reaction catalyst reaches a current density of 63 A gIr −1 at an overpotential of 300 mV versus reversible hydrogen electrode, significantly exceeding a commercial TiO2-supported IrO2 reference catalyst under the same measurement conditions. © 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/adfm.201906670 2020 • 732 Ejector-based nanoparticle sampling from pressures down to 20 mbar
Rosenberger, T. and Neises, J. and Kiesler, D. and Kruis, F.E.
Journal of Aerosol Science 144 (2020)The application of standard online instrumentation, such as scanning mobility particle sizer (SMPS), centrifugal particle mass analyzer or aerosol particle mass analyzer (CPMA/APM), and electrical low-pressure impactor (ELPI+) to low-pressure processes is only possible with extensive modification of the devices and extensive calibrations. A low-pressure ejector is a suitable device to transfer aerosol nanoparticles from low-pressure regions to atmospheric pressure and allows the direct use of standard online instrumentation. In this work, a commercial low-pressure ejector is investigated in the pressure range from 20–180 mbar with fully-sintered and size-selected nanoparticles (15–80 nm) in order to extend the application range of online instruments to low-pressure processes and open up a new variety of analysis methods. Results are compared to our previous work which was limited to pressures above 120 mbar. A change in particle size during the measurements for fully-sintered silver particles was not observed. A particle dilution factor between 60–6500 was found. High particle losses in the ejector for large particle sizes are compensated by a lower gas dilution factor. © 2020 Elsevier Ltdview abstract doi: 10.1016/j.jaerosci.2020.105531 2020 • 731 Electrochemical dealloying as a tool to tune the porosity, composition and catalytic activity of nanomaterials
Rurainsky, C. and Manjón, A.G. and Hiege, F. and Chen, Y.-T. and Scheu, C. and Tschulik, K.
Journal of Materials Chemistry A 8 19405-19413 (2020)Electrochemical dealloying as a post-Treatment can greatly improve the catalytic activity of nanoparticles. To date, selecting suitable conditions to reach desired porosity, composition and catalytic activity is based on trial-And-error-Attempts, due to insufficient understanding of the electrochemically induced morphological and compositional changes of the nanoparticles. These changes are elucidated here by combining electrochemistry with identical location electron microscopy analyses and linking them to the electrocatalytic properties of the obtained nanocatalysts. Using AgAu alloy nanoparticles and the hydrogen evolution reaction as a model system, the influence of cyclic voltammetry parameters on the catalytic activity upon electrochemical dealloying is investigated. Increasing the number of cycles initially results in a decreased Ag content and a sharp improvement in activity. Additional dealloying increases the nanoparticle porosity, while marginally altering their composition, due to surface motion of atoms. Since this is accompanied by particle aggregation, a decrease in catalytic activity results upon extensive cycling. This transition between porosity formation and particle aggregation marks the optimum for nanocatalyst post-production. The gained insights may aid speeding up the development of new materials by electrochemical dealloying as an easy-To-control post-processing route to tune the properties of existing nanoparticles, instead of having to alter usually delicate synthesis routes as a whole. © The Royal Society of Chemistry.view abstract doi: 10.1039/d0ta04880a 2020 • 730 Faceted Branched Nickel Nanoparticles with Tunable Branch Length for High-Activity Electrocatalytic Oxidation of Biomass
Poerwoprajitno, A.R. and Gloag, L. and Watt, J. and Cychy, S. and Cheong, S. and Kumar, P.V. and Benedetti, T.M. and Deng, C. and Wu, K.-H. and Marjo, C.E. and Huber, D.L. and Muhler, M. and Gooding, J.J. and Schuhmann, W. and Wan...
Angewandte Chemie - International Edition 59 15487-15491 (2020)Controlling the formation of nanosized branched nanoparticles with high uniformity is one of the major challenges in synthesizing nanocatalysts with improved activity and stability. Using a cubic-core hexagonal-branch mechanism to form highly monodisperse branched nanoparticles, we vary the length of the nickel branches. Lengthening the nickel branches, with their high coverage of active facets, is shown to improve activity for electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF), as an example for biomass conversion. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaAview abstract doi: 10.1002/anie.202005489 2020 • 729 Ferroelectric nanocomposites: Influence of nanoparticle size distribution on electrocaloric conversion parameters
Shevliakova, H.V. and Morozovska, A.N. and Morozovsky, N.V. and Svechnikov, G.S. and Shvartsman, V.V.
2020 IEEE 40th International Conference on Electronics and Nanotechnology, ELNANO 2020 - Proceedings 2020-April 105-108 (2020)The study of the electrocaloric effect in ensembles of ferroelectric nanoparticles is of significant interest for fundamental research and its practical applications in solidstate coolers. The exploration of electrocaloric cooling is of great importance to finding solutions to environmental and energyefficiency issues in currently available refrigeration technologies. In this work we calculated the polarization, electrocaloric temperature change, and dielectric permittivity of the nanocomposite containing non-interacting ferroelectric nanoparticles with different size distributions, and analyzed the dependences of polarization, dielectric permittivity and electrocaloric temperature change on the distribution function of the particles sizes. As anticipated, the properties of the nanocomposite approach that of the average size nanoparticles with a narrowing in the dispersion of particles sizes within the nanocomposite. A widening in the particles size distribution increases the coercivity (i.e. half-width of the ferroelectric hysteresis loop), but the hysteresis width decreases for the maximum particle radius, which is significantly smaller than the dispersion of the distribution function. © 2020 IEEE.view abstract doi: 10.1109/ELNANO50318.2020.9108206 2020 • 728 Formic Acid-Assisted Selective Hydrogenolysis of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran over Bifunctional Pd Nanoparticles Supported on N-Doped Mesoporous Carbon
Hu, B. and Warczinski, L. and Li, X. and Lu, M. and Bitzer, J. and Heidelmann, M. and Eckhard, T. and Fu, Q. and Schulwitz, J. and Merko, M. and Li, M. and Kleist, W. and Hättig, C. and Muhler, M. and Peng, B.
Angewandte Chemie - International Edition (2020)Biomass-derived 5-hydroxymethylfurfural (HMF) is regarded as one of the most promising platform chemicals to produce 2,5-dimethylfuran (DMF) as a potential liquid transportation fuel. Pd nanoparticles supported on N-containing and N-free mesoporous carbon materials were prepared, characterized, and applied in the hydrogenolysis of HMF to DMF under mild reaction conditions. Quantitative conversion of HMF to DMF was achieved in the presence of formic acid (FA) and H2 over Pd/NMC within 2 h. The reaction mechanism, especially the multiple roles of FA, was explored through a detailed comparative study by varying hydrogen source, additive, and substrate as well as by applying in situ ATR-IR spectroscopy. The major role of FA is to shift the dominant reaction pathway from the hydrogenation of the aldehyde group to the hydrogenolysis of the hydroxymethyl group via the protonation by FA at the C-OH group, lowering the activation barrier of the C−O bond cleavage and thus significantly enhancing the reaction rate. XPS results and DFT calculations revealed that Pd2+ species interacting with pyridine-like N atoms significantly enhance the selective hydrogenolysis of the C−OH bond in the presence of FA due to their high ability for the activation of FA and the stabilization of H−. © 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbHview abstract doi: 10.1002/anie.202012816 2020 • 727 Forming amorphous calcium carbonate within hydrogels by enzyme-induced mineralization in the presence of N-(phosphonomethyl)glycine
Milovanovic, M. and Unruh, M.T. and Brandt, V. and Tiller, J.C.
Journal of Colloid and Interface Science 579 357-368 (2020)Amorphous inorganic materials have a great potential in material science. Amorphous calcium carbonate (ACC) is a widely useable system, however, its stabilization often turns out to be difficult and the synthesis is mostly limited to precipitation in solution as nanoparticles. Stable ACC in bulk phases would create new composite materials. Previous work described the enzyme-induced mineralization of hydrogels with crystalline calcium carbonate by entrapping urease into a hydrogel and treating this with an aqueous mineralization solution containing urea und calcium chloride. Here, this method was modified using a variety of crystallization inhibitors attached to the hydrogel matrix or added to the surrounding mineralization solution. It was found that only N-(phosphonomethyl)glycine (PMGly) in solution completely inhibits the crystallization of ACC in the hydrogel matrix. The stability of the homogeneously precipitated ACC could be accounted to the combination of stabilizing effects of the additive and stabilization through confinement. The crystallization could be accelerated at higher temperatures up to 60 °C. Here, a combination of Mg ions and PMGly was required to stabilize ACC in the hydrogel. Variation of these two compounds can be used to control a number of different calcium carbonate morphologies within the hydrogel. While the ACC nanoparticles within the hydrogel are stable over weeks even in water, a calcite layer grows on the surface of the hydrogel, which might be used as self-hardening mechanism of a surface. © 2020 Elsevier Inc.view abstract doi: 10.1016/j.jcis.2020.06.047 2020 • 726 Iron Nanoparticle Composite Hydrogels for Studying Effects of Iron Ion Release on Red Blood Cell in Vitro Production
Brändle, K. and Bergmann, T.C. and Raic, A. and Li, Y. and Million, N. and Rehbock, C. and Barcikowski, S. and Lee-Thedieck, C.
ACS Applied Bio Materials 3 4766-4778 (2020)Growing numbers of complex surgical interventions increase the need for blood transfusions, which cannot be fulfilled by the number of donors. Therefore, the interest in producing erythrocytes from their precursors-the hematopoietic stem and progenitor cells (HSPCs)-in laboratories is rising. To enable this, in vitro systems are needed, which allow analysis of the effects of essential factors such as iron on erythroid development. For this purpose, iron ion-releasing systems based on poly(ethylene glycol) (PEG)-iron nanocomposites are developed to assess if gradual iron release improves iron bioavailability during in vitro erythroid differentiation. The nanocomposites are synthesized using surfactant-free pulsed laser ablation of iron directly in the PEG solution. The iron concentrations released from the material are sufficient to influence in vitro erythropoiesis. In this way, the production of erythroid cells cultured on flat PEG-iron nanocomposite hydrogel pads can be enhanced. In contrast, erythroid differentiation is not enhanced in the biomimetic macroporous 3D composite scaffolds, possibly because of local iron overload within the pores of the system. In conclusion, the developed iron nanoparticle-PEG composite hydrogel allows constant iron ion release and thus paves the way (i) to understand the role of iron during erythropoiesis and (ii) toward the development of biomaterials with a controlled iron release for directing erythropoiesis in culture. © 2020 American Chemical Society.view abstract doi: 10.1021/acsabm.0c00297 2020 • 725 Laser Fragmentation-Induced Defect-Rich Cobalt Oxide Nanoparticles for Electrochemical Oxygen Evolution Reaction
Yu, M. and Waag, F. and Chan, C.K. and Weidenthaler, C. and Barcikowski, S. and Tüysüz, H.
ChemSusChem 13 520-528 (2020)Sub-5 nm cobalt oxide nanoparticles are produced in a flowing water system by pulsed laser fragmentation in liquid (PLFL). Particle fragmentation from 8 nm to 4 nm occurs and is attributed to the oxidation process in water where oxidative species are present and the local temperature is rapidly elevated under laser irradiation. Significantly higher surface area, crystal phase transformation, and formation of structural defects (Co2+ defects and oxygen vacancies) through the PLFL process are evidenced by detailed structural characterizations by nitrogen physisorption, electron microscopy, synchrotron X-ray diffraction, and X-ray photoelectron spectroscopy. When employed as electrocatalysts for the oxygen evolution reaction under alkaline conditions, the fragmented cobalt oxides exhibit superior catalytic activity over pristine and nanocast cobalt oxides, delivering a current density of 10 mA cm−2 at 369 mV and a Tafel slope of 46 mV dec−1, which is attributed to a larger exposed active surface area, the formation of defects, and an increased charge transfer rate. The study provides an effective approach to engineering cobalt oxide nanostructures in a flowing water system, which shows great potential for sustainable production of active cobalt catalysts. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.view abstract doi: 10.1002/cssc.201903186 2020 • 724 Matrix-specific mechanism of Fe ion release from laser-generated 3D-printable nanoparticle-polymer composites and their protein adsorption properties
Li, Y. and Rehbock, C. and Nachev, M. and Stamm, J. and Sures, B. and Blaeser, A. and Barcikowski, S.
Nanotechnology 31 (2020)Nanocomposites have been widely applied in medical device fabrication and tissue-engineering applications. In this context, the release of metal ions as well as protein adsorption capacity are hypothesized to be two key processes directing nanocomposite-cell interactions. The objective of this study is to understand the polymer-matrix effects on ion release kinetics and their relations with protein adsorption. Laser ablation in macromolecule solutions was employed for synthesizing Au and Fe nanoparticle-loaded nanocomposites based on thermoplastic polyurethane (TPU) and alginate. Confocal microscopy revealed a three-dimensional homogeneous dispersion of laser-generated nanoparticles in the polymer. The physicochemical properties revealed a pronounced dependence upon embedding of Fe and Au nanoparticles in both polymer matrices. Interestingly, the total Fe ion concentration released from alginate gels under static conditions decreased with increasing mass loadings, a phenomenon only found in the Fe-alginate system and not in the Cu/Zn-alginate and Fe-TPU control system (where the effects were proportioonal to the nanoparticle load). A detailed mechanistic examination of iron the ion release process revealed that it is probably not the redox potential of metals and diffusion of metal ions alone, but also the solubility of nano-metal oxides and affinity of metal ions for alginate that lead to the special release behaviors of iron ions from alginate gels. The amount of adsorbed bovine serum albumin (BSA) and collagen I on the surface of both the alginate and TPU composites was significantly increased in contrast to the unloaded control polymers and could be correlated with the concentration of released Fe ions and the porosity of composites, but was independent of the global surface charge. Interestingly, these effects were already highly pronounced at minute loadings with Fe nanoparticles down to 200 ppm. Moreover, the laser-generated Fe or Au nanoparticle-loaded alginate composites were shown to be a suitable bioink for 3D printing. These findings are potentially relevant for ion-sensitive bio-responses in cell differentiation, endothelisation, vascularisation, or wound healing. © 2020 The Author(s). Published by IOP Publishing Ltd.view abstract doi: 10.1088/1361-6528/ab94da 2020 • 723 Nanocellulose-Mediated Transition of Lithium-Rich Pseudo-Quaternary Metal Oxide Nanoparticles into Lithium Nickel Cobalt Manganese Oxide (NCM) Nanostructures
Zehetmaier, P.M. and Zoller, F. and Beetz, M. and Plaß, M.A. and Häringer, S. and Böller, B. and Döblinger, M. and Bein, T. and Fattakhova-Rohlfing, D.
ChemNanoMat 6 618-628 (2020)We report the syntheses of various compounds within the pseudo-quaternary system of the type LiwNixCoyMnzOδ (δ≤1) (pre-NCMs). Four different compositions of this compound were realized as ultrasmall crystalline nanoparticles of 1–4 nm diameter using low-temperature solvothermal reaction conditions in tert-butanol at only 170 °C. All of the pre-NCMs crystallize in the rock-salt structure and their lithium content is between 20% and 30% with respect to the complete metal content. By adjusting the lithium content to 105% stoichiometry in the solvothermal reaction, the pre-NCMs can easily react to the respective Li(NixCoyMnz)O2 (NCM) nanoparticles. Furthermore, nanosized desert-rose structured NCMs were obtained after addition of nanocellulose during the synthesis. By using the mixed metal monoxides as precursor for the NCMs, cation mixing between lithium and nickel is favored and gets more pronounced with increasing nickel content. The cation mixing effect compromises good electrochemical capacity retention, but the desert-rose structure nevertheless enables enhanced stability at high power conditions, especially for NCM333. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.view abstract doi: 10.1002/cnma.201900748 2020 • 722 Origin of Laser-Induced Colloidal Gold Surface Oxidation and Charge Density, and Its Role in Oxidation Catalysis
Ziefuß, A.R. and Haxhiaj, I. and Müller, S. and Gharib, M. and Gridina, O. and Rehbock, C. and Chakraborty, I. and Peng, B. and Muhler, M. and Parak, W.J. and Barcikowski, S. and Reichenberger, S.
Journal of Physical Chemistry C 124 20981-20990 (2020)Laser fragmentation in liquids (LFL) allows the synthesis of fully inorganic, ultrasmall gold nanoparticles, usAu NPs (<3 nm). Although the general method is well established, there is a lack of understanding the chemical processes that are triggered by the laser pulses, which may dictate the surface properties that are highly important in heterogeneous oxidation catalytic reactions. We observed the formation of radical oxygen species during LFL, which suggested that LFL is a physicochemical process that leads to particle size reductions and initiates oxidative processes. When the ionic strength in the nanoenvironment was increased, the oxidation of the first atomic layer saturated at 50%, whereby the surface charge density increases continuously. We found a correlation between the surface charge density after synthesis of colloidal nanoparticles and its behavior in catalysis. The properties of the laser-generated nanoparticles in the colloidal state appear to have predetermined the catalytic performance. We found that a smaller surface charge density of the usAu NPs was beneficial for the catalytic activity in CO and ethanol oxidation, while their peroxidase-like activity was affected less. The catalytic activity was 2 times higher for samples prepared by chloride-free LFL after ozone pretreatment compared to samples prepared in pure water. Copyright © 2020 American Chemical Society.view abstract doi: 10.1021/acs.jpcc.0c06257 2020 • 721 Plasma-assisted gas-phase synthesis and in-line coating of silicon nanoparticles
Dasgupta, M. and Fortugno, P. and Wiggers, H.
Plasma Processes and Polymers 17 (2020)This study investigates the feasibility of plasma-supported in-line functionalization of silicon nanoparticles (NPs) in an atmospheric pressure gas-phase reactor. The approach utilizes the synthesis of core silicon NPs and their subsequent coating downstream of the particle formation zone. In-line coating is accomplished with a cylindrical coating nozzle to achieve homogenous mixing of coating precursor vapors with in-coming NPs. Multiple siloxanes were tested for their coating suitability and their ability towards coating homogeneity. It was found that tetraethyl orthosilicate is favored for thin layers consisting of almost pure silica while hexamethyldisiloxane and octamethylcyclotetrasiloxane (OMCTS) coatings contained reasonable amounts of hydrocarbons. Moreover, OMCTS showed a pronounced tendency towards homogeneous nucleation, thus leading to the additional formation of silica NPs due to homogeneous nucleation. © 2020 The Authors. Plasma Processes and Polymers published by WILEY-VCH Verlag GmbH & Co. KGaAview abstract doi: 10.1002/ppap.201900245 2020 • 720 Polymer nanocomposite ultrafiltration membranes: The influence of polymeric additive, dispersion quality and particle modification on the integration of zinc oxide nanoparticles into polyvinylidene difluoride membranes
Berg, T.D. and Ulbricht, M.
Membranes 10 1-19 (2020)This study aims to improve the understanding of the influence of metal oxide nanofillers on polyvinylidene difluoride (PVDF) ultrafiltration membranes. Zinc oxide nanoparticles were chosen as the model filler material. The membranes were prepared by non-solvent induced phase separation from PVDF solutions in N-methylpyrrolidone. The influences of the addition of polyvinylpyrrolidone (PVP), the nanoparticle dispersion quality, and a surface modification of the ZnO particles with PVP on the nanofiller integration into the polymer matrix and the resulting membrane separation performance, were evaluated. Unmodified and PVP-modified nanoparticles were characterized by evaluation of their Hansen solubility parameters. The membranes were characterized by ultrafiltration experiments, scanning electron microscopy (SEM) and with respect to mechanical properties, while the dope solutions were analyzed by rheology in order to judge about dispersion quality. Pure water permeability and solute rejection data revealed that the dominant effect of the addition of pristine ZnO nanoparticles was a major decrease in permeability caused by pore blocking. In SEM analyses, it was seen that the plain nanofiller did not integrate well into the polymer matrix. Importantly, it was found that the surface modification of the nanofiller, as well as a high dispersion quality, can be strategically used to enhance the integration of the nanofiller and thus suppress pore blocking, leading to membranes with high ultrafiltration rejection and permeability simultaneously. Overall, the study provides relevant insights into a new approach to integrating nanofillers into polymer nanocomposite membranes for improving their properties and performance. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.view abstract doi: 10.3390/membranes10090197 2020 • 719 Preparation of antibiofouling nanocomposite PVDF/Ag-SiO2 membrane and long-term performance evaluation in the MBR system fed by real pharmaceutical wastewater
Ahsani, M. and Hazrati, H. and Javadi, M. and Ulbricht, M. and Yegani, R.
Separation and Purification Technology 249 (2020)In this work, the Ag-SiO2 nanoparticles were successfully synthesized and their antibacterial property was confirmed using the plate colony counting method. The SiO2 and Ag-SiO2 nanoparticles were used to prepare the PVDF/SiO2 and PVDF/Ag-SiO2 nanocomposite membranes, respectively. Pure water flux, contact angle and mechanical strength measurement analyses were conducted to characterize and compare the performance of the neat and nanocomposite membranes. Moreover, in order to investigate the structure of the prepared membranes scanning electron microscope (SEM) was used to obtain surface and cross-section images. A long-term filtration test was carried out in a bench scale submerged membrane bioreactor (MBR) system, fed by real pharmaceutical wastewater, to evaluate the antibiofouling performance of the prepared neat and nanocomposite membranes. In comparison to the neat PVDF, the pure water flux of the nanocomposite PVDF membrane (PVDF/Ag-SiO2; 0.6 wt%) increased about 60% and the water contact angle decreased from about 99° to 89°. The obtained results showed that the nanocomposite PVDF/Ag-SiO2 membrane exhibits considerable antibiofouling properties such that the accumulated dried biofilm as well as the extra cellular polymeric substances (EPSs) collected from the cake layer decreased considerably for the nanocomposite membrane. Moreover, the flux recovery ratio increased from 58% for the neat PVDF membrane to 76% for the nanocomposite PVDF/Ag-SiO2 membrane. The excitation and emission matrix (EEM) fluorescence spectroscopy analysis revealed that the accumulated protein on the surface of nanocomposite membranes decreased considerably in a way that the peak corresponding to tryptophan protein-like substances diminished completely, indicating the high antibiofouling potential of nanocomposite membranes. The chemical oxygen demand (COD) and ammonium removal efficiencies of the neat and nanocomposite membranes were higher than 90% and 95%, respectively, indicating negligible impact of the membrane modification on the effluents’ quality. © 2020view abstract doi: 10.1016/j.seppur.2020.116938 2020 • 718 Properties of α-Brass Nanoparticles. 1. Neural Network Potential Energy Surface
Weinreich, J. and Römer, A. and Paleico, M.L. and Behler, J.
Journal of Physical Chemistry C 124 12682-12695 (2020)Binary metal clusters are of high interest for applications in heterogeneous catalysis and have received much attention in recent years. To gain insights into their structure and composition at the atomic scale, computer simulations can provide valuable information if reliable interatomic potentials are available. In this paper we describe the construction of a high-dimensional neural network potential (HDNNP) intended for simulations of large brass nanoparticles with thousands of atoms, which is also applicable to bulk α-brass and its surfaces. The HDNNP, which is based on reference data obtained from density-functional theory calculations, is very accurate with a root-mean-square error of 1.7 meV/atom for total energies and 39 meV Å-1 for the forces of structures not included in the training set. The potential has been thoroughly validated for a wide range of energetic and structural properties of bulk α-brass, its surfaces as well as clusters of different size and composition demonstrating its suitability for large-scale molecular dynamics and Monte Carlo simulations with first-principles accuracy. © 2020 American Chemical Society.view abstract doi: 10.1021/acs.jpcc.0c00559 2020 • 717 Response to Comment on "high-surface-area corundum by mechanochemically induced phase transformation of boehmite"
Amrute, A.P. and Lodziana, Z. and Schreyer, H. and Weidenthaler, C. and Schüth, F.
Science 368 (2020)Li et al. commented that our report claims that methods reported thus far cannot enable the production of high-purity corundum with surface areas greater than 100 m2g-1, and that our obtained material could be porous aggregates rather than nanoparticles. We disagree with both of these suggestions. © 2020 American Association for the Advancement of Science. All rights reserved.view abstract doi: 10.1126/science.abb0948 2020 • 716 Self-assembled nano-silicon/graphite hybrid embedded in a conductive polyaniline matrix for the performance enhancement of industrial applicable lithium-ion battery anodes
Wiggers, H. and Sehlleier, Y.H. and Kunze, F. and Xiao, L. and Schnurre, S.M. and Schulz, C.
Solid State Ionics 344 (2020)Nano-structured silicon-based composite materials have generated significant excitement for use as anode materials in high-performance Li-ion batteries. For making these materials commercially applicable, a high Coulombic efficiency at the first cycle must be achieved. Additionally, scalable synthesis routes need to be developed to provide access to practically-relevant material quantities. In this work, we propose a strategy for the production of Si/graphite/polyaniline (Si/graphite/PANI) composites that addresses both above mentioned challenges. Si nanoparticles were produced in a pilot-plant-scale microwave-plasma reactor using monosilane (SiH4) as precursor. This process enables the formation of high-purity Si nanoparticles with controllable crystal sizes at a production rate of 45 g/h. Si/graphite hybrids are fabricated through self-assembly by electrostatic attraction. The Si/graphite/PANI nanocomposite is then prepared by in situ polymerization of aniline monomer in the presence of the Si/graphite hybrid. With this approach, ~40 g of Si/graphite/PANI composite per batch can be produced at lab scale. The scalability of the underlying processes enables the use for commercial products. The nanocomposite shows favorable characteristics inherited from its three components: Si nanoparticles provide high capacity, graphite acts as an electrical conductor and gives a high Coulombic efficiency, and the polyaniline coating further enhances the electrical conductivity and protects the entire structure. A very good Coulombic efficiency of 86.2% at the initial cycle is recorded for this nanocomposite material. Galvanostatic charge/discharge tests demonstrate that this material can deliver a discharge capacity of 2000 mAh/g with a very good capacity retention of 76% after 500 cycles at a discharge rate of 0.5C (1.25 A/g). The capacity is 870 mAh/g measured at 5C (12.5 A/g). © 2019 Elsevier B.V.view abstract doi: 10.1016/j.ssi.2019.115117 2020 • 715 Silicon Nanoparticle Films Infilled with Al2O3Using Atomic Layer Deposition for Photosensor, Light Emission, and Photovoltaic Applications
Botas, A.M.P. and Leitão, J.P. and Falcão, B.P. and Wiesinger, M. and Eckmann, F. and Teixeira, J.P. and Wiggers, H. and Stutzmann, M. and Ferreira, R.A.S. and Pereira, R.N.
ACS Applied Nano Materials 3 5033-5044 (2020)Solution-processed thin films of crystalline silicon nanoparticles (Si NPs) have a great potential for a wide variety of electronic and optoelectronic applications. However, such films are inherently unstable due to their huge surface-to-volume ratios and high surface energies, making them prone to degradation associated with spontaneous oxidation in ambient conditions. In this work, we explore the use of atomic layer deposition (ALD) as a means to stabilize and potentially functionalize solution-processed thin films of Si NPs for (opto)electronics, e.g., thin-film transistors, photosensors, light-emitting devices, and photovoltaics. We prepared films of randomly distributed Si NPs with ultrashort surface ligands (Si-H termination) using wet chemistry and spray-coating and then use ALD to infill the films with Al2O3. Through microscopy and optical structural/morphological analysis, we demonstrate the achievability of ALD infilling of films of Si NPs and probe the stability of these films against oxidation. Moreover, we show that the ALD infilling leads to changes in the light emission properties of the Si NP films, including a relative quenching of disorder-related emission features and variations in surface-related dielectric confinement effects. Our studies reveal ALD as a relevant technique toward manufacturing de facto robust, functional nanomaterials based on Si NPs and on nanoscale silicon materials more generally. © 2020 American Chemical Society.view abstract doi: 10.1021/acsanm.0c00116 2020 • 714 Silver clusters shape determination from in-situ XANES data
Timoshenko, J. and Roese, S. and Hövel, H. and Frenkel, A.I.
Radiation Physics and Chemistry 175 (2020)Knowledge of nanoparticle size, shape and morphology and of their in-situ transformations is crucial for establishing structure-properties relationship in nanosized materials that find applications, e.g., in plasmonic devices and heterogenous catalysis. Here we demonstrate that this information can be extracted reliably from in-situ X-ray absorption near edge structure (XANES) data, by combining ab-initio XANES simulations and machine learning (artificial neural network (NN)) approaches. Here we use NN-XANES method to extract information about the size, shape and interatomic distances in silver clusters, and to monitor their changes during the temperature-controlled particle aggregation. © 2019 Elsevier Ltdview abstract doi: 10.1016/j.radphyschem.2018.11.003 2020 • 713 Smart Glycopolymeric Nanoparticles for Multivalent Lectin Binding and Stimuli-Controlled Guest Release
Saha, S. and Klein-Hitpaß, M. and Vallet, C. and Knauer, S.K. and Schmuck, C. and Voskuhl, J. and Giese, M.
Biomacromolecules 21 2356-2364 (2020)The synthesis and self-assembly of a polymer featuring a self-complementary supramolecular binding motif guanidiniocarbonyl pyrrole carboxylate zwitterion (GCP-zwitterion) bearing lactose moieties are reported. The GCP-zwitterion acts as a cross-linker to facilitate self-assembly of the polymeric chain into nanoparticles (NPs) at neutral pH in an aqueous medium. The formation of polymeric NPs can be controlled by addition of external stimuli (acid or base), which disfavors self-assembly of the GCP-zwitterion because of protonation or deprotonation of the GCP units in the polymer chain. The small-sized (<40 nm) NPs have a hydrophobic cavity and accessible lactose units on the outer shell for multivalent lectin binding. The multivalent interaction between NPs and the lectin peanut agglutinin was confirmed by agglutination experiments. In addition, the stimuli-responsive property of NPs was exploited for the uptake and release of a hydrophobic guest Nile red. Furthermore, the selectivity toward different cell lines (HEK 296T, HeLa, and Hep2G) was tested, and a cellular uptake of cargo-loaded NPs was found for Hep2G cells bearing the lactose-specific asialogylcoprotein receptor, whereas all other cells showed no NP interaction. Copyright © 2020 American Chemical Society.view abstract doi: 10.1021/acs.biomac.0c00292 2020 • 712 Sputter deposition of highly active complex solid solution electrocatalysts into an ionic liquid library: Effect of structure and composition on oxygen reduction activity
Manjón, A.G. and Löffler, T. and Meischein, M. and Meyer, H. and Lim, J. and Strotkötter, V. and Schuhmann, W. and Ludwig, Al. and Scheu, C.
Nanoscale 12 23570-23577 (2020)Complex solid solution electrocatalysts (often called high-entropy alloys) present a new catalyst class with highly promising features due to the interplay of multi-element active sites. One hurdle is the limited knowledge about structure-activity correlations needed for targeted catalyst design. We prepared Cr-Mn-Fe-Co-Ni nanoparticles by magnetron sputtering a high entropy Cantor alloy target simultaneously into an ionic liquid library. The synthesized nanoparticles have a narrow size distribution but different sizes (from 1.3 ± 0.1 nm up to 2.6 ± 0.3 nm), different crystallinity (amorphous, face-centered cubic or body-centered cubic) and composition (i.e. high Mn versus low Mn content). The Cr-Mn-Fe-Co-Ni complex solid solution nanoparticles possess an unprecedented intrinsic electrocatalytic activity for the oxygen reduction reaction in alkaline media, some of them even surpassing that of Pt. The highest intrinsic activity was obtained for body-centered cubic nanoparticles with a low Mn and Fe content which were synthesized using the ionic liquid 1-etyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [Emimi][(Tf)2N]. This journal is © The Royal Society of Chemistry.view abstract doi: 10.1039/d0nr07632e 2020 • 711 Structural evolution of bimetallic Co-Cu catalysts in CO hydrogenation to higher alcohols at high pressure
Göbel, C. and Schmidt, S. and Froese, C. and Fu, Q. and Chen, Y.-T. and Pan, Q. and Muhler, M.
Journal of Catalysis 383 33-41 (2020)Bimetallic Co-Cu catalysts are widely applied in higher alcohol synthesis (HAS), but the formation of the final active structure has not yet been fully clarified, especially for Co-rich catalysts. We investigated the structural evolution of a Co-Cu catalyst (Co:Cu = 2) from the hydrotalcite precursor containing additional Al3+ and Zn2+ to the final active state after 80 h under reaction conditions at 280 °C and 60 bar. The reconstruction of the bimetallic Co-Cu nanoparticles obtained by H2 reduction was induced by the feed gas consisting of an equimolar H2 and CO syngas mixture resulting in fast phase separation and sintering of metallic Cu0 and Co0 in the first 2 h time on stream (TOS) and a continuous carbidization of Co0 forming Co2C and its sintering until steady state was reached after 40 h TOS. An intergrowth of metallic Cu0 nanoparticles with Co2C nanoparticles was observed to occur under reaction conditions. The high selectivity to oxygenates amounting to 41% compared with 29% to hydrocarbons is ascribed to the multi-functional Co2C/Cu0 interface enabling dissociative CO adsorption, hydrogenation and CO insertion. The formation of hydrogenated carbon species (CxHy) originating from dissociative CO chemisorption is assumed to be favored by hydrogen spillover from Cu0 to Co2C. The adsorption sites for molecular CO provided by both Cu0 and Co2C facilitate its insertion into the CxHy intermediates thus leading to a higher selectivity to alcohols following the Anderson-Schulz-Flory distribution. © 2020 Elsevier Inc.view abstract doi: 10.1016/j.jcat.2020.01.004 2020 • 710 Superconducting NbN and CaFe0.88Co0.12AsF studied by point-contact spectroscopy with a nanoparticle Au array
Wu, Y.F. and Yu, A.B. and Lei, L.B. and Zhang, C. and Wang, T. and Ma, Y.H. and Huang, Z. and Chen, L.X. and Liu, Y.S. and Schneider, C.M. and Mu, G. and Xiao, H. and Hu, T.
Physical Review B 101 (2020)The point-contact-spectroscopy measurement is a powerful method to detect the superconducting gap and the spin polarization of materials. However, it is difficult to get a stable and clean point contact by conventional techniques. In this work, we fabricate multiple point contacts by depositing Au nanoparticle arrays on the surface of a superconductor through an anodic aluminum oxide patterned shadow mask. We obtained the superconducting gaps of niobium nitride thin film (NbN, Tc=16 K) and iron superconductors CaFe0.88Co0.12AsF single crystals (Ca-1111, Tc=21.3 K) by fitting the point-contact spectroscopy with the Blonder-Tinkham-Klapwijk theory. We found that NbN's gap (Δ) exhibits the BCS-like temperature dependence with Δ≈2.88 meV at 0 K and 2Δ/kBTc≈4.22 in agreement with previous reports. By contrast, Ca-1111 has a multigap structure with Δ1≈1.99 meV and Δ2≈5.01 meV at 0 K, and the ratio between the superconducting gap and Tc is 2Δ1/kBTc=2.2 and 2Δ2/kBTc=5.5, suggesting an unconventional paring mechanism of Ca-1111 also in agreement with previous reports on other Fe-based superconductors. Our multiple point-contacts method thus provides an alternative way to perform measurements of the superconducting gap. © 2020 American Physical Society. ©2020 American Physical Society.view abstract doi: 10.1103/PhysRevB.101.174502 2020 • 709 Synthesis and characterization of PLGA/HAP scaffolds with DNA-functionalised calcium phosphate nanoparticles for bone tissue engineering
Sokolova, V. and Kostka, K. and Shalumon, K.T. and Prymak, O. and Chen, J.-P. and Epple, M.
Journal of Materials Science: Materials in Medicine 31 (2020)Porous scaffolds of poly(lactide-co-glycolide) (PLGA; 85:15) and nano-hydroxyapatite (nHAP) were prepared by an emulsion-precipitation procedure from uniform PLGA–nHAP spheres (150–250 µm diameter). These spheres were then thermally sintered at 83 °C to porous scaffolds that can serve for bone tissue engineering or for bone substitution. The base materials PLGA and nHAP and the PLGA–nHAP scaffolds were extensively characterized by X-ray powder diffraction, infrared spectroscopy, thermogravimetry, differential scanning calorimetry, and scanning electron microscopy. The scaffold porosity was about 50 vol% as determined by relating mass and volume of the scaffolds, together with the computed density of the solid phase (PLGA–nHAP). The cultivation of HeLa cells demonstrated their high cytocompatibility. In combination with DNA-loaded calcium phosphate nanoparticles, they showed a good activity of gene transfection with enhanced green fluorescent protein (EGFP) as model protein. This is expected enhance bone growth around an implanted scaffold or inside a scaffold for tissue engineering. [Figure not available: see fulltext.] © 2020, The Author(s).view abstract doi: 10.1007/s10856-020-06442-1 2020 • 708 Synthesis and intracellular tracing surface-functionalized calcium phosphate nanoparticles by super-resolution microscopy (STORM)
Rojas-Sánchez, L. and Loza, K. and Epple, M.
Materialia 12 (2020)Calcium phosphate nanoparticles with covalently attached fluorescent dye molecules were prepared by copper-catalysed azide-alkyne cycloaddition (CuAAC) and by strain-promoted azide-alkyne cycloaddition (SPAAC), i.e. click chemistry. The reaction kinetics and labeling degrees of the two click reactions were compared and quantified. For oxidation-sensitive molecules, the SPAAC method is preferable due to the milder reaction conditions and the absence of copper(II). The highly fluorescent AF-488-labeled nanoparticles were applied for super-resolution fluorescence microscopy, i.e. stochastic optical reconstruction microscopy (STORM). By this method, individual nanoparticles (diameter about 60 nm) were observed in endolysosomes inside HeLa cells after cellular uptake at a resolution of 20–30 nm. © 2020view abstract doi: 10.1016/j.mtla.2020.100773 2020 • 707 Synthesis, Structure, Properties, and Applications of Bimetallic Nanoparticles of Noble Metals
Loza, K. and Heggen, M. and Epple, M.
Advanced Functional Materials 30 (2020)Bimetallic nanoparticles of noble metals are of high interest in imaging, biomedical devices, including nanomedicine, and heterogeneous catalysis. Synthesis, properties, characterization, biological properties, and practical applicability of nanoparticles on the basis of platinum group metals and the coin metals Ag and Au are discussed, also in comparison with the corresponding monometallic nanoparticles. In addition to the parameters that are required to characterize monometallic nanoparticles (mainly size, size distribution, shape, crystallographic nature, surface functionalization, charge), further information is required for a full characterization of bimetallic nanoparticles. This concerns the overall elemental composition of a bimetallic nanoparticle population (ratio of the two metals) and the internal distribution of the elements in individual nanoparticles (e.g., the presence of homogeneous alloys, core–shell systems, and possible intermediate stages). It is also important to ensure that all particles are identical in terms of elemental composition, that is, that the homogeneity of the particle population is given. Macroscopic properties like light absorption, antibacterial effects, and catalytic activity depend on these properties. The currently available methods for a full characterization of bimetallic nanoparticles are discussed, and future developments in this field are outlined. © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/adfm.201909260 2020 • 706 Tailoring the Size, Inversion Parameter, and Absorption of Phase-Pure Magnetic MgFe2O4Nanoparticles for Photocatalytic Degradations
Bloesser, A. and Kurz, H. and Timm, J. and Wittkamp, F. and Simon, C. and Hayama, S. and Weber, B. and Apfel, U.-P. and Marschall, R.
ACS Applied Nano Materials 3 11587-11599 (2020)Phase-pure magnesium ferrite (MgFe2O4) spinel nanocrystals are synthesized by a fast microwave-assisted route. The elemental composition is optimized via the ratio of the precursor mixture and controlled by energy-dispersive X-ray spectroscopy. Fine-tuning of the magnetic properties without changing the overall elemental composition is demonstrated by superconducting quantum interference device (SQUID) magnetometry and Mössbauer spectroscopy. Together with X-ray absorption spectroscopy and X-ray emission spectroscopy, we confirm that the degree of cation inversion is altered by thermal annealing. We can correlate the magnetic properties with both the nanosize influence and the degree of inversion. The resulting nonlinear course of saturation magnetization (Ms) in correlation with the particle diameter allows to decouple crystallite size and saturation magnetization, by this providing a parameter for the production of very small nanoparticles with high Ms with great potential for magnetic applications like ferrofluids or targeted drug delivery. Our results also suggest that the optical band gap of MgFe2O4 is considerably larger than the fundamental electronic band gap because of the d5 electronic configuration of the iron centers. The presented different electronic transitions contributing to the absorption of visible light are the explanation for the large dissent among the band gaps and band potentials found in the literature. © 2020 American Chemical Society.view abstract doi: 10.1021/acsanm.0c02705 2020 • 705 The importance of nanoscale confinement to electrocatalytic performance
Wordsworth, J. and Benedetti, T.M. and Alinezhad, A. and Tilley, R.D. and Edwards, M.A. and Schuhmann, W. and Gooding, J.J.
Chemical Science 11 1233-1240 (2020)Electrocatalytic nanoparticles that mimic the three-dimensional geometric architecture of enzymes where the reaction occurs down a substrate channel isolated from bulk solution, referred to herein as nanozymes, were used to explore the impact of nano-confinement on electrocatalytic reactions. Surfactant covered Pt-Ni nanozyme nanoparticles, with Ni etched from the nanoparticles, possess a nanoscale channel in which the active sites for electrocatalysis of oxygen reduction are located. Different particle compositions and etching parameters allowed synthesis of nanoparticles with different average substrate channel diameters that have varying amounts of nano-confinement. The results showed that in the kinetically limited regime at low overpotentials, the smaller the substrate channels the higher the specific activity of the electrocatalyst. This is attributed to higher concentrations of protons, relative to bulk solution, required to balance the potential inside the nano-confined channel. However, at higher overpotentials where limitation by mass transport of oxygen becomes important, the nanozymes with larger substrate channels showed higher electrocatalytic activity. A reaction-diffusion model revealed that the higher electrocatalytic activity at low overpotentials with smaller substrate channels can be explained by the higher concentration of protons. The model suggests that the dominant mode of mass transport to achieve these high concentrations is by migration, exemplifying how nano-confinement can be used to enhance reaction rates. Experimental and theoretical data show that under mass transport limiting potentials, the nano-confinement has no effect and the reaction only occurs at the entrance of the substrate channel at the nanoparticle surface. © The Royal Society of Chemistry.view abstract doi: 10.1039/c9sc05611d 2020 • 704 The Influence of the Distribution Function of Ferroelectric Nanoparticles Sizes on Their Electrocaloric and Pyroelectric Properties
Shevliakova, H.V. and Morozovska, A.N. and Morozosky, N.V. and Svechnikov, G.S. and Shvartsman, V.V.
IEEE Transactions on Ultrasonics, Ferroelectrics, and Frequency Control 67 2445-2453 (2020)We consider a model of a nanocomposite based on noninteracting spherical single-domain ferroelectric nanoparticles (NPs) of various sizes embedded in a dielectric matrix. The size distribution function of these NPs is selected as a part of the truncated Gaussian distribution from minimum to maximum radius. For such nanocomposites, we calculate the dependences of the reversible part of the electric polarization, the electrocaloric (EC) temperature change, and the dielectric permittivity on the external electric field, which have the characteristic form of hysteresis loops. We then analyze the change in the shape of the hysteresis loops relative to the particle size distribution parameters. We demonstrate that the remanent polarization, coercive field, dielectric permittivity maximums, and maximums and minimums of the EC temperature change depend most strongly on the most probable radius, moderately on the dispersion, and have the weakest dependence on the maximum radius of the NP. We calculate and analyze the dependences of pyroelectric figures of merit on the average radius of the NPs in the composite. The dependences confirm the presence of a phase transition induced by the size of the NPs, which is characterized by the presence of a maxima near the critical average radius of the particles, the value of which increases with an increasing dispersion of the distribution function. © 1986-2012 IEEE.view abstract doi: 10.1109/TUFFC.2020.3004740 2020 • 703 Tunable and switchable nanoparticle separation with thermo-responsive track-etched membranes prepared by controlled surface-initiated polymerization of poly(N-isopropylacrylamide)
Daumann, K. and Frost, S. and Ulbricht, M.
RSC Advances 10 21028-21038 (2020)This work describes how the control of grafting density and grafted chain length of a thermo-responsive polymer in membrane pores can be utilized to tune the pore size and the switchability of size-based selectivity in the ultrafiltration range. Using a previously established methodology for controlled synthesis, surface-initiated atom transfer polymerization (ATRP) of poly(N-isopropylacrylamide) (PNIPAAm) to the pore walls of poly(ethylene terephthalate) track-etched membranes with experimentally determined pore diameters of 35 nm (PET30) and 110 nm (PET80) is performed. Characterization in this study is mainly done with filtration experiments, making use of the well-defined pore structure of the base membranes. It is demonstrated that both the gravimetrically determined degree of functionalization and the effective pore size determined from water permeability are a linear function of ATRP time. For the grafted PET30 membranes, it is shown that the rejection of lysozyme (diameter ∼ 4 nm) can be switched between 99% at 23 °C and 65% at 45 °C for the membrane with the highest degree of functionalization. For the grafted PET80 membranes, it is found that two different types of membranes can be obtained. Membranes with long grafted chains at low grafting density show very large changes of water permeability as a function of temperature (effective pore size switching ratio of up to 10) and, for example, rejection for 20 nm silica particles of 95% and 23% at 23 °C and 45 °C, respectively. Membranes with PNIPAAm at high grafting density show much lower switching ratios (as low as 1.4, for long enough grafted chains). Effective pore size and thermo-responsive change of pore size can therefore be tuned by the combination of both synthesis parameters, initiator density and ATRP time. The switchable thermo-responsive separation of two colloids with a tailored membrane is demonstrated for mixtures of bovine serum albumin (BSA; ∼7 nm) and silica nanoparticles (20 nm); at 23 °C silica is completely rejected and only BSA is in the permeate; at 40 °C both colloids permeate through the membrane. © The Royal Society of Chemistry 2020.view abstract doi: 10.1039/d0ra03418e 2020 • 702 Ultrasmall gold and silver/gold nanoparticles (2 nm) as autofluorescent labels for poly(D,L-lactide-co-glycolide) nanoparticles (140 nm)
Wey, K. and Epple, M.
Journal of Materials Science: Materials in Medicine 31 (2020)Ultrasmall metallic nanoparticles show an efficient autofluorescence after excitation in the UV region, combined with a low degree of fluorescent bleaching. Thus, they can be used as fluorescent labels for polymer nanoparticles which are frequently used for drug delivery. A versatile water-in-oil-in-water emulsion-evaporation method was developed to load poly(D,L-lactide-co-glycolide) (PLGA) nanoparticles with autofluorescent ultrasmall gold and silver/gold nanoparticles (diameter 2 nm). The metallic nanoparticles were prepared by reduction of tetrachloroauric acid with sodium borohydride and colloidally stabilised with 11-mercaptoundecanoic acid. They were characterised by UV–Vis and fluorescence spectroscopy, showing a large Stokes shift of about 370 nm with excitation maxima at 250/270 nm and emission maxima at 620/640 nm for gold and silver/gold nanoparticles, respectively. The labelled PLGA nanoparticles (140 nm) were characterised by dynamic light scattering (DLS), scanning electron microscopy (SEM), and UV–Vis and fluorescence spectroscopy. Their uptake by HeLa cells was followed by confocal laser scanning microscopy. The metallic nanoparticles remained inside the PLGA particle after cellular uptake, demonstrating the efficient encapsulation and the applicability to label the polymer nanoparticle. In terms of fluorescence, the metallic nanoparticles were comparable to fluorescein isothiocyanate (FITC). [Figure not available: see fulltext.]. © 2020, The Author(s).view abstract doi: 10.1007/s10856-020-06449-8 2020 • 701 Unravelling the nucleation, growth, and faceting of magnetite-gold nanohybrids
Nalench, Y.A. and Shchetinin, I.V. and Skorikov, A.S. and Mogilnikov, P.S. and Farle, M. and Savchenko, A.G. and Majouga, A.G. and Abakumov, M.A. and Wiedwald, U.
Journal of Materials Chemistry B 8 3886-3895 (2020)The chemical synthesis of nanoparticles with a preassigned size and shape is important for an optimized performance in any application. Therefore, systematic monitoring of the synthesis is required for the control and detailed understanding of the nucleation and growth of the nanoparticles. Here, we study Fe3O4-Au hybrid nanoparticles in detail using probes of the reaction mixture during synthesis and their thorough characterization. The proposed approach eliminates the problem of repeatability and reproducibility of the chemical synthesis and was carried out using laboratory equipment (standard transmission electron microscopy, X-ray diffraction, and magnetometry) for typically 10 μL samples instead of, for example, a dedicated synthesis and inspection at a synchrotron radiation facility. From the three independent experimental techniques we extract the nanoparticle size at 12 stages of the synthesis. These diameters show identical trends and good quantitative agreement. Two consecutive processes occur during the synthesis of Fe3O4-Au nanoparticles, the nucleation and the growth of spherical Fe3O4nanoparticles on the surface of Au seeds during the heating stage and their faceting towards octahedral shape during reflux. The final nanoparticles with sizes of 15 nm Fe3O4and 4 nm Au exhibit superparamagnetic behavior at ambient temperature. These are high-quality, close to stoichiometric Fe3O4nanocrystals with nearly volumetric magnetic behavior as confirmed by the presence of the Verwey transition. Understanding the processes occurring during the synthesis allows the nanoparticle size and shape to be adjusted, improving their capabilities in biomedical applications. © The Royal Society of Chemistry 2020.view abstract doi: 10.1039/c9tb02721a 2019 • 700 Ablation target cooling by maximizing the nanoparticle productivity in laser synthesis of colloids
Waag, F. and Gökce, B. and Barcikowski, S.
Applied Surface Science 466 647-656 (2019)Even if ultrashort laser pulses are used during the laser synthesis of colloids, a significant amount of laser energy is converted into thermal energy, which results in heating the ablation target and the colloid. To date, little attention has been paid to these heating effects in the literature. This study was focused on measurements of the process temperature during the high-power, ultrashort-pulsed laser ablation of a nickel target in a continuous water flow setup. Time-resolved monitoring of the temperature of the ablation target and of the colloid indicated that there was an initial rapid uptake of thermal energy followed by a thermally-stable state in which there was very little additional heating. Shifting the focal plane from behind the target onto its surface and further into the fluid provided insight concerning the different mechanisms of heat generation, dissipation, and transfer in the laser synthesis of colloids. It even was possible to distinguish the fluence effects and the colloid re-irradiation effects. New possibilities of process control were identified by correlating the productivity of laser ablation at different focal plane shifts with the measured thermal data. Counterintuitively, the temperature of the target was minimized via ablation cooling when the productivity of the process was maximized. © 2018 Elsevier B.V.view abstract doi: 10.1016/j.apsusc.2018.10.030 2019 • 699 Acoustic emission control avoids fluence shifts caused by target runaway during laser synthesis of colloids
Labusch, M. and Cunha, A.P.A. and Wirtz, S.F. and Reichenberger, S. and Cleve, E. and Söffker, D. and Barcikowski, S.
Applied Surface Science 479 887-895 (2019)Pulsed laser ablation in liquids (PLAL) has been established as a scalable method to synthesize ligand-free nanoparticles. However, for continuous nanoparticle synthesis with high nanoparticle yield, it is mandatory to maintain a constant fluence, demanding a fixed distance between the focusing lens and target. The latter becomes a non-trivial task during continuous gram-scale nanoparticle production due to the quick removal of target material causing a diminishing productivity. Hence, to maintain a stable process, a perpetual optimization of the working distance is required. In this paper, a field programmable gate array-based measurement and control system is used for online adjustment of the working distance based on acoustic emission (AE) measurements. Ablation-characteristic acoustic frequencies were detected at base frequency correlating to the repetition rate as well as higher harmonics of the latter. The harmonic distortion of AE during laser ablation could be correlated to the location of the focal point. The amplitude intensities correlate well with the nanoparticle productivity. The optimal working distance was reproducibly adjusted in 5.79 min ± 0.41 min with a deviation of 0.33 mm ± 0.04 mm. The automated system provides the basis for temporal stability and scalability of the ablation process. © 2019 Elsevier B.V.view abstract doi: 10.1016/j.apsusc.2019.02.080 2019 • 698 Adhesion, proliferation, and osteogenic differentiation of human mesenchymal stem cells on additively manufactured Ti6Al4V alloy scaffolds modified with calcium phosphate nanoparticles
Chudinova, E.A. and Surmeneva, M.A. and Timin, A.S. and Karpov, T.E. and Wittmar, A. and Ulbricht, M. and Ivanova, A. and Loza, K. and Prymak, O. and Koptyug, A. and Epple, M. and Surmenev, R.A.
Colloids and Surfaces B: Biointerfaces 176 130-139 (2019)In the present study, biocomposites based on 3D porous additively manufactured Ti6Al4V (Ti64) scaffolds modified with biocompatible calcium phosphate nanoparticles (CaPNPs) were investigated. Ti64 scaffolds were manufactured via electron beam melting technology using an Arcam machine. Electrophoretic deposition was used to modify the scaffolds with CaPNPs, which were synthesized by precipitation in the presence of polyethyleneimine (PEI). Dynamic light scattering revealed that the CaP/PEI nanoparticles had an average size of 46 ± 18 nm and a zeta potential of +22 ± 9 mV. Scanning electron microscopy (SEM) revealed that the obtained spherical CaPNPs had an average diameter of approximately 90 nm. The titanium-based scaffolds coated with CaPNPs exhibited improved hydrophilic surface properties, with a water contact angle below 5°. Cultivation of human mesenchymal stem cells (hMSCs) on the CaPNPs-coated Ti64 scaffolds indicated that the improved hydrophilicity was beneficial for the attachment and growth of cells in vitro. The Ti6Al4V/CaPNPs scaffold supported an increase in the alkaline phosphatase (ALP) activity of cells. In addition to the favourable cell proliferation and differentiation, Ti6Al4V/CaPNPs scaffolds displayed increased mineralization compared to non-coated Ti6Al4V scaffolds. Thus, the developed composite 3D scaffolds of Ti6Al4V functionalized with CaPNPs are promising materials for different applications related to bone repair. © 2018 Elsevier B.V.view abstract doi: 10.1016/j.colsurfb.2018.12.047 2019 • 697 Cascade Reactions in Nanozymes: Spatially Separated Active Sites inside Ag-Core-Porous-Cu-Shell Nanoparticles for Multistep Carbon Dioxide Reduction to Higher Organic Molecules
O'Mara, P.B. and Wilde, P. and Benedetti, T.M. and Andronescu, C. and Cheong, S. and Gooding, J.J. and Tilley, R.D. and Schuhmann, W.
Journal of the American Chemical Society 141 14093-14097 (2019)Enzymes can perform complex multistep cascade reactions by linking multiple distinct catalytic sites via substrate channeling. We mimic this feature in a generalized approach with an electrocatalytic nanoparticle for the carbon dioxide reduction reaction comprising a Ag core surrounded by a porous Cu shell, providing different active sites in nanoconfined volumes. The architecture of the nanozyme provides the basis for a cascade reaction, which promotes C-C coupling reactions. The first step occurs on the Ag core, and the subsequent steps on the porous copper shell, where a sufficiently high CO concentration due to the nanoconfinement facilitates C-C bond formation. The architecture yields the formation of n-propanol and propionaldehyde at potentials as low as-0.6 V vs RHE. Copyright © 2019 American Chemical Society.view abstract doi: 10.1021/jacs.9b07310 2019 • 696 Catalytic Carbon Monoxide Oxidation over Potassium-Doped Manganese Dioxide Nanoparticles Synthesized by Spray Drying
Ollegott, K. and Peters, N. and Antoni, H. and Muhler, M.
Emission Control Science and Technology (2019)Manganese oxides are promising catalysts for the oxidation of CO as well as the removal of volatile organic compounds from exhaust gases because of their structural versatility and their ability to reversibly change between various oxidation states. MnO2 nanoparticles doped with Na+ or K+ were synthesized by a semi-continuous precipitation method based on spray drying. Specific surface area, crystallite size, and morphology of these particles were predominantly determined by the spray-drying parameters controlling the quenching of the crystallite growth, whereas thermal stability, reducibility, and phase composition were strongly influenced by the alkali ion doping. Pure α-MnO2 was obtained by K+ doping under alkaline reaction conditions followed by calcination at 450 °C, which revealed a superior catalytic activity in comparison to X-ray amorphous or Mn2O3-containing samples. Thus, the phase composition is identified as a key factor for the catalytic activity of manganese oxides, and it was possible to achieve a similar activation of a K+-doped X-ray amorphous catalyst under reaction conditions resulting in the formation of crystalline α-MnO2. The beneficial effect of K+ doping on the catalytic activity of MnO2 is mainly associated with the stabilizing effect of K+ on the α-MnO2 tunnel structure. © 2019, Springer Nature Switzerland AG.view abstract doi: 10.1007/s40825-019-00125-2 2019 • 695 Combination of an atmospheric pressured arc reactor and a magnetron sputter device for the synthesis of novel nanostructured thin films
Tillmann, W. and Kokalj, D. and Stangier, D. and Fu, Q. and Kruis, E.
Thin Solid Films 689 (2019)Nanocomposite coatings are state of the art, nevertheless the possible material combinations are restricted. Therefore, this work demonstrates an approach to synthesize novel nanostructured thin films by producing the nanoparticles and thin films independently. An atmospheric-pressure transferred arc reactor is used to synthesize TiN nanoparticles. The device is linked to a magnetron sputter device with an aerodynamic lens system. The aerodynamic lens enables the in-situ introduction of the synthesized nanoparticles into the PVD chamber by compensating the pressure differences. In this study, the influence of the linkage on the properties of a CrN thin film as well as the chamber conditions (pressure, temperature, bias-voltage, and plasma) on the TiN nanoparticles are analyzed. The CrN thin film is only slightly affected by the incoming working gas of the nanoparticle reactor. The TiN nanoparticles reveal a crystallite size of 9.3 ± 2.3 nm and are successfully introduced into the PVD chamber as agglomerates with sizes of 0.04 μm2 and are then deposited onto substrates. It is shown that the particle distribution, agglomerate size, morphology, and crack behavior can be influenced by the chamber conditions. © 2019 Elsevier B.V.view abstract doi: 10.1016/j.tsf.2019.137528 2019 • 694 Confinement Assembly of ABC Triblock Terpolymers for the High-Yield Synthesis of Janus Nanorings
Steinhaus, A. and Chakroun, R. and Mullner, M. and Nghiem, T.-L. and Hildebrandt, M. and Groschel, A.H.
ACS Nano 13 6269-6278 (2019)Block copolymers are versatile building blocks for the self-assembly of functional nanostructures in bulk and solution. While spheres, cylinders, and bilayer sheets are thermodynamically preferred shapes and frequently observed, ring-shaped nanoparticles are more challenging to realize due to energetic penalties that originate from their anisotropic curvature. Today, a handful of concepts exist that produce core shell nanorings, while more complex (e.g., patchy) nanorings are currently out of reach and have only been predicted theoretically. Here, we demonstrate that confinement assembly of properly designed ABC triblock terpolymers is a general route to synthesize Janus nanorings in high purity. The triblock terpolymer self-assembles in the spherical confinement of nanoemulsion droplets into prolate ellipsoidal microparticles with an axially stacked lamellar-ring (lr)-morphology. We clarified and visualized this complex, yet well-ordered, morphology with transmission electron tomography. Blocks A and C formed stacks of lamellae with the B microdomain sandwiched in-between as nanorings. Cross-linking of the B-rings allowed disassembly of the microparticles into Janus nanorings carrying two strictly separated polymer brushes of A and C on the top and bottom. Decreasing the B volume leads to Janus spheres and rods, while an increase of B results in perforated and filled Janus disks. The confinement assembly of ABC triblock terpolymers is a general process that can be extended to other block chemistries and will allow to synthesize a large variety of complex micro- A nd nanoparticles that inspire studies in self-assembly, interfacial stabilization, colloidal packing, and nanomedicine. © 2019 American Chemical Society.view abstract doi: 10.1021/acsnano.8b09546 2019 • 693 Control of Metal–Organic Framework Crystallization by Metastable Intermediate Pre-equilibrium Species
Yeung, H.H.M. and Sapnik, A.F. and Massingberd-Mundy, F. and Gaultois, M.W. and Wu, Y. and Fraser, D.A.X. and Henke, S. and Pallach, R. and Heidenreich, N. and Magdysyuk, O.V. and Vo, N.T. and Goodwin, A.L.
Angewandte Chemie - International Edition 58 566-571 (2019)There is an increasing amount of interest in metal–organic frameworks (MOFs) for a variety of applications, from gas sensing and separations to electronics and catalysis. However, the mechanisms by which they crystallize remain poorly understood. Herein, an important new insight into MOF formation is reported. It is shown that, prior to network assembly, crystallization intermediates in the canonical ZIF-8 system exist in a dynamic pre-equilibrium, which depends on the reactant concentrations and the progress of reaction. Concentration can, therefore, be used as a synthetic handle to directly control particle size, with potential implications for industrial scale-up and gas sorption applications. These findings enable the rationalization of apparent contradictions between previous studies of ZIF-8 and opens up new opportunities for the control of crystallization in network solids more generally. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/anie.201810039 2019 • 692 Decreased bacterial colonization of additively manufactured Ti6Al4V metallic scaffolds with immobilized silver and calcium phosphate nanoparticles
Surmeneva, M. and Lapanje, A. and Chudinova, E. and Ivanova, A. and Koptyug, A. and Loza, K. and Prymak, O. and Epple, M. and Ennen-Roth, F. and Ulbricht, M. and Rijavec, T. and Surmenev, R.
Applied Surface Science 480 822-829 (2019)The design of an ideal bone graft substitute has been a long-standing effort, and a number of strategies have been developed to improve bone regeneration. Electron beam melting (EBM) is an additive manufacturing method allowing for the production of porous implants with highly defined external dimensions and internal architectures. The increasing surface area of the implant may also increase the abilities of pathogenic microorganisms to adhere to the surfaces and form a biofilm, which may result in serious complications. The aim of this study was to explore the modifications of Ti6Al4V alloy scaffolds to reduce the abilities of bacteria to attach to the EBM-manufactured implant surface. The layers composed of silver (Ag), calcium phosphate (CaP) nanoparticles (NPs) and combinations of both were formed on the EBM-fabricated metallic scaffolds by electrophoretic deposition in order to provide them with antimicrobial properties. The assay of bacterial colonization on the surface was performed with the exposure of scaffold surfaces to Staphylococcus aureus cells for up to 17 h. Principal component analysis (PCA) was used to assess the relationships between different surface features of the studied samples and bacterial adhesion. The results indicate that by modifying the implant surface with appropriate nanostructures that change the hydrophobicity and the surface roughness at the nano scale, physical cues are provided that disrupt bacterial adhesion. Our results clearly show that AgNPs at a concentration of approximately 0.02 mg/сm 2 that were deposited together with CaPNPs covered by positively charge polyethylenimine (PEI) on the surface of EBM-sintered Ti6Al4V scaffolds hindered bacterial growth, as the total number of attached cells (NAC) of S. aureus remained at the same level during the 17 h of exposure, which indicates bacteriostatic activity. © 2019 Elsevier B.V.view abstract doi: 10.1016/j.apsusc.2019.03.003 2019 • 691 Development of a high flow rate aerodynamic lens system for inclusion of nanoparticles into growing PVD films to form nanocomposite thin films
Kiesler, D. and Bastuck, T. and Kennedy, M.K. and Kruis, F.E.
Aerosol Science and Technology 53 630-646 (2019)Hard coatings for wear protection of tools, bearings, and sliding parts play an important role in industrial manufacturing. Nanocomposite coatings are being used in this context to improve the mechanical properties. The technology applied therefore is often based on physical vapor deposition (PVD), in which the different materials are co-deposited. In these processes it is not possible to control the properties of the disperse phase and continuous phase independently. Here, we present a technology which combines aerosol technology with thin film technology to produce nanocomposite coatings directly, which gives us full control over both phases. It is based on an upscaled three-stage aerodynamic lens, which allows to bring nanoparticles from an atmospheric-pressure aerosol reactor into a PVD vacuum chamber operating at low pressure (2 Pa). This requires the use of a higher mass flow rate than conventionally used in aerodynamic lenses, so that a rational upscaling strategy for designing an aerodynamic lens for larger mass flow rates is proposed. Here, an array consisting of eight parallel three-stage aerodynamic lenses having each a mass flow rate of 0.6 slm using argon and 0.71 slm using nitrogen is built and optimized, assisted by CFD and numerical trajectory analysis. The transfer efficiency has been investigated numerically and experimentally. It is possible to transfer 80% of the particles with only 1.3% of the gas into the deposition chamber. A number of coatings consisting of titanium carbonitride nanoparticles embedded in a PVD chromium oxynitride film with varying nanoparticle content were produced. Electron microscopy shows the successful incorporation of the nanoparticles in the thin film. A reduction in film crystallite size with increasing nanoparticle content was found. A reverse Hall–Petch behavior was observed. Copyright © 2019 American Association for Aerosol Research. © 2019, © 2019 American Association for Aerosol Research.view abstract doi: 10.1080/02786826.2019.1587149 2019 • 690 Discrimination of effects leading to gas formation during pulsed laser ablation in liquids
Kalus, M.-R. and Reimer, V. and Barcikowski, S. and Gökce, B.
Applied Surface Science 465 1096-1102 (2019)Pulsed laser ablation of a bulk target in liquid induces the formation of cavitation bubbles and persistent gas bubbles, which both shield subsequent laser pulses leading to a decrease in nanoparticle productivity. A further shielding entity and a source for gas formation when post-irradiated are the synthesized nanoparticles. In this study, an experimental setup is developed, which allows quantitative measurement of the gas volume produced by these shielding entities. It can be shown that 1 cm3 gas is produced in 10 min ablation time when 8 W picosecond-laser power is applied. By a combined experimental and mathematical approach, the gas volumes induced by silver bulk ablation and post-irradiation effects of the produced colloids are discriminated. It is shown that a characteristic nanoparticle mass concentration threshold exists, where post-irradiation effects mostly dominate gas formation. In a synergistic process, the effective laser fluence available for bulk ablation decreases with increasing nanoparticle mass concentration and up to 80% of the laser power is coupled into the nanoparticles. At the same time, the interparticle distance between the nanoparticles decreases favoring the laser-induced breakdown of the liquid. © 2018 Elsevier B.V.view abstract doi: 10.1016/j.apsusc.2018.09.224 2019 • 689 Durability study of platinum nanoparticles supported on gas-phase synthesized graphene in oxygen reduction reaction conditions
Bertin, E. and Münzer, A. and Reichenberger, S. and Streubel, R. and Vinnay, T. and Wiggers, H. and Schulz, C. and Barcikowski, S. and Marzun, G.
Applied Surface Science 467-468 1181-1186 (2019)Ligand-free platinum nanoparticles were prepared by pulsed laser ablation in liquids (PLAL) and employed as a benchmarking catalyst to evaluate the durability of a new gas-phase synthesized graphene support in oxygen reduction conditions. Raman measurements showed that the graphene, as compared to Vulcan, was almost defect free. Transmission electron microscopy and initial electrochemically active surface area measurements confirmed good dispersion of the catalysts on both supports. During durability tests, graphene supported Pt nanoparticles showed much better ECSA retention (75% on graphene as compared to 38% on Vulcan), ultimately retaining a higher ECSA than a commercial sample subjected to the same procedure. © 2018 Elsevier B.V.view abstract doi: 10.1016/j.apsusc.2018.10.061 2019 • 688 Evalution of Drude parameters for liquid Germanium nanoparticles through aerosol-based line-of-sight attenuation measurements
Daun, K.J. and Menser, J. and Asif, M. and Musikhin, S. and Dreier, T. and Schulz, C.
Journal of Quantitative Spectroscopy and Radiative Transfer 226 146-156 (2019)The objective of this study is to infer Drude model parameters for liquid germanium nanoparticles from extinction measurements made across an aerosol within a microwave plasma reactor using a halogen lamp (410–700 nm) and a laser-driven light source (205–585 nm). The plasma frequency and relaxation time are inferred using Rayleigh theory, Mie theory, and a fourth-order Mie approximation. These parameters are compared with those found using the ellipsometry-derived complex dielectric function as well as the bulk density and electrical resistivity of liquid germanium. The analysis is carried out in a probabilistic context using Bayesian inference, which accounts for both the measurement noise and model error. While all the candidate models can reproduce the shape of the experimentally-derived extinction spectra, the Bayesian inference showed that extinction-derived parameters differed from those obtained from the density and electrical resistivity in a statistically-significant way. This highlights the limitations of the free-electron model that underpins Drude theory, and suggests potential opportunities for model refinement. © 2019 Elsevier Ltdview abstract doi: 10.1016/j.jqsrt.2019.01.021 2019 • 687 Evolution of the Ligand Shell Around Small ZnO Nanoparticles During the Exchange of Acetate by Catechol: A Small Angle Scattering Study
Schindler, T. and Lin, W. and Schmutzler, T. and Lindner, P. and Peukert, W. and Segets, D. and Unruh, T.
ChemNanoMat 5 116-123 (2019)The core-shell structure of colloids surrounded by ligands is of great importance for their later application as it can significantly alter the chemical and physical properties of the nanoparticles (NPs). A combination of small angle X-ray and neutron scattering (SAXS/SANS) in the native solution with additional ex situ measurements (titration-UV) was applied to study the NP/ligand interface of ZnO NPs after functionalization with catechol derivatives. Based on SAXS data, it was found that within the multimodal particle size distribution the fraction of agglomerates is shifted to smaller sizes and nearly disappeared upon the binding of ethyl 3,4-dihydroxybenzoate (CAT) molecules. This is ascribed to improved stabilization at the primary particle level by CAT molecules. By combining the neutron scattering contrast with the input of bound CAT molecules from a previously developed titration-UV method, the heterogeneous composition of the ligand shell became accessible for the first time. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/cnma.201800465 2019 • 686 Excellent Oxygen Reduction Reaction Performance in Self-Assembled Amyloid-β/Platinum Nanoparticle Hybrids with Effective Platinum-Nitrogen Bond Formation
Jindal, A. and Tashiro, K. and Kotani, H. and Takei, T. and Reichenberger, S. and Marzun, G. and Barcikowski, S. and Kojima, T. and Yamamoto, Y.
ACS Applied Energy Materials 2 6536-6541 (2019)The development of highly efficient catalysts for electrochemical oxygen reduction reactions (ORRs) is crucial for energy applications such as metal-air batteries and fuel cells. Here, we show an enhanced electrocatalytic activity of a new functional material composed of Pt nanoparticles (PtNPs) and self-assembled β-sheet peptides (βPs). The PtNP/βP hybrids, under an optimized assembly condition, display an ORR electrocatalytic activity that is higher than that of a commercially available benchmark Pt/C electrocatalyst in terms of the onset potential and reaction kinetics. Moreover, the PtNP/βP hybrids show one order of magnitude higher ORR mass activity than previously reported peptide-based ORR electrocatalysts. The superb ORR activity with high durability is derived from the well-dispersed PtNPs on βPs, where 50% of the amine groups on the side chain bound with Pt to form Pt-N bonds that function as active sites for the catalytic reaction. This work opens new avenues for efficient ORR electrocatalysts using self-assembled peptides. Copyright © 2019 American Chemical Society.view abstract doi: 10.1021/acsaem.9b01103 2019 • 685 First PEM fuel cell based on ligand-free, laser-generated platinum nanoparticles
Kohsakowski, S. and Streubel, R. and Radev, I. and Peinecke, V. and Barcikowski, S. and Marzun, G. and Reichenberger, S.
Applied Surface Science 467-468 486-492 (2019)For the first time, surfactant-free platinum nanoparticles (Pt-NPs) prepared by pulsed laser ablation in liquids were employed in a real proton exchange membrane fuel cell (PEMFC). Laser-generated Pt-NPs show a larger size in comparison to a commercial Pt/C catalyst, being 6.6 nm for the laser-based and 3.8 nm for the reference, respectively. The laser-based Pt/C electrocatalyst was synthesized by colloidal deposition of laser-generated Pt-NPs onto carbonic Vulcan as support. The durability tests showed a much better stability of the laser-based catalyst in the electrochemical active surface area (ECSA) with an ECSA retention of 88% of its initial area. This better durability is probably caused by a reduced Pt dissolution rate which is higher for the reference catalyst containing NPs smaller than 3 nm. The occurrence of Pt dissolution is further indicated by X-ray photoelectron spectroscopy (XPS) of the electrodes after electrocatalytic testing showing no Pt signal in case of the reference catalyst. Performance tests of both PEMFC show a 20% higher mass-specific power density for the laser-based proton exchange membrane fuel cell. © 2018 Elsevier B.V.view abstract doi: 10.1016/j.apsusc.2018.10.145 2019 • 684 Functionalization of titania nanotubes with electrophoretically deposited silver and calcium phosphate nanoparticles: Structure, composition and antibacterial assay
Chernozem, R.V. and Surmeneva, M.A. and Krause, B. and Baumbach, T. and Ignatov, V.P. and Prymak, O. and Loza, K. and Epple, M. and Ennen-Roth, F. and Wittmar, A. and Ulbricht, M. and Chudinova, E.A. and Rijavec, T. and Lapanje, A...
Materials Science and Engineering C 97 420-430 (2019)Herein TiO2 nanotubes (NTs) were fabricated via electrochemical anodization and coated with silver and calcium phosphate (CaP) nanoparticles (NPs) by electrophoretic deposition. Scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) revealed that Ag and CaP NPs were successfully deposited onto the TiO2 NTs. Using X-ray diffraction, only anatase and Ti were observed after deposition of Ag and CaP NPs. However, X-ray photoelectron spectroscopy (XPS) analysis revealed that the binding energy (BE) of the Ag and CaP NP core levels corresponded to metallic Ag, hydroxyapatite and amorphous calcium phosphate, based on the knowledge that CaP NPs synthesized by precipitation have the nanocrystalline structure of hydroxyapatite. The application of Ag NPs allows for decreasing the water contact angle and thus increasing the surface free energy. It was concluded that the CaP NP surfaces are superhydrophilic. A significant antimicrobial effect was observed on the TiO2 NT surface after the application of Ag NPs and/or CaP NPs compared with that of the pure TiO2 NTs. Thus, fabrication of TiO2 NTs, Ag NPs and CaP NPs with PEI is promising for diverse biomedical applications, such as in constructing a biocompatible coating on the surface of Ti that includes an antimicrobial effect. © 2018 Elsevier B.V.view abstract doi: 10.1016/j.msec.2018.12.045 2019 • 683 Induction of herpes simplex virus type 1 cell-to-cell spread inhibiting antibodies by a calcium phosphate nanoparticle-based vaccine
Kopp, M. and Aufderhorst, U.W. and Alt, M. and Dittmer, U. and Eis-Hübinger, A.-M. and Giebel, B. and Roggendorf, M. and Epple, M. and Krawczyk, A.
Nanomedicine: Nanotechnology, Biology, and Medicine 16 138-148 (2019)Herpes simplex viruses 1 and 2 are among the most ubiquitous human infections and persist lifelong in their host. Upon primary infection or reactivation from ganglia, the viruses spread by direct cell–cell contacts (cell-to-cell spread) and thus escape from the host immune response. We have developed a monoclonal antibody (mAb 2c), which inhibits the HSV cell-to-cell spread, thereby protecting from lethal genital infection and blindness in animal models. In the present study we have designed a nanoparticle-based vaccine to induce protective antibody responses exceeding the cell-to-cell spread inhibiting properties of mAb 2c. We used biodegradable calcium phosphate (CaP) nanoparticles coated with a synthetic peptide that represents the conformational epitope on HSV-1 gB recognized by mAb 2c. The CaP nanoparticles additionally contained a TLR-ligand CpG m and were formulated with adjuvants to facilitate the humoral immune response. This vaccine effectively protected mice from lethal HSV-1 infection by inducing cell-to-cell spread inhibiting antibodies. © 2018 The Authorsview abstract doi: 10.1016/j.nano.2018.12.002 2019 • 682 Investigating temporal variation in the apparent volume fraction measured by time-resolved laser-induced incandescence
Sipkens, T.A. and Menser, J. and Mansmann, R. and Schulz, C. and Daun, K.J.
Applied Physics B: Lasers and Optics 125 (2019)In many time-resolved laser-induced incandescence (TiRe-LII) experiments, it is common practice to relate the intensity emitted by laser-heated nanoparticles to the detected LII signal through a factor (here called the intensity scaling factor, ISF) that includes the particle volume fraction and other parameters that may not be the focus of the analysis. While, in the absence of evaporation or sublimation, the ISF should theoretically remain constant with respect to time, recent multi-wavelength measurements show that, in reality, it may vary with both time and fluence. We consider four candidate effects that contribute to this behavior: particle annealing; polydispersity in the nanoparticle-size distribution; background luminosity due to emission from nanoparticles in the line-of-sight before and behind the probe volume; and the temporal resolution of the detector. We demonstrate these effects by simulating TiRe-LII data for in-flame soot at atmospheric pressure, using new simplified heat transfer and annealing models. Analysis of experimental signals collected from flame-generated soot at atmospheric pressure reveals trends in the ISF similar to those predicted by simulations. These temporal variations provide important insights that can help to diagnose problems in TiRe-LII experiments and improve TiRe-LII models. © 2019, Springer-Verlag GmbH Germany, part of Springer Nature.view abstract doi: 10.1007/s00340-019-7251-7 2019 • 681 Microwave plasma-assisted silicon nanoparticles: Cytotoxic, molecular, and numerical responses against cancer cells
Wahab, R. and Khan, F. and Gupta, A. and Wiggers, H. and Saquib, Q. and Faisal, M. and Ansari, S.M.
RSC Advances 9 13336-13347 (2019)Silicon nanoparticles (SiNPs), which have a special place in material science due to their strong luminescent property and wide applicability in various physicochemical arenas, such as solar cells and LEDs, were synthesised by a microwave plasma-assisted process using an argon-silane mixture. Several characterization tools were applied to check the crystallinity (XRD) and morphological (FESEM, TEM, ∼20 ± 2 nm size) and topographical (AFM, ∼20 nm) details of the NPs. The high-purity SiNPs were applied on myoblast cancer cells to investigate the reactivity of the NPs at different doses (200, 1000 and 2000 ng mL-1) for different incubation periods (24 h, 48 h & 72 h). The MTT assay was utilized to determine the percentage of viable and non-viable cells, while the cell organization was observed via microscopy and CLSM. Additionally, the molecular responses (RT-PCR), such as apoptosis, were analyzed in presence of caspase 3 and 7, and the results showed an upregulation with SiNPs. To validate the obtained data, analytical studies were also performed for the SiNPs via statistical analysis and the most reliable data values were evaluated and acceptable as per the ICH guidelines. © 2019 The Royal Society of Chemistry.view abstract doi: 10.1039/c8ra10185j 2019 • 680 Modular Pd/Zeolite Composites Demonstrating the Key Role of Support Hydrophobic/Hydrophilic Character in Methane Catalytic Combustion
Losch, P. and Huang, W. and Vozniuk, O. and Goodman, E.D. and Schmidt, W. and Cargnello, M.
ACS Catalysis 9 4742-4753 (2019)Complete catalytic oxidation of methane in the presence of steam at low temperatures (T < 400 °C) is a crucial reaction for emission control, yet it presents profound challenges. The activation of the strong C-H bond of methane at low temperature is difficult, and the water present in any realistic application poisons the active surface and promotes sintering of Pd particles during the reaction. Finding materials that can deliver high reaction rates while being more resistant to the presence of water is imperative for advancing several technological applications of natural gas-based systems. However, methods to fairly compare the activity of Pd catalysts (the most active metal for methane combustion) are needed in order to perform useful structure-property relationship studies. Here, we report a method to study how zeolite hydrophobicity affects the activity of Pd nanoparticles in the reaction, which led to a significant improvement in the water resistance. Mesoporous zeolites were synthesized starting from commercially available microporous zeolites. In this way, a variety of hierarchically porous zeolites, with different hydrophobic/hydrophilic character, were prepared. Preformed colloidal Pd nanoparticles could be deposited within mesostructured zeolites. This approach enabled the systematic study of key parameters such as zeolite framework, Al content, and the Pd loading while maintaining the same Pd particle size and structure for all the samples. Detailed catalytic studies revealed an optimum hydrophobic/hydrophilic character, and a promising steam-resistant catalyst, namely, 3.2 nm Pd particles supported on mesoporous zeolite beta or USY with a Si/Al ratio of 40, emerged from this multiparametric study with a T50 of 355 °C and T90 of 375 °C (where T50 and T90 are temperature values at which the samples reach 50% and 90% methane conversion, respectively) in steam-containing reaction conditions. Finally, we verified that the designed catalysts were stable by in-depth postcatalysis characterization and operando diffuse-reflectance infrared Fourier-transform spectroscopy (DRIFTS) analyses confirming that water adsorbs less strongly on the active PdO surface due to interaction with the zeolite acid sites. This method can be of general use to study how zeolite supports affect the reactivity of supported metals in several catalytic applications. © 2019 American Chemical Society.view abstract doi: 10.1021/acscatal.9b00596 2019 • 679 Nanoscale Physical and Chemical Structure of Iron Oxide Nanoparticles for Magnetic Particle Imaging
Hufschmid, R. and Landers, J. and Shasha, C. and Salamon, S. and Wende, H. and Krishnan, K.M.
Physica Status Solidi (A) Applications and Materials Science 216 (2019)In this work, the role of the nanoscale chemical and magnetic structure on relaxation dynamics of iron oxide nanoparticles in the context of magnetic particle imaging (MPI) is investigated with Mössbauer spectroscopy (MS) and electron energy loss spectroscopy (EELS). Two samples of 27 nm monodisperse iron oxide nanoparticles are compared, with and without an additional oxidation optimization step, with corresponding differences in structure and properties. Iron oxide nanoparticles synthesized in the presence of sufficient oxygen form single crystalline, inverse-spinel magnetite (Fe 3 O 4 ) and display magnetic properties suitable for MPI. A secondary wüstite (FeO) phase is observed in the diffraction pattern of unoptimized nanoparticles, which is antiferromagnetic and therefore unsuitable for MPI. Mössbauer spectra confirm the composition of the optimized nanoparticles to be ≈70% magnetite, with the remaining 30% oxidized to maghemite; in contrast, the as-synthesized particles (without the oxidation step) contained about 40% wüstite and 60% magnetite. The authors use scanning transmission electron microscopy (STEM) with electron energy loss spectroscopy (EELS) to probe iron 2p-3d electronic transitions and correlate their intensities with the oxidation state with sub-nanometer spatial resolution. The optimally oxidized nanoparticles are uniform in crystallography and phase, while the mixed phase nanoparticles are core-shell wüstite/magnetite. Further confirming the core-shell structure of the mixed phase nanoparticles, considerable spin canting in the in-field Mössbauer spectrum, likely caused by interface coupling, is observed. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/pssa.201800544 2019 • 678 Nanosized Lithium-Rich Cobalt Oxide Particles and Their Transformation to Lithium Cobalt Oxide Cathodes with Optimized High-Rate Morphology
Zehetmaier, P.M. and Cornélis, A. and Zoller, F. and Böller, B. and Wisnet, A. and Döblinger, M. and Böhm, D. and Bein, T. and Fattakhova-Rohlfing, D.
Chemistry of Materials (2019)We report the formation of crystalline dispersible LixCo1-xOy (with y 1) nanoparticles with an unusual rock-salt phase containing â¼15 at. % Li in the crystalline structure. This is the first time that this composition was formed at temperatures as low as 150 °C under conditions of a solvothermal process, although it is referred to as a higherature metastable phase in a very limited number of known publications. The Li0.15Co0.85Oy nanoparticles of 2-3 nm size completely transform to higherature LiCoO2 (HT-LCO) nanoparticles at 560 °C in the presence of slightly overstoichiometric amounts of Li source. The presence of lithium in the CoO lattice slows down the kinetics of its phase transformation, enabling to obtain very small HT-LCO nanocrystals during the subsequent calcination. The HT-LCO particles formed after this transformation have an elongated shape with a mean size of about 17 × 60 nm, which is targeted as an optimum size for battery applications. An attractive feature of the Li0.15Co0.85Oy nanoparticles is their high dispersibility enabling their assembly into different nanostructures with optimized morphology. Open porous HT-LCO electrodes prepared via self-assembly of Li0.15Co0.85Oy nanoparticles and Pluronic F127 as a structure-directing agent demonstrate very good performances at high current densities representing short charge/discharge times below 10 min. Even at a charge/discharge time of 72 s (50C), 50% of the theoretical capacity has been preserved. After 250 cycles at a charge/discharge time of 6 min (10C), over 60% of the initial discharge capacity was retained. © 2019 American Chemical Society.view abstract doi: 10.1021/acs.chemmater.9b02231 2019 • 677 Nitrogen-Doped Mesostructured Carbon-Supported Metallic Cobalt Nanoparticles for Oxygen Evolution Reaction
Bähr, A. and Moon, G.-H. and Tüysüz, H.
ACS Applied Energy Materials 2 6672-6680 (2019)A series of metallic cobalt nanoparticles supported on mesostructured nitrogen-doped carbons was successfully synthesized through soft-templating by using poly(ethylene oxide)-b-polystyrene (PEO-b-PS) as a structure directing agent. The formation of metallic cobalt nanoparticles and nitrogen-doping into carbon structures were simultaneously achieved by ammonia treatment. The physicochemical properties of the resulting materials and consequently their performance for the oxygen evolution were systematically altered by varying the cobalt loading (5-89 wt %), pyrolysis atmosphere (argon or ammonia), and temperature (600-800 °C). Thereby, up to 37 wt % of the cobalt nanoparticles were confined in the pores of the mesostructured nitrogen-doped carbon materials with a high BET surface area. At temperatures above 700 °C, the cobalt additionally catalyzes the graphitization of the carbon support. The catalyst with a cobalt loading of 37 wt % pyrolyzed at 700 °C under an ammonia atmosphere shows the highest turnover frequency (TOF) of 311 h-1 in the oxygen evolution reaction due to the improved electronic properties of the carbon support from the incorporation of nitrogen atoms combined with a large amount of accessible cobalt sites. This class of materials shows even higher activity in comparison with ordered mesoporous Co3O4. © 2019 American Chemical Society.view abstract doi: 10.1021/acsaem.9b01183 2019 • 676 Optimizing the synthesis of Co/Co–Fe nanoparticles/N-doped carbon composite materials as bifunctional oxygen electrocatalysts
Medina, D. and Barwe, S. and Masa, J. and Seisel, S. and Schuhmann, W. and Andronescu, C.
Electrochimica Acta 318 281-289 (2019)A future widespread application of electrochemical energy conversion and storage technologies strongly depends on the substitution of precious metal-based electrocatalysts for the high-overpotential oxygen reduction and oxygen evolution reactions. We report a novel Co/Co–Fe nanoparticles/N-doped carbon composite electrocatalyst (Co/CoxFey/NC) obtained by pyrolysis of CoFe layered double hydroxide (CoFe LDH) embedded in a film of a bisphenol A and tetraethylenepentamine-based polybenzoxazine poly(BA-tepa). During pyrolysis poly(BA-tepa) forms a highly conductive nitrogen-doped carbon matrix encapsulating Co/Co–Fe nanoparticles, thereby circumventing the need of any additional binder material and conductive additives. Optimization with respect to pyrolysis temperature, the CoFe LDH/BA-tepa ratio, as well as of the gas atmosphere used during the thermal treatment was performed. The optimized Co/CoxFey/NC composite material catalyst exhibits remarkable bifunctional activity towards oxygen reduction (ORR) and oxygen evolution (OER) reactions in 0.1 M KOH represented by a potential difference of only 0.77 V between the potentials at which current densities of −1 mA cm−2 for the ORR and 10 mA cm−2 for the OER were recorded. Moreover, the Co/CoxFey/NC composite material pyrolyzed in ammonia atmosphere exhibits promising stability during both the ORR and the OER. © 2019 Elsevier Ltdview abstract doi: 10.1016/j.electacta.2019.06.048 2019 • 675 Perspective of Surfactant-Free Colloidal Nanoparticles in Heterogeneous Catalysis
Reichenberger, S. and Marzun, G. and Muhler, M. and Barcikowski, S.
ChemCatChem 11 4489-4518 (2019)Due to material gaps and synthesis-related cross-correlations in heterogeneous catalysis, chemists and physicists are constantly motivated to develop novel catalyst preparation methods for independent control of morphology, size, and composition. Within this article, advances, opportunities, and the current limits of laser-based catalyst preparation technique, as well as synergies with conventional methods will be reviewed in terms of purity, particle size, morphology, composition, and nanoparticle-support interaction. It will be shown, that the surfactant-free particles represent ideal model materials to validate kinetic models and conduct parametric activity studies by independent adjustment of functional properties like nanoparticle size, composition, and load. Consequently, the importance of transient plasma dynamics tailoring nanoparticle formation will be pointed out, comparing experimental studies with own calculations and novel simulations taken from literature. Finally, perspectives of surfactant-free colloidal nanoparticles for unrevealing active sites in heterogeneous catalysts are presented. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/cctc.201900666 2019 • 674 Piece by Piece—Electrochemical Synthesis of Individual Nanoparticles and their Performance in ORR Electrocatalysis
Evers, M.V. and Bernal, M. and Roldan Cuenya, B. and Tschulik, K.
Angewandte Chemie - International Edition 58 8221-8225 (2019)The impact of individual HAuCl4 nanoreactors is measured electrochemically, which provides operando insights and precise control over the modification of electrodes with functional nanoparticles of well-defined size. Uniformly sized micelles are loaded with a dissolved metal salt. These solution-phase precursor entities are then reduced electrochemically—one by one—to form nanoparticles (NPs). The charge transferred during the reduction of each micelle is measured individually and allows operando sizing of each of the formed nanoparticles. Thus, particles of known number and sizes can be deposited homogenously even on nonplanar electrodes. This is demonstrated for the decoration of cylindrical carbon fibre electrodes with 25±7 nm sized Au particles from HAuCl4-filled micelles. These Au NP-decorated electrodes show great catalyst performance for ORR (oxygen reduction reaction) already at low catalyst loadings. Hence, collisions of individual precursor-filled nanocontainers are presented as a new route to nanoparticle-modified electrodes with high catalyst utilization. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/anie.201813993 2019 • 673 Platinum nanoparticles supported on reduced graphene oxide prepared in situ by a continuous one-step laser process
Haxhiaj, I. and Tigges, S. and Firla, D. and Zhang, X. and Hagemann, U. and Kondo, T. and Nakamura, J. and Marzun, G. and Barcikowski, S.
Applied Surface Science 469 811-820 (2019)A large research emphasis is still placed on improvement of production routes of nanosized materials with enhanced catalytic properties. Here we developed a continuous process for generation of platinum (Pt) nanoparticles supported on reduced graphene oxide (rGO) in situ via pulsed laser ablation in liquid (PLAL) dispersion of rGO. This in situ PLAL technique is a single step procedure that allows the synthesis of heterogeneous catalysts with a simultaneous control of particle size and mass loading. By this method, Pt particles with mean particle diameters around 2.5 nm and in a regime of 3–4 nm have been produced in ethanol and saline water, respectively, and adsorbed on rGO with up to 50 wt%. Both inorganic and organic solvents used during in situ synthesis lead to production of CO tolerant Pt/rGO catalysts, which are relevant for fuel cell applications due to the remarkably low CO desorption temperatures around 65–80 °C. © 2018 Elsevier B.V.view abstract doi: 10.1016/j.apsusc.2018.10.257 2019 • 672 Review on experimental and theoretical investigations of the early stage, femtoseconds to microseconds processes during laser ablation in liquid-phase for the synthesis of colloidal nanoparticles
Kanitz, A. and Kalus, M.-R. and Gurevich, E.L. and Ostendorf, A. and Barcikowski, S. and Amans, D.
Plasma Sources Science and Technology 28 (2019)Laser ablation in liquid-phase (LAL) has been developed since the 1990s, but the interest in laser synthesis of colloids has emerged in the last decade due to a significant improvement in the production rate, proven comparative advantages in biomedical and catalysis applications, and recent commercialization. However, the method relies on highly transient phenomena, so that the fundamental understanding lacks behind the LAL synthesis refinement research. The complexity of the physics and chemistry involved has led to experimental and theoretical investigations that attempt to provide a basic description of the underlying processes but face the challenge of temporal and spatial resolution as well as non-equilibrium conditions. It appears that the processes occurring at the early time scales, ranging from femtoseconds to several microseconds are critical in the definition of the final product. The review is mainly dedicated to the comprehensive description of the processes occurring at early time scales, which include the description of laser-matter interaction for ultrashort and short laser pulses, plasma formation processes as well as comparison of the measured plasma parameters at these time scales, and subsequent description of the cavitation bubble dynamics. Furthermore, the plasma and cavitation bubble chemistry are addressed, and their impact on the nanoparticle formation is emphasized. © 2019 IOP Publishing Ltd.view abstract doi: 10.1088/1361-6595/ab3dbe 2019 • 671 Scalable classification of nanoparticles: A proof of principle for process design
Menter, C. and Segets, D.
Advanced Powder Technology 30 2801-2811 (2019)Nanoparticles like quantum confined ZnS semiconductor nanocrystals, exhibit unique structure-property relationships. Narrow particle size distributions (PSDs) become one of the most important factors to tailor product performance. Size selective precipitation has already been proven to be an effective post processing strategy for ZnS nanoparticles. It is based on the titration of a poor liquid into a stable dispersion, which leads to the preferred flocculation of larger particles. Afterwards, these flocks must be separated from the continuous phase. While on lab scale the formed flocks can be easily separated by centrifugation from the fine fraction, for larger scale production using continuous processes, new concepts are urgently needed. Herein we developed a filtration process for flock removal that allows the handling of larger quantities. For process design, we first investigated the flock properties in order to know how stable the generated flocks are and how the flock properties can be controlled. Then, we replaced the classical flock separation by centrifugation through separation by surface filtration under the constraint that the underlying separation efficiency was not affected. By the future use of properly controlled, alternating filtration modules, our work opens the door for establishing an urgently needed, scalable post-processing for sub-10 nm nanoparticles. © 2019 Society of Powder Technology Japanview abstract doi: 10.1016/j.apt.2019.08.027 2019 • 670 Scanning Electrochemical Cell Microscopy Investigation of Single ZIF-Derived Nanocomposite Particles as Electrocatalysts for Oxygen Evolution in Alkaline Media
Tarnev, T. and Aiyappa, H.B. and Botz, A. and Erichsen, T. and Ernst, A. and Andronescu, C. and Schuhmann, W.
Angewandte Chemie - International Edition 58 14265-14269 (2019)“Single entity” measurements are central for an improved understanding of the function of nanoparticle-based electrocatalysts without interference arising from mass transfer limitations and local changes of educt concentration or the pH value. We report a scanning electrochemical cell microscopy (SECCM) investigation of zeolitic imidazolate framework (ZIF-67)-derived Co−N-doped C composite particles with respect to the oxygen evolution reaction (OER). Surmounting the surface wetting issues as well as the potential drift through the use of a non-interfering Os complex as free-diffusing internal redox potential standard, SECCM could be successfully applied in alkaline media. SECCM mapping reveals activity differences relative to the number of particles in the wetted area of the droplet landing zone. The turnover frequency (TOF) is 0.25 to 1.5 s−1 at potentials between 1.7 and 1.8 V vs. RHE, respectively, based on the number of Co atoms in each particle. Consistent values at locations with varying number of particles demonstrates OER performance devoid of macroscopic film effects. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.view abstract doi: 10.1002/anie.201908021 2019 • 669 Selective 2-Propanol Oxidation over Unsupported Co3O4 Spinel Nanoparticles: Mechanistic Insights into Aerobic Oxidation of Alcohols
Anke, S. and Bendt, G. and Sinev, I. and Hajiyani, H. and Antoni, H. and Zegkinoglou, I. and Jeon, H. and Pentcheva, R. and Roldan Cuenya, B. and Schulz, S. and Muhler, M.
ACS Catalysis 9 5974-5985 (2019)Crystalline Co3O4 nanoparticles with a uniform size of 9 nm as shown by X-ray diffraction (XRD) and transmission electron microscopy (TEM) were synthesized by thermal decomposition of cobalt acetylacetonate in oleylamine and applied in the oxidation of 2-propanol after calcination. The catalytic properties were derived under continuous flow conditions as a function of temperature up to 573 K in a fixed-bed reactor at atmospheric pressure. Temperature-programmed oxidation, desorption (TPD), surface reaction (TPSR), and 2-propanol decomposition experiments were performed to study the interaction of 2-propanol and O2 with the exposed spinel surfaces. Co3O4 selectively catalyzes the oxidative dehydrogenation of 2-propanol, yielding acetone and H2O and only to a minor extent the total oxidation to CO2 and H2O at higher temperatures. The high catalytic activity of Co3O4 reaching nearly full conversion with 100% selectivity to acetone at 430 K is attributed to the high amount of active Co3+ species at the catalyst surface as well as surface-bound reactive oxygen species observed in the O2 TPD, 2-propanol TPD, TPSR, and 2-propanol decomposition experiments. Density functional theory calculations with a Hubbard U term support the identification of the 5-fold-coordinated octahedral surface Co5c3+ as the active site, and oxidative dehydrogenation involving adsorbed atomic oxygen was found to be the energetically most favored pathway. The consumption of surface oxygen and reduction of Co3+ to Co2+ during 2-propanol oxidation derived from X-ray absorption spectroscopy and X-ray photoelectron spectroscopy measurements before and after reaction and poisoning by strongly bound carbonaceous species result in the loss of the low-temperature activity, while the high-temperature reaction pathway remained unaffected. © 2019 American Chemical Society.view abstract doi: 10.1021/acscatal.9b01048 2019 • 668 Size-Selective Optical Printing of Silicon Nanoparticles through Their Dipolar Magnetic Resonance
Zaza, C. and Violi, I.L. and Gargiulo, J. and Chiarelli, G. and Schumacher, L. and Jakobi, J. and Olmos-Trigo, J. and Cortes, E. and König, M. and Barcikowski, S. and Schlücker, S. and Sáenz, J.J. and Maier, S.A. and Stefani, F.D.
ACS Photonics 6 815-822 (2019)Silicon nanoparticles possess unique size-dependent optical properties due to their strong electric and magnetic resonances in the visible range. However, their widespread application has been limited, in comparison with other (e.g., metallic) nanoparticles, because their preparation on monodisperse colloids remains challenging. Exploiting the unique properties of Si nanoparticles in nano- and microdevices calls for methods able to sort and organize them from a colloidal suspension onto specific positions of solid substrates with nanometric precision. We demonstrate that surfactant-free silicon nanoparticles of a predefined and narrow (σ < 10 nm) size range can be selectively immobilized on a substrate by optical printing from a polydisperse colloidal suspension. The size selectivity is based on differential optical forces that can be applied on nanoparticles of different sizes by tuning the light wavelength to the size-dependent magnetic dipolar resonance of the nanoparticles. © 2019 American Chemical Society.view abstract doi: 10.1021/acsphotonics.8b01619 2019 • 667 Smart Polymeric Membranes with Magnetic Nanoparticles for Switchable Separation
Ulbricht, M.
RSC Smart Materials 2019-January 297-328 (2019)This chapter provides an overview on the topic of magneto-responsive membranes for switchable mass separation. The combination of concepts, materials and methods in the field of filtration membranes with the application of magnetic materials and magnetic fields is described. Combining organic polymer-based membranes with inorganic magnetic nanoparticles is the most efficient approach to obtain "smart" membranes that can show large and reversible changes in barrier and surface properties upon activation with static or alternating magnetic fields of different frequencies. Two general approaches can be distinguished: (i) addressing secondary interactions during membrane separation such as concentration polarization or fouling, or (ii) focussing on intrinsic membrane barrier properties. Until now, the most progress toward switchable separations has been achieved by membranes that change effective pore size in the micro- or ultrafiltration range, either via reversible deformations induced by static or low frequency magnetic fields or via the synergistic combination of magneto-heating by stimulation with high frequency alternating magnetic fields and thermo-responsive hydrogels as building blocks for mixed matrix composite membranes. This pioneering work will trigger much more research and development toward real applications, e.g., in bioseparations and/or for bioanalytical or biomedical applications, wherever the option of remote-controlled switching of separation selectivity is of interest. © The Royal Society of Chemistry 2019.view abstract doi: 10.1039/9781788016377-00297 2019 • 666 Structures of carbonaceous nanoparticles formed in various pyrolysis systems
Jander, H. and Borchers, C. and Böhm, H. and Emelianov, A. and Schulz, C.
Carbon 150 244-258 (2019)In the pyrolysis of different hydrocarbon/carbon suboxid fuels formation of carbon particles with the special view to their structures was examined. For this, the following three very different pyrolysis systems were investigated experimentally i)a pyrolysis reactor, ii)a shock tube and iii)a plasma reactor with respect to the influence of varying reaction parameters on the carbonaceous nanoparticles. The particles formed in these reaction systems were studied in view of their morphology and state of crystallization by use of electron microscopy (Philips CM30)at low- and high resolution combined with micro-diffraction measurements. As to be seen at low resolution of the transmission electron microscopy studies, the particle sizes in the pyrolysis reactor and shock tube do not differ significantly, but distinguished considerably from those particle sizes obtained in the plasma reactor. While the particles obtained in the pyrolysis reactor and shock-tube had particle diameters of about d≈ 30 nm, the particles in the plasma reactor consisted of fluffy-like units, and their sizes were about d≈ 4 nm. The various carbon layers consisted of different polyaromatic hydrocarbon units with variable sizes arranged to diverse states in the course of graphitization. © 2019 Elsevier Ltdview abstract doi: 10.1016/j.carbon.2019.02.034 2019 • 665 Synergism between Specific Halide Anions and pH Effects during Nanosecond Laser Fragmentation of Ligand-Free Gold Nanoparticles
Ziefuß, A.R. and Barcikowski, S. and Rehbock, C.
Langmuir (2019)Gold nanoclusters (AuNCs) with diameters smaller than 3 nm are an emerging field of research because they possess interesting optical properties, such as photoluminescence. However, to date, it is still difficult to distinguish whether these properties originate from the cores of the nanoparticles or from the adsorbates on their surfaces. Hence, there is a high demand for ligand-free, ultra-small particles because they make it possible to study ligand and core effects separately. Pulsed laser fragmentation in liquids (LFL) is a convenient route for the synthesis of ligand-free AuNCs. The influence of physical parameters, such as melting and evaporation, on the LFL process is well understood both theoretically and experimentally. However, the impact of the chemical composition of the medium during LFL, which critically affects the particle formation process, has been less well examined. Therefore, in this work, we elucidate the extent to which the ionic strength, the pH value, and the nature of the halide anion that is present, that is, F-, Cl-, Br-, or I-, influence the particle size distribution of the LFL product and the mean yield of small particles (<3 nm) of the product. We showed that the yield of small particles can be enhanced by the synergism between pH and specific ion effects, which probably is attributable to the adsorption of specific anions. In addition, our findings indicated that anion-based stabilization depends critically on the type of anion. A direct Hofmeister effect was observed for anions in the neutral pH regime, whereas an indirect Hofmeister series was reported in alkaline solution, which probably was due to the more hydrophilic surfaces of the AuNCs that were formed. © 2019 American Chemical Society.view abstract doi: 10.1021/acs.langmuir.9b00418 2019 • 664 Synthesis of silicon nanoparticles in a pilot-plant-scale microwave plasma reactor: Impact of flow rates and precursor concentration on the nanoparticle size and aggregation
Kunze, F. and Kuns, S. and Spree, M. and Hülser, T. and Schulz, C. and Wiggers, H. and Schnurre, S.M.
Powder Technology 342 880-886 (2019)This work is devoted to scale-up the microwave plasma synthesis of silicon nanoparticles from gaseous precursor monosilane (SiH4), previously investigated in lab-scale processes, to the pilot-plant-scale with production rates up to 200 g/h. The aim is to ensure reproducible, long-term operation of the reactor through gas-dynamic stabilization of the reacting flow and to control particle size and morphology via the gas flow velocity and the precursor concentration. Based on a newly designed nozzle, the lab-scale approach of stabilizing the plasma flow via a tangential sheath gas flow and an axial precursor gas flow was successfully transferred to the pilot-plant scale. At precursor concentrations up to 16 vol% of SiH4 diluted in argon and hydrogen, the as-synthesized particles have similar characteristics compared to those from lab-scale reactors. They are spherical, crystalline, mostly soft-agglomerated, and show a log-normal size distribution with a geometric standard deviation around 1.45 as expected for self-preserving aerosol size-distributions. In contrast to lab-scale experiments, an increase in SiH4 concentration up to 48 vol% does not lead to further growth of isolated primary particles but promotes aggregate formation from smaller primary particles. This is attributed to massive initial nucleation of very small particles due to strong supersaturation and their subsequent strong aggregation while suppressing complete coalescence due to the limited residence time at high temperature. © 2018 Elsevier B.V.view abstract doi: 10.1016/j.powtec.2018.10.042 2019 • 663 Tailoring the Surface Structure of Silicon Carbide Support for Copper Catalyzed Ethanol Dehydrogenation
Li, M.-Y. and Lu, W.-D. and He, L. and Schüth, F. and Lu, A.-H.
ChemCatChem 11 481-487 (2019)The production of acetaldehyde through biomass-derived ethanol dehydrogenation is a sustainable alternative compared to the fossil-feedstock based process, for which Cu-based catalysts are considered to be the most efficient. Herein, we modified the surface of silicon carbide (SiC) to alter the properties of the interface from SiO2-rich to C-rich, and we prepared a series of Cu-supported catalysts (Cu/SiC, Cu/SiO2/SiC, and Cu/C/SiC) with the aim of insight into the effect of the interface structure and composition on catalytic dehydrogenation of ethanol. At 280 °C, the Cu/SiO2/SiC catalyst exhibits high ethanol conversion due to the excellent dispersion of Cu nanoparticles promoted by SiO2-rich interface. In contrast, Cu nanoparticles dispersed on C/SiC shows somewhat lower activity but excellent acetaldehyde selectivity with trace amounts of by-products under identical reaction conditions. This difference is attributed to the fast removal of acetaldehyde because of its low affinity for the relatively inert C-rich interface (C/SiC). This work provides an in-depth understanding of Cu−Si−C multi-interfacial structure and the ethanol dehydrogenation behavior, which may shed light on the design of novel catalysts with tailored interfacial structures. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/cctc.201801742 2019 • 662 Template-Free Synthesis and Selective Filling of Janus Nanocups
Qiang, X. and Steinhaus, A. and Chen, C. and Chakroun, R. and Gröschel, A.H.
Angewandte Chemie - International Edition 58 7122-7126 (2019)We report on the formation of shape- and surface-anisotropic Janus nanocups (JNCs) by evaporation-induced confinement assembly (EICA) of ABC triblock terpolymers. During microphase separation in spherical confinement, the triblock terpolymer spontaneously adopted a hemispherical shape with an inner concentric lamella–lamella (ll) morphology. Cross-linking and disassembly of the microparticles resulted in well-defined JNCs with different chemistry on the inside and outside. By synthesizing polymers with increasing length of the cross-linkable block, we tuned the mechanical stability of the nanocups, which is relevant to control opening and closing of the cup cavity. We utilize the Janus properties for selective uptake of cargo exemplified by the filling of JNCs with polymer or gold nanoparticles. The directional properties of JNCs suggest applications in locomotion, oil-spill recovery, storage and release, templating, and as nanoreactors with attoliter volume. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/anie.201814014 2019 • 661 Templated Dealloying: Designing Ultrastructures by Memory Effect
Kamp, M. and Tymoczko, A. and Schürmann, U. and Jakobi, J. and Rehbock, C. and Barcikowski, S. and Kienle, L.
Crystal Growth and Design 19 4957-4963 (2019)Tailoring the morphology of nanoporous structures widens the scope of applications in catalysis and sensing. The synthesis of versatile nanoporous morphologies with the spatial distribution of porosity is permitted by the dealloying of unique, metastable Au-Fe alloy template nanoparticles generated by laser ablation in liquids. This approach opens the door to a novel process, which involves a special transformation mechanism, including oxidation and Kirkendall effect, which is decisive for the stabilization of hollow structures with the spatial distribution of porosity and represents a memory effect of morphology. Within this work, nanoporous Au particles, hollow nanoporous Au shells with the spatial distribution of porosity, and yolk-shell-like Au nanoparticles encapsulated in ultrathin Au shells are synthesized. A distinct variation of crystallinity and an increased lattice strain is observed, which implies an improved catalytic activity for oxidation reactions. © 2019 American Chemical Society.view abstract doi: 10.1021/acs.cgd.9b00175 2019 • 660 Time and Mechanism of Nanoparticle Functionalization by Macromolecular Ligands during Pulsed Laser Ablation in Liquids
Letzel, A. and Reich, S. and Dos Santos Rolo, T. and Kanitz, A. and Hoppius, J. and Rack, A. and Olbinado, M.P. and Ostendorf, A. and Gökce, B. and Plech, A. and Barcikowski, S.
Langmuir 35 3038-3047 (2019)Laser ablation of gold in liquids with nanosecond laser pulses in aqueous solutions of inorganic electrolytes and macromolecular ligands for gold nanoparticle size quenching is probed inside the laser-induced cavitation bubble by in situ X-ray multicontrast imaging with a Hartmann mask (XHI). It is found that (i) the in situ size quenching power of sodium chloride (NaCl) in comparison to the ablation in pure water can be observed by the scattering contrast from XHI already inside the cavitation bubble, while (ii) for polyvinylpyrrolidone (PVP) as a macromolecular model ligand an in situ size quenching cannot be observed. Complementary ex situ characterization confirms the overall size quenching ability of both additive types NaCl and PVP. The macromolecular ligand as well as its monomer N-vinylpyrrolidone (NVP) are mainly effective for growth quenching of larger nanoparticles on later time scales, leading to the conclusion of an alternative interaction mechanism with ablated nanoparticles compared to the electrolyte NaCl, probably outside of the cavitation bubble, in the surrounding liquid phase. While monomer and polymer have similar effects on the particle properties, with the polymer being slightly more efficient, only the polymer is effective against hydrodynamic aggregation. © 2019 American Chemical Society.view abstract doi: 10.1021/acs.langmuir.8b01585 2019 • 659 Toward a Paradigm Shift in Electrocatalysis Using Complex Solid Solution Nanoparticles
Löffler, T. and Savan, A. and Garzón-Manjón, A. and Meischein, M. and Scheu, C. and Ludwig, Al. and Schuhmann, W.
ACS Energy Letters 4 1206-1214 (2019)Complex solid solution (CSS) nanoparticles were recently discovered as efficient electrocatalysts for a variety of reactions. As one of many advantages, they exhibit the potential to replace noble-metal catalysts with multinary combinations of transition metals because they offer formation of new unique and tailorable active sites of multiple elements located next to each other. This Perspective reports on the current state and on challenges of the (combinatorial) synthesis of multinary nanoparticles and advanced electron microscopy characterization techniques for revealing structure-activity correlations on an atomic scale. We discuss what distinguishes this material class from common catalysts to highlight their potential to act as electrocatalysts and rationalize their nontypical electrochemical behavior. We provide an overview about challenges in synthesis, characterization, and electrochemical evaluation and propose guidelines for future design of CSS catalysts to achieve further progress in this research field, which is still in its infancy. © 2019 American Chemical Society.view abstract doi: 10.1021/acsenergylett.9b00531 2019 • 658 Tuning the optical, structural and multiferroic properties of Bismuth Ferrite (BiFeO3) Nanoparticles by Doping with Ba
Dubey, A. and Castillo, M.E. and Shvartsman, V.V. and Lupascu, D.C. and Salamon, S. and Wende, H.
2019 IEEE International Symposium on Applications of Ferroelectrics, ISAF 2019 - Proceedings (2019)Bismuth Ferrite Nanoparticles (BiFeO3 NPs) are interesting single-phase multiferroic materials due to their notable magnetoelectric properties at room temperature. We enhance the magnetization of BFO NPs via doping 5 % Ba at the Bi site. These NPs were synthesized by a modified and reproducible sol-gel technique and further characterized by XRD (x-ray diffraction), VSM (Vibrating Sample Magnetometer), PFM (Piezoresponse Force Microscopy), DSC (Differential Scanning Calorimetry) and UV-Vis (Absorption spectroscopy) techniques. Rietveld refinement unveils a lattice distortion and shows that the average crystallite size is reduced from 43.7 to 38.4 nm after Ba incorporation. 5 % Ba enhances the ferromagnetism from 0.71 to 0.86 Am2/kg at 300 K. DSC curves confirm no significant variation in magnetic transition temperature (TN) after Ba doping. Moreover, PFM data show the ferroelectric behavior of 5 % Ba doped NPs with reduced piezoresponse. UV-Vis spectra show the presence of crystal field transition and a doubly degenerate d-d transition, whereas the band gap of 5 % Ba doped BFO NPs increases from 2.18 eV for BFO NPs to 2.23 eV. © 2019 IEEE.view abstract doi: 10.1109/ISAF43169.2019.9034963 2019 • 657 Vacancy doping and charge transport in B i2 S3 nanoparticle films for photovoltaic applications
Mock, J. and Klingebiel, B. and Schillings, D. and Nuys, M. and Flohre, J. and Wang, S. and Kirchartz, T. and Carius, R.
Physical Review Materials 3 (2019)Native point defect doping via thermal treatment is an easy and promising method to tune the electrical transport properties of semiconductors made for renewable-energy conversion. In this study, we investigate the vacancy doping of the lowly toxic semiconductor Bi2S3 using electrical conductivity as well as thermoelectric power measurements. We enhance the electrical conductivity of bismuth sulfide nanoparticle layers by more than four orders of magnitude by a stepwise thermal treatment in a moderate temperature range (300-480 K). Via thermoelectric power measurements we attribute this enhancement to an increase in charge-carrier mobility by two orders of magnitude and to an increase in charge-carrier density by more than two orders of magnitude. We find that the energetic position of the electron-doping sulfur vacancies of bismuth sulfide nanoparticles is significantly shallower than previously reported for bulk material. Subsequently, we implement Bi2S3 nanoparticles doped with sulfur vacancies by thermal annealing in photovoltaic devices using P3HT as an electron donor molecule. We find that annealing up to 383 K yields the best compromise between improving charge-carrier transport and increasing defect densities. ©2019 American Physical Society.view abstract doi: 10.1103/PhysRevMaterials.3.105406 2018 • 656 A new approach to coat PA12 powders with laser-generated nanoparticles for selective laser sintering
Hupfeld, T. and Laumer, T. and Stichel, T. and Schuffenhauer, T. and Heberle, J. and Schmidt, M. and Barcikowski, S. and Gökce, B.
Procedia CIRP 74 244-248 (2018)The modification of selective laser sintering (SLS) powder materials by nanoadditives offers the possibility to adapt the powder properties to the laser sintering process or the resulting part properties. To avoid agglomeration of the nanofiller, a new approach in which surfactant-free laser-generated colloidal nanoparticles are adsorbed onto the polymer surface directly in an aqueous solution is demonstrated. Based on this novel approach, polyamide 12 (PA12) powders are decorated with metal and oxide nanoparticles and processed via SLS. Electron microscopy and confocal laser scanning imaging are utilized to analyze the dispersion of the filler. © 2018 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license.view abstract doi: 10.1016/j.procir.2018.08.103 2018 • 655 Agglomeration-Free Preparation of Modified Silica Nanoparticles for Emulsion Polymerization - A Well Scalable Process
Hübner, C. and Fettkenhauer, C. and Voges, K. and Lupascu, D.C.
Langmuir 34 376-383 (2018)To prepare modified silica nanospheres for emulsion polymerization, a new agglomeration-free change of dispersion media has been developed. Nanosized silica spheres were synthesized by the Stöber method and directly modified with a silane coupling agent. To prepare these particles for subsequent polymerization, the dispersion medium was changed in a two-step process from ethanol to water without agglomeration of the particles. The emulsion polymerization leads to hemispherical single-core-structured silica-polystyrene composite particles. The thickness of the polymer shell can be altered by varying the amount of styrene. The developed change of dispersion media provides nonagglomerated modified silica particles for the encapsulation with polystyrene and enables the synthesis of narrowly distributed single-core composite particles. The developed process is a promising approach for the preparation of nanoparticles for subsequent polymerization and can be scaled-up for industrial applications. © 2017 American Chemical Society.view abstract doi: 10.1021/acs.langmuir.7b03753 2018 • 654 Bifunctional Oxygen Reduction/Oxygen Evolution Activity of Mixed Fe/Co Oxide Nanoparticles with Variable Fe/Co Ratios Supported on Multiwalled Carbon Nanotubes
Elumeeva, K. and Kazakova, M.A. and Morales, D.M. and Medina, D. and Selyutin, A. and Golubtsov, G. and Ivanov, Y. and Kuznetzov, V. and Chuvilin, A. and Antoni, H. and Muhler, M. and Schuhmann, W. and Masa, J.
ChemSusChem 11 1204-1214 (2018)A facile strategy is reported for the synthesis of Fe/Co mixed metal oxide nanoparticles supported on, and embedded inside, high purity oxidized multiwalled carbon nanotubes (MWCNTs) of narrow diameter distribution as effective bifunctional catalysts able to reversibly drive the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR) in alkaline solutions. Variation of the Fe/Co ratio resulted in a pronounced trend in the bifunctional ORR/OER activity. Controlled synthesis and in-depth characterization enabled the identification of an optimal Fe/Co composition, which afforded a low OER/OER reversible overvoltage of only 0.831 V, taking the OER at 10 mA cm−2 and the ORR at −1 mA cm−2. Importantly, the optimal catalyst with a Fe/Co ratio of 2:3 exhibited very promising long-term stability with no evident change in the potential for both the ORR and the OER after 400 charge/discharge (OER/ORR) cycles at 15 mA cm−2 in 6 m KOH. Moreover, detailed investigation of the structure, size, and phase composition of the mixed Fe/Co oxide nanoparticles, as well as their localization (inside of or on the surface of the MWCNTs) revealed insight of the possible contribution of the individual catalyst components and their synergistic interaction in the catalysis. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/cssc.201702381 2018 • 653 Cluster Assemblies Produced by Aggregation of Preformed Ag Clusters in Ionic Liquids
Roese, S. and Kononov, A. and Timoshenko, J. and Frenkel, A.I. and Hövel, H.
Langmuir 34 4811-4819 (2018)Room-temperature ionic liquids (RTILs) can be used as electrosterical stabilizers for nanoparticles without adding stabilizing agents. However, the nanoparticle stability and its mechanisms are still in discussion. We deposited preformed 2 nm ±0.6 nm silver clusters into the ionic liquid C4MIM PF6 using in situ UV/vis absorption to monitor the deposition process. The time- and temperature-dependent cluster aggregation process was studied with ex situ UV/vis absorption spectroscopy analyzed with electrodynamic calculations using generalized Mie theory. On an atomistic level, the sample structure was investigated using EXAFS and a neural network based analysis of XANES. The combination of all methods shows that an aggregation of the original 2 nm clusters without coalescence takes place, which can be controlled or stopped by choosing an appropriate sample temperature. This approach allows the controlled production of chainlike cluster aggregates in RTIL, promising for a number of applications. © 2018 American Chemical Society.view abstract doi: 10.1021/acs.langmuir.7b03984 2018 • 652 Comparative biological effects of spherical noble metal nanoparticles (Rh, Pd, Ag, Pt, Au) with 4-8 nm diameter
Rostek, A. and Breisch, M. and Pappert, K. and Loza, K. and Heggen, M. and Köller, M. and Sengstock, C. and Epple, M.
Beilstein Journal of Nanotechnology 9 2763-2774 (2018)For a comparative cytotoxicity study, nanoparticles of the noble metals Rh, Pd, Ag, Pt, and Au (spherical, average diameter 4 to 8 nm) were prepared by reduction in water and colloidally stabilized with poly(N-vinyl pyrrolidone) (PVP). Thus, their shape, size, and surface functionalization were all the same. Size and morphology of the nanoparticles were determined by dynamic light scattering (DLS), analytical disc centrifugation (differential centrifugal sedimentation, DCS), and high-resolution transmission electron microscopy (HRTEM). Cell-biological experiments were performed to determine the effect of particle exposure on the viability of human mesenchymal stem cells (hMSCs). Except for silver, no adverse effect of any of the metal nanoparticles was observed for concentrations up to 50 ppm (50 mg L-1) incubated for 24 h, indicating that noble metal nanoparticles (rhodium, palladium, platinum, gold) that do not release ions are not cytotoxic under these conditions. © 2018 Rostek et al.view abstract doi: 10.3762/bjnano.9.258 2018 • 651 Covalent Surface Functionalization of Calcium Phosphate Nanoparticles with Fluorescent Dyes by Copper-Catalysed and by Strain-Promoted Azide-Alkyne Click Chemistry
Rojas-Sánchez, L. and Sokolova, V. and Riebe, S. and Voskuhl, J. and Epple, M.
ChemNanoMat (2018)Spherical calcium phosphate nanoparticles with a solid core diameter around 90 nm (from scanning electron microscopy, SEM) were coated with a silica shell and then covalently functionalized by azide groups. To these azide groups, all kinds of alkyne-carrying molecules can be covalently attached by copper-catalysed azide-alkyne cycloaddition (CuAAC) and by strain-promoted azide-alkyne cycloaddition (SPAAC) at a very high density. This was demonstrated for a number of dyes (FAM, TAMRA, Cy5, Alexa Fluor™ 488, and an aromatic thioether with aggregation-induced emission (AIE) properties). It was also possible to attach more than one molecule to the surface of one particle by two-step click reaction, permitting the synthesis of multimodal nanoparticles that are stable under biological conditions. The nanoparticles have a hydrodynamic diameter of around 200 nm (from dynamic light scattering, DLS), which makes them suitable for uptake by cells. The strongly fluorescing nanoparticles were easily taken up by cells as demonstrated by fluorescence microscopy, confocal laser scanning microscopy (CLSM), and structured illuminated microscopy (SIM). © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/cnma.201800509 2018 • 650 Crystallographic characterization of laser-generated, polymer-stabilized 4 nm silver-gold alloyed nanoparticles
Prymak, O. and Jakobi, J. and Rehbock, C. and Epple, M. and Barcikowski, S.
Materials Chemistry and Physics 207 442-450 (2018)Monometallic silver and gold nanoparticles and bimetallic silver-gold (AgAu) nanoparticles were prepared by laser ablation in liquids in the atomic composition range of Ag:Au from 0:100 to 100:0 with steps of 10 at% and colloidally stabilized with poly(N-vinylpyrrolidone) (PVP). As metallic bulk targets for laser ablation, pure silver, pure gold, and alloyed AgAu foils with the desired composition were used. Size separation by centrifugation and freeze-drying gave monodisperse spherical nanoparticles with a diameter of 4 nm as determined by differential centrifugal sedimentation (DCS) and transmission electron microscopy (TEM). A crystallographic characterization of the nanoparticles was carried out by X-ray powder diffraction (XRD) and Rietveld refinement, leading to highly precise cubic lattice parameters (fcc crystal system) and crystallite sizes. For comparison, the same analysis including the determination of the microstrain was carried out for the bulk target materials (AgAu alloys in the full concentration range). Both nanoparticles and bulk target materials obeyed Vegard's rule, with only slight deviations. The fact that the crystallite size as determined by XRD was identical to the hydrodynamic diameter by DCS and the Feret diameter by TEM indicates that the particles consist of only one domain, i.e. they are single crystals. The combination of UV-vis spectroscopy with energy-dispersive X-ray spectroscopy (EDX) as line scan along the nanoparticle showed a homogenous distribution of the gold and silver inside the nanoparticles, indicating solid solution alloys, in contrast to what was observed earlier for chemically prepared AgAu nanoparticles by reduction of metal ions in water. © 2018 Elsevier B.V.view abstract doi: 10.1016/j.matchemphys.2017.12.080 2018 • 649 Cytotoxicity of doxorubicin-conjugated poly[N-(2-hydroxypropyl)methacrylamide]-modified ?-Fe2O3 nanoparticles towards human tumor cells
Plichta, Z. and Kozak, Y. and Panchuk, R. and Sokolova, V. and Epple, M. and Kobylinska, L. and Jendelová, P. and Horák, D.
Beilstein Journal of Nanotechnology 9 2533-2545 (2018)Doxorubicin-conjugated magnetic nanoparticles containing hydrolyzable hydrazone bonds were developed using a non-toxic poly[N-(2-hydroxypropyl)methacrylamide] (PHPMA) coating, which ensured good colloidal stability in aqueous media and limited internalization by the cells, however, enabled adhesion to the cell surface. While the neat PHPMA-coated particles proved to be non-toxic, doxorubicin-conjugated particles exhibited enhanced cytotoxicity in both drug-sensitive and drug-resistant tumor cells compared to free doxorubicin. The newly developed doxorubicin-conjugated PHPMA-coated magnetic particles seem to be a promising magnetically targeted vehicle for anticancer drug delivery. © 2018 Plichta et al.view abstract doi: 10.3762/bjnano.9.236 2018 • 648 Determination of Hansen parameters for particles: A standardized routine based on analytical centrifugation
Süß, S. and Sobisch, T. and Peukert, W. and Lerche, D. and Segets, D.
Advanced Powder Technology 29 1550-1561 (2018)The Hansen Solubility Parameters (HSP) are powerful descriptors to evaluate interactions of (polymer) molecules and their solubility in different liquids. Although approaches do exist to transfer the HSP-concept to the question of dispersibility of particles, HSP determination of slowly sedimenting (nano)particles (NPs) is time consuming and depends on the subjective evaluation of the experimenter. Herein, we introduce a new method for HSP determination for colloidal systems using analytical centrifugation (AC) which was applied to standardize and accelerate the experimental procedure. However, as not dissolution but dispersion is in focus, we propose to use the term Hansen Dispersibility Parameters (HDP) instead of HSP whenever dispersibility and stability of particles against agglomeration/flocculation are to be discussed. First, we implemented a standard dispersion routine for the well-known, industrially highly relevant pigment carbon black (CB). Then, a standardized method for the evaluation of measured AC profiles and appropriate ranking of NPs dispersibility in different media was developed. We demonstrate outstanding reproducibility of our results by comparing HDP derived for the same CB material from independent experiments performed at two different affiliations. Finally, we show the predictive power of HDP and the accuracy of our approach by evaluating the dispersibility of CB in additional liquids and mixtures of so-called “good” and “poor” liquid media crossing the border from stable to unstable medium conditions. Our study evidences the enormous potential of AC to determine the HDP of colloidal systems using a standardized and non-subjective method to access particle interactions and colloidal stability. © 2018 The Society of Powder Technology Japanview abstract doi: 10.1016/j.apt.2018.03.018 2018 • 647 Determination of pore size gradients of virus filtration membranes using gold nanoparticles and their relation to fouling with protein containing feed streams
Kosiol, P. and Müller, M.T. and Schneider, B. and Hansmann, B. and Thom, V. and Ulbricht, M.
Journal of Membrane Science 548 598-608 (2018)Virus filtration membranes contribute to the virus safety of biopharmaceutical drugs due to their capability to retain virus particles mainly based on size-exclusion mechanisms. Typical product molecules like monoclonal antibodies with 9–12 nm in hydrodynamic diameter have to be transmitted by >95% while small viruses, e.g. parvoviridae (B19, MVM, PPV) with a diameter of 18–26 nm, have to be retained by at least 99.99%. Therefore, membrane fouling caused by product aggregates, which are similar in size compared to the viruses that have to be retained, is a common observation. Minimal membrane fouling is a requirement for economical processes and is influenced by both the membrane surface chemistry and the membrane structure, particularly with regard to the pore size gradient (PSG). In this work, virus filtration membranes were challenged with gold nanoparticles (GNPs) in order to determine PSGs for a wide range of different commercial and non-commercial parvovirus retentive membranes differing in structure, material and surface chemistry. GNP adsorption to the membrane material was suppressed by the use of an anionic surfactant, allowing to gain insights into size-exclusion properties of the membranes. Membrane performance with regard to fouling was further investigated by determination of protein mass throughputs up-to a defined membrane flux decay using solutions containing intravenous immunoglobulin (IVIG) as model protein. Additionally, the fouling mechanism of IVIG was investigated and confirmed to be caused by trace amounts of species larger than IVIG monomers and dimers, which were already present in the feed. The fouling results are discussed in relationship to the determined PSGs, since the porous support structure of virus filtration membranes can act as a depth pre-filter protecting the separation-active layer from particulate foulants. © 2017 Elsevier B.V.view abstract doi: 10.1016/j.memsci.2017.11.048 2018 • 646 Development of a low-cost FPGA-based measurement system for real-time processing of acoustic emission data: Proof of concept using control of pulsed laser ablation in liquids
Wirtz, S.F. and Cunha, A.P.A. and Labusch, M. and Marzun, G. and Barcikowski, S. and Söffker, D.
Sensors (Switzerland) 18 (2018)Today, the demand for continuous monitoring of valuable or safety critical equipment is increasing in many industrial applications due to safety and economical requirements. Therefore, reliable in-situ measurement techniques are required for instance in Structural Health Monitoring (SHM) as well as process monitoring and control. Here, current challenges are related to the processing of sensor data with a high data rate and low latency. In particular, measurement and analyses of Acoustic Emission (AE) are widely used for passive, in-situ inspection. Advantages of AE are related to its sensitivity to different micro-mechanical mechanisms on the material level. However, online processing of AE waveforms is computationally demanding. The related equipment is typically bulky, expensive, and not well suited for permanent installation. The contribution of this paper is the development of a Field Programmable Gate Array (FPGA)-based measurement system using ZedBoard devlopment kit with Zynq-7000 system on chip for embedded implementation of suitable online processing algorithms. This platform comprises a dual-core Advanced Reduced Instruction Set Computer Machine (ARM) architecture running a Linux operating system and FPGA fabric. A FPGA-based hardware implementation of the discrete wavelet transform is realized to accelerate processing the AE measurements. Key features of the system are low cost, small form factor, and low energy consumption, which makes it suitable to serve as field-deployed measurement and control device. For verification of the functionality, a novel automatically realized adjustment of the working distance during pulsed laser ablation in liquids is established as an example. A sample rate of 5 MHz is achieved at 16 bit resolution. © 2018 by the authors. Licensee MDPI, Basel, Switzerland.view abstract doi: 10.3390/s18061775 2018 • 645 Effect of Antigen Retrieval Methods on Nonspecific Binding of Antibody-Metal Nanoparticle Conjugates on Formalin-Fixed Paraffin-Embedded Tissue
Zhang, Y. and Wang, X.-P. and Perner, S. and Bankfalvi, A. and Schlücker, S.
Analytical Chemistry 90 760-768 (2018)Immunohistochemical analysis of formalin-fixed paraffin-embedded (FFPE) tissues provides important diagnostic and prognostic information in pathology. Metal nanoparticles (NPs) and, in particular, surface-enhanced Raman scattering (SERS) nanotags as a new class of labeling reagents are promising to be used for multiplexed protein profiling on tissue sections. However, nonspecific binding of NPs onto the tissue specimens greatly hampers their clinical applications. In this study, we found that the antigen retrieval method strongly influences the extent of nonspecific binding of the antibody-SERS NP conjugates to the tissue. Our SERS labels comprised ca. 70 nm Au nanostars coated with ethylene glycol-modified Raman reporter molecules for hydrophilic stabilization and subsequent covalent bioconjugation to antibodies. We systematically investigated the influence of heat- and protease-induced epitope retrieval (HIER and PIER, respectively) on the immunostaining quality of prostate-specific antigen (PSA) on human prostate tissue sections. The best staining results were obtained with PIER. Pretreatment of the tissue sections by HIER led to selective but nonspecific adsorption of the antibody-Au nanostar conjugates onto epithelial cells, while enzymatic treatment within PIER did not. In addition to gold nanostars, also other types of metal NPs with different shapes and sizes (including ca. 20 nm quasi-spherical Au NPs and ca. 60 nm quasi-spherical Au/Ag nanoshells) as well as tissue sections from different organs (including prostate and breast) were tested; in each case the same tendency was observed, i.e., PIER yielded better results than HIER. Therefore, we recommend PIER for future NP-based tissue immunostaining such as immuno-SERS microscopy. Alternatively, for antigens that can only be unmasked by heating, PEGylation of the NPs is recommended to avoid nonspecific binding. © 2017 American Chemical Society.view abstract doi: 10.1021/acs.analchem.7b03144 2018 • 644 Ejector-based sampling from low-pressure aerosol reactors
Rosenberger, T. and Münzer, A. and Kiesler, D. and Wiggers, H. and Kruis, F.E.
Journal of Aerosol Science 123 105-115 (2018)Online measurements of nanoparticles are necessary when rapid information about the particle size and mass distribution is needed. Currently, the application of online measurement techniques with commonly used instruments such as SMPS, CPMA and ELPI+ is not possible at low-pressure conditions. In this work, a commercial vacuum ejector is used as a simple tool to transfer nanoparticles from a low-pressure region to atmospheric pressure. The vacuum ejector is investigated for different process pressures between 120 and 170 mbar to measure size-selected aerosols in the range from 10 to 100 nm. It was found that the sampling with the vacuum ejector does not change the particle size. The gas and particle dilution factors as well as the particle losses are determined, so that quantitative measurements of the aerosol size distribution can be obtained. Additionally, the applicability of the vacuum ejector is tested during particle synthesis in a low-pressure microwave plasma reactor with a combination of online instrumentation. The direct transfer of the aerosol to atmospheric pressure allows real-time measurements. The primary particle size, mass mobility exponent and effective density are calculated exemplary based on parallel online ELPI+, SMPS and CPMA measurements and are compared to offline TEM analysis. © 2018 Elsevier Ltdview abstract doi: 10.1016/j.jaerosci.2018.06.003 2018 • 643 Fluoride doped γ-Fe2O3 nanoparticles with increased MRI relaxivity
Jones, N.E. and Burnett, C.A. and Salamon, S. and Landers, J. and Wende, H. and Lazzarini, L. and Gibbs, P. and Pickles, M. and Johnson, B.R.G. and Evans, D.J. and Archibald, S.J. and Francesconi, M.G.
Journal of Materials Chemistry B 6 3665-3673 (2018)Iron oxide nanoparticles (IONs) are being actively researched and experimented with as contrast agents for Magnetic Resonance Imaging (MRI), as well as image-directed delivery of therapeutics. The efficiency of an MRI contrast agent can be described by its longitudinal and transverse relaxivities, r1 and r2. γ-Fe2O3 nanoparticles-doped with fluoride in a controlled manner and functionalised with citric acid-showed a 3-fold increase in r1 and a 17-fold increase in r2 in a magnetic field of 3 T and almost 6-fold increase in r1 and a 14-fold increase in r2 at 11 T. Following fluorination, PXRD shows that the crystal structure of γ-Fe2O3 is maintained, Mössbauer spectroscopy shows that the oxidation state of the Fe cation is unchanged and HREM shows that the particle size does not vary. However, magnetisation curves show a large increase in the coercive field, pointing towards a large increase in the magnetic anisotropy for the fluorinated nanoparticles compared to the un-doped γ-Fe2O3 nanoparticles. Therefore, a chemically induced increase in magnetic anisotropy appears to be the most relevant parameter responsible for the large increase in relaxivity for γ-Fe2O3 nanoparticles. © 2018 The Royal Society of Chemistry.view abstract doi: 10.1039/c8tb00360b 2018 • 642 Formation of nickel nanoparticles and magnetic matrix in nickel phthalocyanine by doping with potassium
Manukyan, A.S. and Avakyan, L.A. and Elsukova, A.E. and Zubavichus, Y.V. and Sulyanov, S.N. and Mirzakhanyan, A.A. and Kolpacheva, N.A. and Spasova, M. and Kocharian, A.N. and Farle, M. and Bugaev, L.A. and Sharoyan, E.G.
Materials Chemistry and Physics 214 564-571 (2018)A method for synthesis of nickel nanoparticles in a magnetic nickel phthalocyanine anions matrix has been developed. The method is based on intercalation of potassium atoms to the nickel phthalocyanine (NiPc) polycrystalline powder at 300 °C. The structure of (K2NiPc) was investigated by using high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) spectroscopes. Magnetic properties were studied by SQUID magnetometry and magnetic resonances methods. It is revealed that the resultant compound contains of 1 wt% Ni nanoparticles with the average size of 15 nm. The measured values of the magnetization and absorption of the ferromagnetic resonance considerably exceed the magnetism which can be attributed to metallic Ni nanoparticles. The obtained results indicate the presence of room temperature molecular ferromagnetism caused by anionic molecules of NiPc. © 2018 Elsevier B.V.view abstract doi: 10.1016/j.matchemphys.2018.04.068 2018 • 641 Formation of Polymeric Particles by Direct Polymerization on the Surface of a Supramolecular Template
Li, M. and Zellermann, E. and Schmuck, C.
Chemistry - A European Journal 24 9061-9065 (2018)Formation of polymeric materials on the surface of supramolecular assemblies is rather challenging because of the often weak noncovalent interactions between the self-assembled template and the monomers before polymerization. We herein show that the introduction of a supramolecular anion recognition motif, the guanidiniocarbonyl pyrrole cation (GCP), into a short Fmoc-dipeptide 1 leads to self-assembled spherical nanoparticles in aqueous solution. Negatively charged diacetylene monomers can be attached onto the surface of these nanoparticles, which, after UV polymerization, leads to the formation of a polymer shell around the self-assembled template. The hybrid supramolecular and polymeric nanoparticles demonstrate intriguing thermal hysteresis phenomena. The template nanoparticles could be disassembled upon treatment with organic base, which cleaved the Fmoc moiety on 1. This strategy thus showed that a supramolecular anion recognition motif allows the post-assembly formation of polymeric nanomaterials from anionic monomers around a cationic self-assembled template. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/chem.201705209 2018 • 640 Glycerol Oxidation Using MgO- and Al2O3-supported Gold and Gold–Palladium Nanoparticles Prepared in the Absence of Polymer Stabilizers
Dodekatos, G. and Abis, L. and Freakley, S.J. and Tüysüz, H. and Hutchings, G.J.
ChemCatChem 10 1351-1359 (2018)Au and AuPd nanoparticles supported on MgO and Al2O3 were employed for the selective aqueous phase oxidation of glycerol under basic conditions. Catalysts were prepared by sol-immobilization without the addition of a stabilizing agent such as polyvinyl alcohol (PVA), which is generally added to stabilize the noble metal sol prior to immobilization. The obtained materials prepared with and without stabilizing agent were active for glycerol oxidation and showed similar catalytic performances—implying that the stabilizing polymer is not required to obtain active materials. Depending on the support used, it was possible to tailor the selectivity towards the desired oxidation products by using catalysts prepared with or without stabilizing agent. PVA-free Au/γ-Al2O3 exhibited a remarkably high selectivity towards tartronic acid (40 % at 97 % conversion), which was not observed for Au/γ-Al2O3 prepared with PVA (27 % at isoconversion). Selective glycerol oxidation performed under base-free conditions over AuPd/MgO catalysts also corroborated the previous results that the presence of a stabilizing polymer is not required to prepare active catalysts by sol-immobilization. Thus, a facile way to circumvent the inherent drawbacks encountered by the use of polymer stabilizers during catalyst preparation is presented herein. Experimental results suggest that the presence of the polymer stabilizers can affect the reaction pathways and control selectivity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/cctc.201800074 2018 • 639 Ideal Dimers of Gold Nanospheres for Precision Plasmonics: Synthesis and Characterization at the Single-Particle Level for Identification of Higher Order Modes
Yoon, J.H. and Selbach, F. and Langolf, L. and Schlücker, S.
Small 14 (2018)Ideal dimers comprising gold nanoparticles with a smooth surface and high sphericity are synthesized by a substrate-based assembly strategy with efficient cetyltrimethylammonium bromide removal. An unprecedented structural and plasmonic uniformity at the single-particle level is observed since inhomogeneities resulting from variations in gap morphology are eliminated. Single ideal dimers are analyzed by polarization-resolved dark-field scattering spectroscopy. Contributions from transverse as well as quadrupolar and octupolar longitudinal plasmon coupling modes can be discriminated because of their orthogonal polarization behavior. The assignment of these higher order coupling modes is supported by computer simulations. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/smll.201702754 2018 • 638 Improved Models for Metallic Nanoparticle Cores from Atomic Pair Distribution Function (PDF) Analysis
Banerjee, S. and Liu, C.-H. and Lee, J.D. and Kovyakh, A. and Grasmik, V. and Prymak, O. and Koenigsmann, C. and Liu, H. and Wang, L. and Abeykoon, A.M.M. and Wong, S.S. and Epple, M. and Murray, C.B. and Billinge, S.J.L.
Journal of Physical Chemistry C 122 29498-29506 (2018)X-ray atomic pair distribution functions (PDFs) were collected from a range of canonical metallic nanomaterials, both elemental and alloyed, prepared using different synthesis methods and exhibiting drastically different morphological properties. Widely applied shape-tuned attenuated crystal (AC) fcc models proved inadequate, yielding structured, coherent, and correlated fit residuals. However, equally simple discrete cluster models could account for the largest amplitude features in these difference signals. A hypothesis testing based approach to nanoparticle structure modeling systematically ruled out effects from crystallite size, composition, shape, and surface faceting as primary factors contributing to the AC misfit. On the other hand, decahedrally twinned cluster cores were found to be the origin of the AC structure misfits for a majority of the nanomaterials reported here. It is further motivated that the PDF can readily differentiate between the arrangement of domains in these multiply twinned motifs. Most of the nanomaterials surveyed also fall within the sub-5 nm size regime where traditional electron microscopy cannot easily detect and quantify domain structures, with sampling representative of the average nanocrystal synthesized. The results demonstrate that PDF analysis is a powerful method for understanding internal atomic interfaces in small noble metallic nanomaterials. Such core cluster models, easily built algorithmically, should serve as starting structures for more advanced models able to capture atomic positional disorder, ligand induced or otherwise, near nanocrystal surfaces. © 2018 American Chemical Society.view abstract doi: 10.1021/acs.jpcc.8b05897 2018 • 637 Local Structure of Nanocrystalline Aluminum Nitride
Ognjanović, S.M. and Zähres, M. and Mayer, C. and Winterer, M.
Journal of Physical Chemistry C 122 23749-23757 (2018)The local structure of chemical-vapor-synthesized (CVS) crystalline AlN nanoparticles is investigated by combining magic angle spinning nuclear magnetic resonance and X-ray absorption spectroscopies. Extended X-ray absorption fine structure data are analyzed by reverse Monte Carlo method, and X-ray absorption near edge structure is interpreted by first principles FEFF calculations. The measurements show behavior characteristic of partially disordered systems. Nevertheless, combined analysis of the data, supported by Rietveld refinement of X-ray diffraction patterns, leads to the conclusion that the observed behavior is due to the small size (large surface to volume ratios) of the nanoparticles (dXRD < 6 nm) and that highly crystalline wurtzite AlN is formed during the CVS process. © 2018 American Chemical Society.view abstract doi: 10.1021/acs.jpcc.8b06610 2018 • 636 Nano Impact Electrochemistry: Effects of Electronic Filtering on Peak Height, Duration and Area
Kanokkanchana, K. and Saw, E.N. and Tschulik, K.
ChemElectroChem 5 3000-3005 (2018)Nano impact electrochemistry is used to measure a transient signal while a nanoparticle (NP) hits an electrode due to its motion in a solution. A variety of information can be obtained from this current pulse, yet its accurate measurement is challenging due to its short duration (μs to s) and small amplitude (≤10 nA). A typically used low bandwidth low-pass filter can improve the signal-to-noise ratio, but it may cost severely in the accuracy of the data. Here, we demonstrate the effects of electronic filters by using generated current impulses with duration from 125 μs to 8 ms. Initially, a system dedicated to measure short and low current impulses was employed. There, an 8th order Bessel filter was used and the effect of varying the cut-off frequency between 50 Hz and 20 kHz on the impulse response is studied. Even though the charge is generally conserved by the filter, amplitude and duration of the pulse vary greatly in dependence of the cut-off frequency. In comparison, the response of widely used potentiostats was tested and significant deviations of the measured signal from the input were detected. Supported by destructive nano impact experiments with Ag NPs in KCl(aq), we show how the filtering affects the experimentally determined size of Ag NPs and Cl− diffusion coefficient, using impact charges and duration, respectively. As a result, we suggest a general guideline to researchers for accurate electrochemical nano impact measurements, in particular with respect to current peak duration analysis. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/celc.201800738 2018 • 635 Oxygen Reduction Activity and Reversible Deactivation of Single Silver Nanoparticles during Particle Adsorption Events
Öhl, D. and Clausmeyer, J. and Barwe, S. and Botz, A. and Schuhmann, W.
ChemElectroChem 5 1886-1890 (2018)The activity towards the oxygen reduction reaction (ORR) of single silver nanoparticles (AgNP) was quantified by using AgNP impacts on dual-bore carbon nanoelectrodes in highly alkaline media. We found suitable conditions for the particles to adhere sufficiently stably for detailed electrochemical characterization of a single particle. The special electrode design opens the possibility to dose gaseous oxygen to the nanoparticle under study. Deactivation of the catalytic activity of the AgNP upon excessive exposure to oxygen as well as the recovery of catalytic activity under reducing conditions is presumably attributed to hydrogen evolution at the applied low potentials. The proposed approach allows mechanistic parameters for the ORR to be extracted at a single AgNP in highly alkaline media in the absence of any binder materials and under exclusion of averaging ensemble effects. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/celc.201800094 2018 • 634 Primary particle diameter differentiation and bimodality identification by five analytical methods using gold nanoparticle size distributions synthesized by pulsed laser ablation in liquids
Letzel, A. and Gökce, B. and Menzel, A. and Plech, A. and Barcikowski, S.
Applied Surface Science 435 743-751 (2018)For a known material, the size distribution of a nanoparticle colloid is a crucial parameter that defines its properties. However, measured size distributions are not easy to interpret as one has to consider weighting (e.g. by light absorption, scattering intensity, volume, surface, number) and the way size information was gained. The radius of a suspended nanoparticle can be given as e.g. sphere equivalent, hydrodynamic, Feret or radius of gyration. In this study, gold nanoparticles in water are synthesized by pulsed-laser ablation (LAL) and fragmentation (LFL) in liquids and characterized by various techniques (scanning transmission electron microscopy (STEM), small-angle X-ray scattering (SAXS), analytical disc centrifugation (ADC), dynamic light scattering (DLS) and UV–vis spectroscopy with Mie-Gans Theory) to study the comparability of different analytical techniques and determine the method that is preferable for a given task related to laser-generated nanoparticles. In particular, laser-generated colloids are known to be bimodal and/or polydisperse, but bimodality is sometimes not analytically resolved in literature. In addition, frequently reported small size shifts of the primary particle mode around 10 nm needs evaluation of its statistical significance related to the analytical method. Closely related to earlier studies on SAXS, different colloids in defined proportions are mixed and their size as a function of the nominal mixing ratio is analyzed. It is found that the derived particle size is independent of the nominal mixing ratio if the colloid size fractions do not overlap considerably. Conversely, the obtained size for colloids with overlapping size fractions strongly depends on the nominal mixing ratio since most methods cannot distinguish between such fractions. Overall, SAXS and ADC are very accurate methods for particle size analysis. Further, the ability of different methods to determine the nominal mixing ratio of sizes fractions is studied experimentally. © 2017 Elsevier B.V.view abstract doi: 10.1016/j.apsusc.2017.11.130 2018 • 633 Production, deformation and mechanical investigation of magnetic alginate capsules
Zwar, E. and Kemna, A. and Richter, L. and Degen, P. and Rehage, H.
Journal of Physics Condensed Matter 30 (2018)In this article we investigated the deformation of alginate capsules in magnetic fields. The sensitivity to magnetic forces was realised by encapsulating an oil in water emulsion, where the oil droplets contained dispersed magnetic nanoparticles. We solved calcium ions in the aqueous emulsion phase, which act as crosslinking compounds for forming thin layers of alginate membranes. This encapsulating technique allows the production of flexible capsules with an emulsion as the capsule core. It is important to mention that the magnetic nanoparticles were stable and dispersed throughout the complete process, which is an important difference to most magnetic alginate-based materials. In a series of experiments, we used spinning drop techniques, capsule squeezing experiments and interfacial shear rheology in order to determine the surface Young moduli, the surface Poisson ratios and the surface shear moduli of the magnetically sensitive alginate capsules. In additional experiments, we analysed the capsule deformation in magnetic fields. In spinning drop and capsule squeezing experiments, water droplets were pressed out of the capsules at elevated values of the mechanical load. This phenomenon might be used for the mechanically triggered release of water-soluble ingredients. After drying the emulsion-filled capsules, we produced capsules, which only contained a homogeneous oil phase with stable suspended magnetic nanoparticles (organic ferrofluid). In the dried state, the thin alginate membranes of these particles were rather rigid. These dehydrated capsules could be stored at ambient conditions for several months without changing their properties. After exposure to water, the alginate membranes rehydrated and became flexible and deformable again. During this swelling process, water diffused back in the capsule. This long-term stability and rehydration offers a great spectrum of different applications as sensors, soft actuators, artificial muscles or drug delivery systems. © 2018 IOP Publishing Ltd.view abstract doi: 10.1088/1361-648X/aaa6f5 2018 • 632 Prolonged release of bone morphogenetic protein-2 in vivo by gene transfection with DNA-functionalized calcium phosphate nanoparticle-loaded collagen scaffolds
Tenkumo, T. and Vanegas Sáenz, J.R. and Nakamura, K. and Shimizu, Y. and Sokolova, V. and Epple, M. and Kamano, Y. and Egusa, H. and Sugaya, T. and Sasaki, K.
Materials Science and Engineering C 92 172-183 (2018)In the combination of scaffolds immersed in growth factor solutions, the release of growth factors mainly depends on scaffold degradation. However, the release of bone morphogenetic protein (BMP)-2 at an appropriate concentration during the stage of tissue regeneration would enhance bone regeneration. To achieve this condition, the present study was performed to investigate the effects of scaffolds combined with gene transfection using non-viral vectors. Nanohydroxyapatite-collagen (nHAC) scaffolds cross-linked with 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) or ascorbic acid/copper chloride, and a collagen scaffold (Terdermis®) were prepared, loaded with BMP-2-encoding plasmid DNA-functionalized calcium phosphate nanoparticles (CaP), naked plasmid DNA, or BMP-2 solution, and implanted in rats. The yield of released BMP-2 and its releasing period, respectively, were larger and longer from the scaffolds loaded with CaP than from those incubated with BMP-2 solution. In addition, the alkaline phosphatase activity induced by the CaP-loaded scaffolds was higher. Histological analysis showed that released BMP-2 could be observed on the macrophages or multinuclear giant cells surrounding the nHAC fragments or collagen fibres. TRAP-positive or OCN-positive sites were observed in all groups and a mineralization area was observed in the Terdermis®/CaP sample. The present study demonstrates that gene transfection by scaffold loaded with CaP gene transfer vectors induces a larger yield of BMP-2 for a longer period than by scaffolds loaded with BMP-2 solution or naked plasmid. © 2018 Elsevier B.V.view abstract doi: 10.1016/j.msec.2018.06.047 2018 • 631 Quantitative evaluation of nanoparticle classification by size-exclusion chromatography
Süß, S. and Metzger, C. and Damm, C. and Segets, D. and Peukert, W.
Powder Technology 339 264-272 (2018)Although few attempts for classification of nanoparticles (NPs) in labscale do exist, the transfer to industrial applications is still challenging. One promising separation method, which is already established for biological molecules, is chromatography. Herein, we study the classification of differently sized gold NPs (AuNPs) by size-exclusion chromatography (SEC). First, we investigated the interactions of AuNPs with potential stationary phases in order to identify a suitable material for the chromatographic process where irreversible NP adhesion is excluded. Then, we demonstrate the high reproducibility of our SEC experiments by multiple sample injections that lead to constant peak areas. In particular, we show the size-dependent elution behavior of AuNP mixtures resulting in bimodal elution peaks, where size separation was confirmed by inline measured UV/Vis spectra. Finally, NP classification results by using a fraction collector are characterized by retention time, mass balances and size-dependent separation efficiencies. The adjustment of the particle size distributions (PSDs) is demonstrated by changing the switching time of the fraction collector. Our study evidences the high potential of SEC for preparative and continuous separation of NPs. © 2018 The Authorsview abstract doi: 10.1016/j.powtec.2018.08.008 2018 • 630 Rechargeable, flexible and mediator-free biosupercapacitor based on transparent ITO nanoparticle modified electrodes acting in µM glucose containing buffers
Bobrowski, T. and González Arribas, E. and Ludwig, R. and Toscano, M.D. and Shleev, S. and Schuhmann, W.
Biosensors and Bioelectronics 101 84-89 (2018)We present a transparent and flexible self-charging biosupercapacitor based on an optimised mediator- and membrane-free enzymatic glucose/oxygen biofuel cell. Indium tin oxide (ITO) nanoparticles were spray-coated on transparent conducting ITO supports resulting in a flocculent, porous and nanostructured electrode surface. By this, high capacitive currents caused by an increased electrochemical double layer as well as enhanced catalytic currents due to a higher number of immobilised enzyme molecules were obtained. After a chemical pre-treatment with a silane derivative, bilirubin oxidase from Myrothecium verrucaria was immobilized onto the ITO nanostructured electrode surface under formation of a biocathode, while bioanodes were obtained by either immobilisation of cellobiose dehydrogenase from Corynascus thermophilus or soluble PQQ-dependent glucose dehydrogenase from Acinetobacter calcoaceticus. The latter showed a lower apparent KM value for glucose conversion and higher catalytic currents at µM glucose concentrations. Applying the optimised device as a biosupercapacitor in a discontinuous charge/discharge mode led to a generated power output of 0.030 mW/cm2 at 50 µM glucose, simulating the glucose concentration in human tears. This represents an enhancement by a factor of 350 compared to the power density obtained from the continuously operating biofuel cell with a maximum power output of 0.086 µW/cm2 under the same conditions. After 17 h of charging/discharging cycles a remarkable current enhancement was still measured. The entire device was transferred to flexible materials and applied for powering a flexible display showing its potential applicability as an intermittent power source in smart contact lenses. © 2017 Elsevier B.V.view abstract doi: 10.1016/j.bios.2017.10.016 2018 • 629 Retention mechanisms of 1.7 nm ZnS quantum dots and sub-20 nm Au nanoparticles in ultrafiltration membranes
Lee, H. and Segets, D. and Süß, S. and Peukert, W. and Chen, S.-C. and Pui, D.Y.H.
Journal of Membrane Science 567 58-67 (2018)Membrane processes are considered to be a very effective and promising method for drinking water and wastewater treatments. However, particle removal mechanisms have not been fully elucidated due to complex surface interactions between colloids and membranes, especially for very small colloidal particles. In this study, a series of systematic filtration tests for eight different types of membrane filters, having nominal pore sizes from 0.005 to 0.1 µm, against 1.7 nm ZnS quantum dots (QDs) and 5, 10 and 20 nm Au nanoparticles (NPs) was performed to understand their retention mechanisms, including rejection in front of the filter surface and adsorption inside the filter. By comparing rejection, adsorption and recovery, it was found that the predominant retention mechanisms for retaining small NPs varied from filter to filter. For instance, electrostatic repulsion played a significant role for the rejection of NPs, i.e. impeding them entering the membrane pores in most membranes. In comparison, the Nylon membrane had a significant adsorption retention ability for Au NPs due to electrostatic attraction. Besides, it was found that filtration flow rate, or flux, was also an important parameter for the final retention because the enhanced hydrodynamic drag could trigger the detachment of deposited NPs or press NPs flowing through the superficial entrance leading to penetration. Tests of 10 nm Au NP retention using five different membranes with the same nominal pore size of 0.1 µm showed large variation of NP retention efficiencies demonstrating that pore size should not be used as the only criterion for rating filter performance, especially for small NPs. Our results provide not only detailed insights into the retention mechanisms of various membranes but also suggestions on how to select membrane filters for different filtration purposes. © 2018 Elsevier B.V.view abstract doi: 10.1016/j.memsci.2018.09.033 2018 • 628 Segregation Phenomena in Size-Selected Bimetallic CuNi Nanoparticle Catalysts
Pielsticker, L. and Zegkinoglou, I. and Divins, N.J. and Mistry, H. and Chen, Y.-T. and Kostka, A. and Boscoboinik, J.A. and Cuenya, B.R.
Journal of Physical Chemistry B 122 919-926 (2018)Surface segregation, restructuring, and sintering phenomena in size-selected copper-nickel nanoparticles (NPs) supported on silicon dioxide substrates were systematically investigated as a function of temperature, chemical state, and reactive gas environment. Using near-ambient pressure (NAP-XPS) and ultrahigh vacuum X-ray photoelectron spectroscopy (XPS), we showed that nickel tends to segregate to the surface of the NPs at elevated temperatures in oxygen- or hydrogen-containing atmospheres. It was found that the NP pretreatment, gaseous environment, and oxide formation free energy are the main driving forces of the restructuring and segregation trends observed, overshadowing the role of the surface free energy. The depth profile of the elemental composition of the particles was determined under operando CO2 hydrogenation conditions by varying the energy of the X-ray beam. The temperature dependence of the chemical state of the two metals was systematically studied, revealing the high stability of nickel oxides on the NPs and the important role of high valence oxidation states in the segregation behavior. Atomic force microscopy (AFM) studies revealed a remarkable stability of the NPs against sintering at temperatures as high as 700 °C. The results provide new insights into the complex interplay of the various factors which affect alloy formation and segregation phenomena in bimetallic NP systems, often in ways different from those previously known for their bulk counterparts. This leads to new routes for tuning the surface composition of nanocatalysts, for example, through plasma and annealing pretreatments. © 2017 American Chemical Society.view abstract doi: 10.1021/acs.jpcb.7b06984 2018 • 627 Shape-Dependent Dissolution and Cellular Uptake of Silver Nanoparticles
Graf, C. and Nordmeyer, D. and Sengstock, C. and Ahlberg, S. and Diendorf, J. and Raabe, J. and Epple, M. and Köller, M. and Lademann, J. and Vogt, A. and Rancan, F. and Rühl, E.
Langmuir 34 1506-1519 (2018)The cellular uptake and dissolution of trigonal silver nanoprisms (edge length 42 ± 15 nm, thickness 8 ± 1 nm) and mostly spherical silver nanoparticles (diameter 70 ± 25 nm) in human mesenchymal stem cells (hMSC's) and human keratinocytes (HaCaT cells) were investigated. Both particles are stabilized by polyvinylpyrrolidone (PVP), with the prisms additionally stabilized by citrate. The nanoprisms dissolved slightly in pure water but strongly in isotonic saline or at pH 4, corresponding to the lowest limit for the pH during cellular uptake. The tips of the prisms became rounded within minutes due to their high surface energy. Afterward, the dissolution process slowed down due to the presence of both PVP stabilizing Ag{100} sites and citrate blocking Ag{111} sites. On the contrary, nanospheres, solely stabilized by PVP, dissolved within 24 h. These results correlate with the finding that particles in both cell types have lost >90% of their volume within 24 h. hMSC's took up significantly more Ag from nanoprisms than from nanospheres, whereas HaCaT cells showed no preference for one particle shape. This can be rationalized by the large cellular interaction area of the plateletlike nanoprisms and the bending stiffness of the cell membranes. hMSC's have a highly flexible cell membrane, resulting in an increased uptake of plateletlike particles. HaCaT cells have a membrane with a 3 orders of magnitude higher Young's modulus than for hMSC. Hence, the energy gain due to the larger interaction area of the nanoprisms is compensated for by the higher energy needed for cell membrane deformation compared to that for spheres, leading to no shape preference. © 2017 American Chemical Society.view abstract doi: 10.1021/acs.langmuir.7b03126 2018 • 626 Simultaneous Rayleigh/Mie and Raman/Fluorescence Characterization of Molecularly Functionalized Colloids by Correlative Single-Particle Real-Time Imaging in Suspension
Wissler, J. and Wehmeyer, M. and Bäcker, S. and Knauer, S. and Schlücker, S.
Analytical Chemistry 90 723-728 (2018)Many applications of nano- and microparticles require molecular functionalization. Assessing the heterogeneity of a colloidal sample in terms of its molecular functionalization is highly desirable but not accessible by conventional ensemble experiments. Retrieving this information necessitates single-particle experiments which simultaneously detect both functionalized and nonfunctionalized particles via two separate imaging channels. In this contribution, we present an optical setup for performing correlative single-particle imaging using laser light-sheet illumination: the first detection channel records elastic light scattering (Rayleigh/Mie), while the second channel detects inelastic light scattering (Raman) or fluorescence. The instrument is tested with Raman reporter-functionalized SERS-active metal nanoparticles (core/satellite silver nanoparticles, dimers and monomers of gold nanoparticles) and fluorophore-functionalized colloids (fluorescent polymer microparticles, dye-labeled protein on gold nanoparticles). © 2017 American Chemical Society.view abstract doi: 10.1021/acs.analchem.7b02528 2018 • 625 Single Nanoparticle Growth from Nanoparticle Tracking Analysis: From Monte Carlo Simulations to Nanoparticle Electrogeneration
Brasiliense, V. and Noël, J.-M. and Wonner, K. and Tschulik, K. and Combellas, C. and Kanoufi, F.
ChemElectroChem 5 3036-3043 (2018)By scrutinizing the trajectory of individual nanoparticles (NPs) in solution, NP tracking analysis (NTA) allows sizing individual NPs and providing meaningful complementary information to single NP electrochemistry. Herein, a model is developed to extend NTA to allow dynamic NP sizing and to analyze the kinetics of growth of NPs in solution. Interpreting the NP trajectories as scaled Brownian motion, Monte Carlo simulations produce stochastic trajectories of growing NPs (under diffusion-controlled growth). These trajectories are grounds for determining a strategy to estimate the growth parameters of individual NPs from the time evolution analysis of the mean square displacement (MSD) curves. In particular, we evaluate the accuracy and precision of the parameter estimates from MSD analysis. In addition, the strategy is illustrated to depict the homogeneous electrosynthesis of silver NPs from the oxidation of a sacrificial Ag ultramicroelectrode (UME) in Fe2+ solution. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/celc.201800742 2018 • 624 Size-selected Fe3O4-Au hybrid nanoparticles for improved magnetism-based theranostics
Efremova, M.V. and Nalench, Y.A. and Myrovali, E. and Garanina, A.S. and Grebennikov, I.S. and Gifer, P.K. and Abakumov, M.A. and Spasova, M. and Angelakeris, M. and Savchenko, A.G. and Farle, M. and Klyachko, N.L. and Majouga, A....
Beilstein Journal of Nanotechnology 9 2684-2699 (2018)Size-selected Fe3O4-Au hybrid nanoparticles with diameters of 6-44 nm (Fe3O4) and 3-11 nm (Au) were prepared by high temperature, wet chemical synthesis. High-quality Fe3O4 nanocrystals with bulk-like magnetic behavior were obtained as confirmed by the presence of the Verwey transition. The 25 nm diameter Fe3O4-Au hybrid nanomaterial sample (in aqueous and agarose phantom systems) showed the best characteristics for application as contrast agents in magnetic resonance imaging and for local heating using magnetic particle hyperthermia. Due to the octahedral shape and the large saturation magnetization of the magnetite particles, we obtained an extraordinarily high r2-relaxivity of 495 mM-1·s-1 along with a specific loss power of 617 W·gFe-1 and 327 W·gFe-1 for hyperthermia in aqueous and agarose systems, respectively. The functional in vitro hyperthermia test for the 4T1 mouse breast cancer cell line demonstrated 80% and 100% cell death for immediate exposure and after precultivation of the cells for 6 h with 25 nm Fe3O4-Au hybrid nanomaterials, respectively. This confirms that the improved magnetic properties of the bifunctional particles present a next step in magnetic-particle-based theranostics. © 2018 Efremova et al.view abstract doi: 10.3762/bjnano.9.251 2018 • 623 Strong Deformation of Ferrofluid-Filled Elastic Alginate Capsules in Inhomogenous Magnetic Fields
Wischnewski, C. and Zwar, E. and Rehage, H. and Kierfeld, J.
Langmuir 34 13534-13543 (2018)We present a new system based on alginate gels for the encapsulation of a ferrofluid drop, which allows us to create millimeter-sized elastic capsules that are highly deformable by inhomogeneous magnetic fields. We use a combination of experimental and theoretical work in order to characterize and quantify the deformation behavior of these ferrofluid-filled capsules. We introduce a novel method for the direct encapsulation of unpolar liquids by sodium alginate. By adding 1-hexanol to the unpolar liquid, we can dissolve sufficient amounts of CaCl2 in the resulting mixture for ionotropic gelation of sodium alginate. The addition of polar alcohol molecules allows us to encapsulate a ferrofluid as a single phase rather than an emulsion without impairing ferrofluid stability. This encapsulation method increases the amount of encapsulated magnetic nanoparticles resulting in high deformations of approximately 30% (in height-to-width ratio) in inhomogeneous magnetic field with magnetic field variations of 50 mT over the size of the capsule. This offers possible applications of capsules as actuators, switches, or valves in confined spaces like microfluidic devices. We determine both elastic moduli of the capsule shell, Young's modulus and Poisson's ratio, by employing two independent mechanical methods, spinning capsule measurements and capsule compression between parallel plates. We then show that the observed magnetic deformation can be fully understood from magnetic forces exerted by the ferrofluid on the capsule shell if the magnetic field distribution and magnetization properties of the ferrofluid are known. We perform a detailed analysis of the magnetic deformation by employing a theoretical model based on nonlinear elasticity theory. Using an iterative solution scheme that couples a finite element/boundary element method for the magnetic field calculation to the solution of the elastic shape equations, we achieve quantitative agreement between theory and experiment for deformed capsule shapes using the Young modulus from mechanical characterization and the surface Poisson ratio as a fit parameter. This detailed analysis confirms the results from mechanical characterization that the surface Poisson ratio of the alginate shell is close to unity, that is, deformations of the alginate shell are almost area conserving. © 2018 American Chemical Society.view abstract doi: 10.1021/acs.langmuir.8b02357 2018 • 622 Suppression of the Verwey Transition by Charge Trapping
Schmitz-Antoniak, C. and Schmitz, D. and Warland, A. and Darbandi, M. and Haldar, S. and Bhandary, S. and Sanyal, B. and Eriksson, O. and Wende, H.
Annalen der Physik (2018)The Verwey transition in Fe3O4 nanoparticles with a mean diameter of 6.3 nm is suppressed after capping the particles with a 3.5 nm thick shell of SiO2. By X-ray absorption spectroscopy and its associated X-ray magnetic circular dichroism this suppression can be correlated to localized Fe2+ states and a reduced double exchange visible in different site-specific magnetization behavior in high magnetic fields. The results are discussed in terms of charge trapping at defects in the Fe3O4/ SiO2 interface and the consequent difficulties in the formation of the common phases of Fe3O4. By comparison to X-ray absorption spectra of bare Fe3O4 nanoparticles in course of the Verwey transition, particular changes in the spectral shape could be correlated to changes in the number of unoccupied d states for Fe ions at different lattice sites. These findings are supported by density functional theory calculations. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/andp.201700363 2018 • 621 Suspension- and powder-based derivation of Hansen dispersibility parameters for zinc oxide quantum dots
Süß, S. and Lin, W. and Getmanenko, O. and Pflug, L. and Sobisch, T. and Peukert, W. and Lerche, D. and Segets, D.
Particuology (2018)For most particle-based applications, formulation in the liquid phase is a decisive step, and thus, particle interactions and stability in liquid media are of major importance. The concept of Hansen solubility parameters (HSP) was initially invented to describe the interactions of (polymer) molecules and their solubility in different liquids and is increasingly being used in particle technology to describe dispersibility. Because dispersions are not thermodynamically stable, the term Hansen dispersibility parameters (HDP) is used instead of HSP (Süß Sobisch, Peukert, Lerche, & Segets, 2018). Herein, we extend a previously developed standardized and non-subjective method for determination of Hansen parameters based on analytical centrifugation to the important class of quantum materials. As a technically relevant model system, zinc oxide quantum dots (QDs) were used to transfer our methodology to nanoparticles (NPs) with sizes below 10 nm. The results obtained using the standard procedure starting from a dried powder were compared with those obtained through redispersion from the wet sediment produced during the typical washing procedure of QDs, and drying was observed to play an important role. In conclusion, our study reveals the high potential of HDP for quantifying the interfacial properties of NPs as well as their link to dispersibility. © 2018 Chinese Society of Particuology and Institute of Process Engineering, Chinese Academy of Sciencesview abstract doi: 10.1016/j.partic.2018.05.010 2018 • 620 Temperature-Dependent Ultrastructure Transformation of Au-Fe Nanoparticles Investigated by in Situ Scanning Transmission Electron Microscopy
Kamp, M. and Tymoczko, A. and Schürmann, U. and Jakobi, J. and Rehbock, C. and Rätzke, K. and Barcikowski, S. and Kienle, L.
Crystal Growth and Design 18 5434-5440 (2018)Three-dimensional morphology changes of bimetallic nanoparticles (NPs) with nominal composition Au50Fe50 and Au20Fe80, generated by pulsed laser ablation in liquid, are monitored in situ and ex situ via scanning transmission electron microscopy and electron tomography. The samples are made up of a chemically segregated core-shell (CS) NPs structure, with an Au-rich shell and Fe-rich core, and solid solution (SS) NPs in the pristine state. Further, the examinations reveal information about a sequence of characteristic changes from the pristine metastable and intermediate ultrastructures up to thermodynamically stable products. In the case of the Au20Fe80 sample, a metastable spherical CS morphology is transformed at equilibrium conditions into a cube-shaped Fe-rich core faceted by truncated Au-rich pyramids. For the Au50Fe50 sample, the Au-rich shell is solved into the Fe-rich core, and chemically homogeneous (SS) NPs are formed. Interestingly, this transformation was proven to occur via an intermediate ultrastructure with lamellar segregation, not previously reported as a transient state during in situ heating. On the basis of these observations, a correlation between the composition and the morphology at equilibrium is suggested, in accordance with the bulk phase diagram of Au-Fe. At the same time, our examinations directly prove that laser ablation synthesis creates nonequilibrium NP morphologies, frozen in metastable, spherical core-shell particles. Copyright © 2018 American Chemical Society.view abstract doi: 10.1021/acs.cgd.8b00809 2018 • 619 The Role of Composition of Uniform and Highly Dispersed Cobalt Vanadium Iron Spinel Nanocrystals for Oxygen Electrocatalysis
Chakrapani, K. and Bendt, G. and Hajiyani, H. and Lunkenbein, T. and Greiner, M.T. and Masliuk, L. and Salamon, S. and Landers, J. and Schlögl, R. and Wende, H. and Pentcheva, R. and Schulz, S. and Behrens, M.
ACS Catalysis 8 1259-1267 (2018)Cation substitution in transition-metal oxides is an important approach to improve electrocatalysts by the optimization of their composition. Herein, we report on phase-pure spinel-type CoV2-xFexO4 nanoparticles with 0 ≤ x ≤ 2 as a new class of bifunctional catalysts for the oxygen evolution (OER) and oxygen reduction reactions (ORR). The mixed-metal oxide catalysts exhibit high catalytic activity for both OER and ORR that strongly depends on the V and Fe content. CoV2O4 is known to exhibit a high conductivity, while in CoFe2O4 the cobalt cation distribution is expected to change due to the inversion of the spinel structure. The optimized catalyst, CoV1.5Fe0.5O4, shows an overpotential for the OER of â300 mV for 10 mA cm-2 with a Tafel slope of 38 mV dec-1 in alkaline electrolyte. DFT+U+SOC calculations on cation ordering confirm the tendency toward the inverse spinel structure with increasing Fe concentration in CoV2-xFexO4 that starts to dominate already at low Fe contents. The theoretical results also show that the variations of oxidation states are related to the surface region, where the redox activity was found experimentally to be manifested in the transformation of V3+ ↠V2+. The high catalytic activity, facile synthesis, and low cost of the CoV2-xFexO4 nanoparticles render them very promising for application in bifunctional electrocatalysis. © 2017 American Chemical Society.view abstract doi: 10.1021/acscatal.7b03529 2018 • 618 Thermodynamic properties of selenoether-functionalized ionic liquids and their use for the synthesis of zinc selenide nanoparticles
Klauke, K. and Zaitsau, D.H. and Bülow, M. and He, L. and Klopotowski, M. and Knedel, T.-O. and Barthel, J. and Held, C. and Verevkin, S.P. and Janiak, C.
Dalton Transactions 47 5083-5097 (2018)Three selenoether-functionalized ionic liquids (ILs) of N-[(phenylseleno)methylene]pyridinium (1), N-(methyl)- (2) and N-(butyl)-N'-[(phenylseleno)methylene]imidazolium (3) with bis(trifluoromethanesulfonyl)imide anions ([NTf2]) were prepared from pyridine, N-methylimidazole and N-butylimidazole with in situ obtained phenylselenomethyl chloride, followed by ion exchange to give the desired compounds. The crystal structures of the bromide and tetraphenylborate salts of the above cations (1-Br, 2-BPh4 and 3-BPh4) confirm the formation of the desired cations and indicate a multitude of different supramolecular interactions besides the dominating Coulomb interactions between the cations and anions. The vaporization enthalpies of the synthesized [NTf2]-containing ILs were determined by means of a quartz-crystal microbalance method (QCM) and their densities were measured with an oscillating U-tube. These thermodynamic data have been used to develop a method for assessment of miscibility of conventional solvents in the selenium-containing ILs by using Hildebrandt solubility parameters, as well as for modeling with the electrolyte perturbed-chain statistical associating fluid theory (ePC-SAFT) method. Furthermore, structure-property relations between selenoether-functionalized and similarly shaped corresponding aryl-substituted imidazolium- and pyridinium-based ILs were analyzed and showed that the contribution of the selenium moiety to the enthalpy of vaporization of an IL is equal to the contribution of a methylene (CH2) group. An incremental approach to predict vaporization enthalpies of ILs by a group contribution method has been developed. The reaction of these ILs with zinc acetate dihydrate under microwave irradiation led to ZnSe nanoparticles of an average diameter between 4 and 10 nm, depending on the reaction conditions. © The Royal Society of Chemistry 2018.view abstract doi: 10.1039/c8dt00233a 2018 • 617 X-ray spectroscopic and stroboscopic analysis of pulsed-laser ablation of Zn and its oxidation
Reich, S. and Göttlicher, J. and Letzel, A. and Gökce, B. and Barcikowski, S. and dos Santos Rolo, T. and Baumbach, T. and Plech, A.
Applied Physics A: Materials Science and Processing 124 (2018)Pulsed laser ablation in liquids (PLAL) as an attractive process for ligand-free nanoparticle synthesis represents a multiscale problem to understand the mechanisms and achieve control. Atomic and nanoscale processes interacting with macroscale dynamics in the liquid demand for sensitive tools for in-situ and structural analysis. By adding X-ray methods, we enlarge the available information on millimeter-scale bubble formation down to atomic-scale nanoparticle reactions. X-ray spectroscopy (XAS) can resolve the chemical speciation of the ablated material during the ablation from a zinc wire target showing a first oxidation step from zinc to zinc oxide within some 10 min followed by a slower reaction to hydrozincite. X-ray imaging investigations also give additional information on the bubble dynamics as we demonstrate by comparing the microsecond radiography and optical stroboscopy. We show different features of the detachment of the ablation bubble from a free wire. The location of the first collapse occurs in front of the target. While a first rebound bubble possesses an homogeneous interior, the subsequent rebound consists merely of a cloud of microbubbles. © 2017, Springer-Verlag GmbH Germany, part of Springer Nature.view abstract doi: 10.1007/s00339-017-1503-3 2017 • 616 Adhesion properties of a three-layer system based on RF-magnetron sputter deposited calcium-phosphate coating and silver nanoparticles
Tkachev, M.S. and Melnikov, E.S. and Surmeneva, M.A. and Sharonova, A.A. and Surmenev, R.A. and Korneva, O.S. and Shulepov, I.A. and Loza, K. and Epple, M.
Proceedings of the 11th International Forum on Strategic Technology, IFOST 2016 88-90 (2017)A three-layer system of hydroxyapatite (HA) coating - Ag nanoparticles - HA coating with an overall thickness of 1.2 μm was prepared. The radio-frequency (RF) magnetron sputtering was used to prepare the first layer of hydroxyapatite coating on titanium. Then electrophoretic deposition of silver nanoparticles on the prepared HA layer was done followed by deposition of the second layer of HA by RFmagnetron sputtering. The adhesion strength was investigated by the scratch test method. Scanning electron microscopy and optical microscopy allowed to qualitatively estimate the deformation mechanisms of the biocomposites after the scratch test. © 2016 IEEE.view abstract doi: 10.1109/IFOST.2016.7884197 2017 • 615 Advanced SERS Sensor Based on Capillarity-Assisted Preconcentration through Gold Nanoparticle-Decorated Porous Nanorods
Xue, L. and Xie, W. and Driessen, L. and Domke, K.F. and Wang, Y. and Schlücker, S. and Gorb, S.N. and Steinhart, M.
Small (2017)A preconcentrating surface-enhanced Raman scattering (SERS) sensor for the analysis of liquid-soaked tissue, tiny liquid droplets and thin liquid films without the necessity to collect the analyte is reported. The SERS sensor is based on a block-copolymer membrane containing a spongy-continuous pore system. The sensor's upper side is an array of porous nanorods having tips functionalized with Au nanoparticles. Capillarity in combination with directional evaporation drives the analyte solution in contact with the flat yet nanoporous underside of the SERS sensor through the continuous nanopore system toward the nanorod tips where non-volatile components of the analyte solution precipitate at the Au nanoparticles. The nanorod architecture increases the sensor surface in the detection volume and facilitates analyte preconcentration driven by directional solvent evaporation. The model analyte 5,5'-dithiobis(2-nitrobenzoic acid) can be detected in a 1 × 10-3m solution ≈300 ms after the sensor is brought into contact with the solution. Moreover, a sensitivity of 0.1 ppm for the detection of the dissolved model analyte is achieved. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/smll.201603947 2017 • 614 Airborne engineered nanomaterials in the workplace—a review of release and worker exposure during nanomaterial production and handling processes
Ding, Y. and Kuhlbusch, T.A.J. and Van Tongeren, M. and Jiménez, A.S. and Tuinman, I. and Chen, R. and Alvarez, I.L. and Mikolajczyk, U. and Nickel, C. and Meyer, J. and Kaminski, H. and Wohlleben, W. and Stahlmecke, B. and Clava...
Journal of Hazardous Materials 322 17-28 (2017)For exposure and risk assessment in occupational settings involving engineered nanomaterials (ENMs), it is important to understand the mechanisms of release and how they are influenced by the ENM, the matrix material, and process characteristics. This review summarizes studies providing ENM release information in occupational settings, during different industrial activities and using various nanomaterials. It also assesses the contextual information — such as the amounts of materials handled, protective measures, and measurement strategies — to understand which release scenarios can result in exposure. High-energy processes such as synthesis, spraying, and machining were associated with the release of large numbers of predominantly small-sized particles. Low-energy processes, including laboratory handling, cleaning, and industrial bagging activities, usually resulted in slight or moderate releases of relatively large agglomerates. The present analysis suggests that process-based release potential can be ranked, thus helping to prioritize release assessments, which is useful for tiered exposure assessment approaches and for guiding the implementation of workplace safety strategies. The contextual information provided in the literature was often insufficient to directly link release to exposure. The studies that did allow an analysis suggested that significant worker exposure might mainly occur when engineering safeguards and personal protection strategies were not carried out as recommended. © 2016 Elsevier B.V.view abstract doi: 10.1016/j.jhazmat.2016.04.075 2017 • 613 Albumin-derived perfluorocarbon-based artificial oxygen carriers: A physico-chemical characterization and first in vivo evaluation of biocompatibility
Wrobeln, A. and Laudien, J. and Groß-Heitfeld, C. and Linders, J. and Mayer, C. and Wilde, B. and Knoll, T. and Naglav, D. and Kirsch, M. and Ferenz, K.B.
European Journal of Pharmaceutics and Biopharmaceutics 115 52-64 (2017)Until today, artificial oxygen carriers have not been reached satisfactory quality for routine clinical treatments. To bridge this gap, we designed albumin-derived perfluorocarbon-based nanoparticles as novel artificial oxygen carriers and evaluated their physico-chemical and pharmacological performance. Our albumin-derived perfluorocarbon-based nanoparticles (capsules), composed of an albumin shell and a perfluorodecalin core, were synthesized using ultrasonics. Their subsequent analysis by physico-chemical methods such as scanning electron-, laser scanning- and dark field microscopy as well as dynamic light scattering revealed spherically-shaped, nano-sized particles, that were colloidally stable when dispersed in 5% human serum albumin solution. Furthermore, they provided a remarkable maximum oxygen capacity, determined with a respirometer, reflecting a higher oxygen transport capacity than the competitor Perftoran®. Intravenous administration to healthy rats was well tolerated. Undesirable effects on either mean arterial blood pressure, hepatic microcirculation (determined by in vivo microscopy) or any deposit of capsules in organs, except the spleen, were not observed. Some minor, dose-dependent effects on tissue damage (release of cellular enzymes, alterations of spleen's micro-architecture) were detected. As our promising albumin-derived perfluorocarbon-based nanoparticles fulfilled decisive physico-chemical demands of an artificial oxygen carrier while lacking severe side-effects after in vivo administration they should be advanced to functionally focused in vivo testing conditions. © 2017 Elsevier B.V.view abstract doi: 10.1016/j.ejpb.2017.02.015 2017 • 612 Amine-Functionalized Silica Nanoparticles Incorporating Covalently Linked Visible-Light-Excitable Eu3+ Complexes: Synthesis, Characterization, and Cell-Uptake Studies
Francis, B. and Neuhaus, B. and Reddy, M.L.P. and Epple, M. and Janiak, C.
European Journal of Inorganic Chemistry 2017 3205-3213 (2017)We report the synthesis, characterization, photophysical investigations, and cell-uptake studies of luminescent silica nanoparticles incorporating covalently linked visible-light-excitable Eu3+ complexes. Visible-light excitation was accomplished by using highly conjugated carbazole-based β-diketonate ligands. Covalent incorporation of the Eu3+ complexes into the silica nanoparticles was achieved by modification of the bidentate phosphine oxide 4,6-bis(diphenylphosphoryl)-10H-phenoxazine (DPOXPO), which was used as the neutral donor for the Eu3+ ion. The surface amine functionalization of the nanoparticles was carried out using aminopropyltriethoxysilane (APTES). The prepared nanoparticles (Eu@Si-OH and Eu@Si-NH2) are around 35–40 nm in diameter, monodisperse, stable in aqueous dispersion, and also retain the luminescent properties of the incorporated Eu3+ complex. The synthesized nanoparticles exhibit a promising luminescence quantum yield of 38 % and an excited-state lifetime of 638 µs at physiological pH. The photobleaching experiments revealed that the developed nanoparticles are more photostable than the parent Eu3+ complex 1. In vitro experiments with Eu@Si-NH2 nanoparticles on HeLa cells showed that they are biocompatible and are readily taken up by cells. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/ejic.201700240 2017 • 611 Automated synthesis of quantum dot nanocrystals by hot injection: Mixing induced self-focusing
Salaheldin, A.M. and Walter, J. and Herre, P. and Levchuk, I. and Jabbari, Y. and Kolle, J.M. and Brabec, C.J. and Peukert, W. and Segets, D.
Chemical Engineering Journal 320 232-243 (2017)The hot injection technique for the synthesis of quantum dots (QDs) is a well-established and widely used method in the lab. However, scale-up rules do not exist. One reason is that in particular the role of process parameters like mixing on particle formation is largely unknown, as systematic examination of the latter is impossible for the laborious and complex manual synthesis. Herein we studied the mixing induced self-focusing of particle size distributions (PSDs) of CdSe QDs using automation in combination with a defined stirrer geometry. Basis for our study is a platform that allows parallelization with inline temperature monitoring, defined injection rate, accurate sampling times as well as controlled stirring. Reproducibility in terms of optical product properties was analyzed by absorption and emission whereas reproducibility in terms of the PSD was verified by deconvolution of UV/Vis absorbance spectra and especially by analytical ultracentrifugation (AUC) complemented by transmission electron microscopy (TEM). In line with previous results, AUC confirmed that even QDs made by hot injection in an automated setup are polydisperse with multimodal size distributions. Finally, reproducibility in combination with early stage sampling and controlled mixing allowed us for the first time to analyze the influence of stirring on focusing and defocusing of PSDs, that has been expressed in terms of the evolution of the relative standard deviation (RSD). Our work paves the way to gain in-depth understanding of often forgotten process-structure relationships of colloidal nanoparticles which eventually is a first step in the direction of the development of scalable synthesis and reliable application of high-quality QDs in technical applications. © 2017 Elsevier B.V.view abstract doi: 10.1016/j.cej.2017.02.154 2017 • 610 Avidin-conjugated calcium phosphate nanoparticles as a modular targeting system for the attachment of biotinylated molecules in vitro and in vivo
van der Meer, S.B. and Knuschke, T. and Frede, A. and Schulze, N. and Westendorf, A.M. and Epple, M.
Acta Biomaterialia 57 414-425 (2017)Avidin was covalently conjugated to the surface of calcium phosphate nanoparticles, coated with a thin silica shell and terminated by sulfhydryl groups (diameter of the solid core about 50 nm), with a bifunctional crosslinker connecting the amino groups of avidin to the sulfhydryl group on the nanoparticle surface. This led to a versatile nanoparticle system where all kinds of biotinylated (bio-)molecules can be easily attached to the surface by the non-covalent avidin-biotin-complex formation. It also permits the attachment of different biomolecules on the same nanoparticle (heteroavidity), creating a modular system for specific applications in medicine and biology. The variability of the binding to the nanoparticle surface of the was demonstrated with various biotinylated molecules, i.e. fluorescent dyes and antibodies. The accessibility of the conjugated avidin was demonstrated by a fluorescence-quenching assay. About 2.6 binding sites for biotin were accessible on each avidin tetramer. Together with a number of about 240 avidin tetramer units per nanoparticle, this offers about 600 binding sites for biotin on each nanoparticle. The uptake of fluorescently labelled avidin-conjugated calcium phosphate nanoparticles by HeLa cells showed the co-localization of fluorescent avidin and fluorescent biotin, indicating the stability of the complex under cell culture conditions. CD11c-antibody functionalized nanoparticles specifically targeted antigen-presenting immune cells (dendritic cells; DCs) in vitro and in vivo (mice) with high efficiency. Statement of significance Calcium phosphate nanoparticles have turned out to be very useful transporters for biomolecules into cells, both in vitro and in vivo. However, their covalent surface functionalization with antibodies, fluorescent dyes, or proteins requires a separate chemical synthesis for each kind of surface molecule. We have therefore developed avidin-terminated calcium phosphate nanoparticles to which all kinds of biotinylated molecules can be easily attached, also as a mixture of two or more molecules. This non-covalent bond is stable both in cell culture and after injection into mice in vivo. Thus, we have created a highly versatile system for many applications, from the delivery of biomolecules over the targeting of cells and tissue to in vivo imaging. © 2017 Acta Materialia Inc.view abstract doi: 10.1016/j.actbio.2017.05.049 2017 • 609 Changes within the stabilizing layer of ZnO nanoparticles upon washing
Schindler, T. and Schmutzler, T. and Schmiele, M. and Lin, W. and Segets, D. and Peukert, W. and Appavou, M.-S. and Kriele, A. and Gilles, R. and Unruh, T.
Journal of Colloid and Interface Science 504 356-362 (2017)ZnO nanoparticles (NPs) are highly relevant for various industrial applications, however, after synthesis of the NPs residual chemicals need to be removed from the colloidal raw product by washing, as they may influence the performance of the final device. In the present study we focus on the effect of washing by antisolvent flocculation with subsequent redispersion of the NPs on the stabilizing acetate shell. Purification of the ZnO nanoparticles is reported to be optimal with respect to zeta potential that has a maximum after one washing cycle. In this work, we will shed light on this observation using small angle X-ray and neutron scattering (SAXS, SANS) by demonstrating that after the first washing cycle the content of acetate in the ligand shell around the ZnO NPs increases. In detail, it was observed that the diffuse acetate shell shrinks to the size of a monolayer upon washing but the acetate content of this monolayer is higher than within the diffuse shell of the particles of the native dispersion. A second washing cycle reduces the acetate concentration within the stabilizing shell and the stability of the dispersion drops accordingly. After another (third) washing cycle strong agglomeration was observed for all investigated samples. © 2017 Elsevier Inc.view abstract doi: 10.1016/j.jcis.2017.05.059 2017 • 608 Characterization of anisotropically shaped silver nanoparticle arrays via spectroscopic ellipsometry supported by numerical optical modeling
Gkogkou, D. and Shaykhutdinov, T. and Oates, T.W.H. and Gernert, U. and Schreiber, B. and Facsko, S. and Hildebrandt, P. and Weidinger, I.M. and Esser, N. and Hinrichs, K.
Applied Surface Science 421 460-464 (2017)The present investigation aims to study the optical response of anisotropic Ag nanoparticle arrays deposited on rippled silicon substrates by performing a qualitative comparison between experimental and theoretical results. Spectroscopic ellipsometry was used along with numerical calculations using finite-difference time-domain (FDTD) method and rigorous coupled wave analysis (RCWA) to reveal trends in the optical and geometrical properties of the nanoparticle array. Ellipsometric data show two resonances, in the orthogonal x and y directions, that originate from localized plasmon resonances as demonstrated by the calculated near-fields from FDTD calculations. The far-field calculations by RCWA point to decoupled resonances in x direction and possible coupling effects in y direction, corresponding to the short and long axis of the anisotropic nanoparticles, respectively. © 2016 Elsevier B.V.view abstract doi: 10.1016/j.apsusc.2016.10.105 2017 • 607 Chemoenzymatic one-pot reaction of noncompatible catalysts: Combining enzymatic ester hydrolysis with Cu(i)/bipyridine catalyzed oxidation in aqueous medium
Sand, H. and Weberskirch, R.
RSC Advances 7 33614-33626 (2017)The combination of chemical catalysts and biocatalysts in a one-pot reaction has attracted considerable interest in the past years. However, since each catalyst requires very different reaction conditions, chemoenzymatic one-pot reactions in aqueous media remain challenging and are limited today to metal-catalysts that display high activity in aqueous media. Here, we report the first combination of two incompatible catalytic systems, a lipase based ester hydrolysis with a water-sensitive Cu/bipyridine catalyzed oxidation reaction, in a one-pot reaction in aqueous medium (PBS buffer). Key to the solution was the compartmentalization of the Cu/bipyridine catalyst in a core-shell like nanoparticle. We show the synthesis and characterization of the Cu/bipyridine functionalized nanoparticles and the application in the oxidation of allylic and benzylic alcohols in aqueous media. Furthermore, the work demonstrates the implementation of a one-pot reaction process with optimized reaction conditions involving a lipase (CAL-B) to hydrolyze various acetate ester substrates in the first step, followed by oxidation of the resulting alcohols to the corresponding aldehydes under aerobic conditions in aqueous media. © 2017 The Royal Society of Chemistry.view abstract doi: 10.1039/c7ra05451c 2017 • 606 Choosing the right nanoparticle size-designing novel ZnO electrode architectures for efficient dye-sensitized solar cells
Pfau, M.W. and Kunzmann, A. and Segets, D. and Peukert, W. and Wallace, G.G. and Officer, D.L. and Clark, T. and Costa, R.D. and Guldi, D.M.
Journal of Materials Chemistry A 5 7516-7522 (2017)A novel concept for constructing optimized ZnO-based photoanodes as integrative components of dye-sensitized solar cells (DSSCs) is realized by deploying differently sized nanoparticles, ranging from 2 to 10 nm, together with commercially available 20 nm nanoparticles. The 2 nm nanoparticles were used to construct an efficient buffer layer for transparent electrodes based on 10 nm nanoparticles, resulting in a relative increase of device efficiency from 1.8 to 3.0% for devices without and with a buffer layer, respectively. A mixture of 10 and 20 nm nanoparticles was optimized to maximize the diffuse reflection and to minimize the charge transport resistance in a light-scattering layer. This optimization resulted in a homogenous layer of more than 15 μm that provided a device efficiency of 3.3%. The buffer layer, transparent electrode, and light-scattering electrode, were then combined to give an overall efficiency of around 5%. Thus, this work demonstrates that varying the electrode architecture with nanoparticles of different diameters is a powerful strategy for improving the overall efficiency of ZnO-based DSSCs. © The Royal Society of Chemistry.view abstract doi: 10.1039/c6ta11012f 2017 • 605 Co3O4@Co/NCNT Nanostructure Derived from a Dicyanamide-Based Metal-Organic Framework as an Efficient Bi-functional Electrocatalyst for Oxygen Reduction and Evolution Reactions
Sikdar, N. and Konkena, B. and Masa, J. and Schuhmann, W. and Maji, T.K.
Chemistry - A European Journal 23 18049-18056 (2017)There has been growing interest in the synthesis of efficient reversible oxygen electrodes for both the oxygen reduction reaction (ORR) and the oxygen evolution reactions (OER), for their potential use in a variety of renewable energy technologies, such as regenerative fuel cells and metal-air batteries. Here, a bi-functional electrocatalyst, derived from a novel dicyanamide based nitrogen rich MOF {[Co(bpe)2(N(CN)2)]⋅(N(CN)2)⋅(5 H2O)}n [Co-MOF-1, bpe=1,2-bis(4-pyridyl)ethane, N(CN)2 −=dicyanamide] under different pyrolysis conditions is reported. Pyrolysis of the Co-MOF-1 under Ar atmosphere (at 800 °C) yielded a Co nanoparticle-embedded N-doped carbon nanotube matrix (Co/NCNT-Ar) while pyrolysis under a reductive H2/Ar atmosphere (at 800 °C) and further mild calcination yielded Co3O4@Co core–shell nanoparticle-encapsulated N-doped carbon nanotubes (Co3O4@Co/NCNT). Both catalysts show bi-functional activity towards ORR and OER, however, the core–shell Co3O4@Co/NCNT nanostructure exhibited superior electrocatalytic activity for both the ORR with a potential of 0.88 V at a current density of −1 mA cm−2 and the OER with a potential of 1.61 V at 10 mA cm−2, which is competitive with the most active bi-functional catalysts reported previously. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/chem.201704211 2017 • 604 Cobalt boride modified with N-doped carbon nanotubes as a high-performance bifunctional oxygen electrocatalyst
Elumeeva, K. and Masa, J. and Medina, D. and Ventosa, E. and Seisel, S. and Kayran, Y.U. and Genç, A. and Bobrowski, T. and Weide, P. and Arbiol, J. and Muhler, M. and Schuhmann, W.
Journal of Materials Chemistry A 5 21122-21129 (2017)The development of reversible oxygen electrodes, able to drive both the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR), is still a great challenge. We describe a very efficient and stable bifunctional electrocatalytic system for reversible oxygen electrodes obtained by direct CVD growth of nitrogen-doped carbon nanotubes (NCNTs) on the surface of cobalt boride (CoB) nanoparticles. A detailed investigation of the crystalline structure and elemental distribution of CoB before and after NCNT growth reveals that the NCNTs grow on small CoB nanoparticles formed in the CVD process. The resultant CoB/NCNT system exhibited outstanding activity in catalyzing both the OER and the ORR in 0.1 M KOH with an overvoltage difference of only 0.73 V between the ORR at -1 mA cm-2 and the OER at +10 mA cm-2. The proposed CoB/NCNT catalyst showed stable performance during 50 h of OER stability assessment in 0.1 M KOH. Moreover, CoB/NCNT spray-coated on a gas diffusion layer as an air-breathing electrode proved its high durability during 170 galvanostatic charge-discharge (OER/ORR) test cycles (around 30 h) at ±10 mA cm-2 in 6 M KOH, making it an excellent bifunctional catalyst for potential Zn-air battery application. © 2017 The Royal Society of Chemistry.view abstract doi: 10.1039/c7ta06995b 2017 • 603 Colloidal Stability and Surface Chemistry Are Key Factors for the Composition of the Protein Corona of Inorganic Gold Nanoparticles
Johnston, B.D. and Kreyling, W.G. and Pfeiffer, C. and Schäffler, M. and Sarioglu, H. and Ristig, S. and Hirn, S. and Haberl, N. and Thalhammer, S. and Hauck, S.M. and Semmler-Behnke, M. and Epple, M. and Hühn, J. and Del Pino, ...
Advanced Functional Materials 27 (2017)To study the influence of colloidal stability on protein corona formation, gold nanoparticles are synthesized with five distinct surface modifications: coating with citric acid, bis(p-sulfonatophenyl)phenylphosphine dihydrate dipotassium salt, thiol-terminated methoxy-polyethylene glycol, dodecylamine-grafted poly(isobutylene-alt-maleic anhydride), and dodecylamine-grafted poly(isobutylene-alt-maleic anhydride) conjugated with polyethylene glycol. The nanoparticles are incubated with serum or bronchoalveolar lavage fluid from C57BL/6 mice (15 min or 24 h) to assess the effect of differential nanoparticle surface presentation on protein corona formation in the air–blood barrier exposure pathway. Proteomic quantification and nanoparticle size measurements are used to assess protein corona formation. We show that surface modification has a clear effect on the size and the composition of the protein corona that is related to the colloidal stability of the studied nanoparticles. Additionally, differences in the composition and size of the protein corona are shown between biological media and duration of exposure, indicating evolution of the corona through this exposure pathway. Consequently, a major determinant of protein corona formation is the colloidal stability of nanoparticles in biological media and chemical or environmental modification of the nanoparticles alters the surface presentation of the functional epitope in vivo. Therefore, the colloidal stability of nanoparticles has a decisive influence on nano–bio interactions. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/adfm.201701956 2017 • 602 Comparison between periodicity and randomness from an effective refractive index point of view; Applicable to thin-film solar cells
Jalali, M. and Nadgaran, H. and Erni, D.
Scientia Iranica 24 3536-3541 (2017)In this paper, embedding plasmonic nanoparticles inside the solar cell's active layer, both in a periodic and in a random manner, is extensively investigated. The aim of this study is to investigate optical mechanisms inside the active layer as a consequence of nanoparticle inclusion as well as to compare periodicity and randomness in such structures, where the intended maximization of the ultra-broadband absorption renders the analysis complicated. To perform such study, an effective refractive index analysis is employed to simultaneously cover the influential parameters. The results show that although fully periodic structures are more desirable in narrow-band applications such as grating-assisted waveguide coupling, random inclusion of plasmonic nanoparticles in the solar cell's active layer yields a much higher optical absorption. Furthermore, random inclusion of nanoparticles is easier and much cheaper than periodic inclusion to implement in solar cell fabrication. © 2017 Sharif University of Technology. All rights reserved.view abstract doi: 10.24200/sci.2017.4596 2017 • 601 Concentrating light in Cu-In;Ga-Se2 solar cells
Schmid, M. and Yin, G. and Song, A.M. and Duan, S. and Heidmann, B. and Sancho-Martinez, D. and Kämmer, S. and Köhler, T. and Manley, P. and Lux-Steiner, M.Ch.
Journal of Photonics for Energy 7 (2017)Light concentration has proven beneficial for solar cells, most notably for highly efficient but expensive absorber materials using high concentrations and large scale optics. Here, we investigate the light concentration for cost-efficient thin-film solar cells that show nano- or microtextured absorbers. Our absorber material of choice is CuIn; GaSe2 (CIGSe), which has a proven stabilized record efficiency of 22.6% and which-despite being a polycrystalline thin-film material-is very tolerant to environmental influences. Taking a nanoscale approach, we concentrate light in the CIGSe absorber layer by integrating photonic nanostructures made from dielectric materials. The dielectric nanostructures give rise to resonant modes and field localization in their vicinity. Thus, when inserted inside or adjacent to the absorber layer, absorption and efficiency enhancement are observed. In contrast to this internal absorption enhancement, external enhancement is exploited in the microscaled approach: mm-sized lenses can be used to concentrate light onto CIGSe solar cells with lateral dimensions reduced down to the micrometer range. These micro solar cells come with the benefit of improved heat dissipation compared with the large scale concentrators and promise compact high-efficiency devices. Both approaches of light concentration allow for reduction in material consumption by restricting the absorber dimension either vertically (ultrathin absorbers for dielectric nanostructures) or horizontally (microabsorbers for concentrating lenses) and have significant potential for efficiency enhancement. ©2017 Society of Photo-Optical Instrumentation Engineers (SPIE).view abstract doi: 10.1117/1.JPE.7.018001 2017 • 600 Decoupling the Effects of High Crystallinity and Surface Area on the Photocatalytic Overall Water Splitting over β-Ga2O3 Nanoparticles by Chemical Vapor Synthesis
Lukic, S. and Menze, J. and Weide, P. and Busser, G.W. and Winterer, M. and Muhler, M.
ChemSusChem 10 4190-4197 (2017)Chemical vapor synthesis (CVS) is a unique method to prepare well-defined photocatalyst materials with both large specific surface area and a high degree of crystallinity. The obtained β-Ga2O3 nanoparticles were optimized for photocatalysis by reductive photodeposition of the Rh/CrOx co-catalyst system. The influence of the degree of crystallinity and the specific surface area on photocatalytic aqueous methanol reforming and overall water splitting (OWS) was investigated by synthesizing β-Ga2O3 samples in the temperature range from 1000 °C to 1500 °C. With increasing temperature, the specific surface area and the microstrain were found to decrease, whereas the degree of crystallinity and the crystallite size increased. Whereas the photocatalyst with the highest specific surface area showed the highest aqueous methanol reforming activity, the highest OWS activity was that for the sample with an optimum ratio between high degree of crystallinity and specific surface area. Thus, it was possible to show that the facile aqueous methanol reforming and the demanding OWS have different requirements for high photocatalytic activity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/cssc.201701309 2017 • 599 Delivery of the autofluorescent protein Rphycoerythrin by calcium phosphate nanoparticles into four different eukaryotic cell lines (HeLa, HEK293T, MG-63, MC3T3): Highly efficient, but leading to endolysosomal proteolysis in HeLa and MC3T3 cells
Kopp, M. and Rotan, O. and Papadopoulos, C. and Schulze, N. and Meyer, H. and Epple, M.
PLoS ONE 12 (2017)Nanoparticles can be used as carriers to transport biomolecules like proteins and synthetic molecules across the cell membrane because many molecules are not able to cross the cell membrane on their own. The uptake of nanoparticles together with their cargo typically occurs via endocytosis, raising concerns about the possible degradation of the cargo in the endolysosomal system. As the tracking of a dye-labelled protein during cellular uptake and processing is not indicative of the presence of the protein itself but only for the fluorescent label, a label-free tracking was performed with the red-fluorescing model protein R-phycoerythrin (R-PE). Four different eukaryotic cell lines were investigated: HeLa, HEK293T, MG-63, and MC3T3. Alone, the protein was not taken up by any cell line; only with the help of calcium phosphate nanoparticles, an efficient uptake occurred. After the uptake into HeLa cells, the protein was found in early endosomes (shown by the marker EEA1) and lysosomes (shown by the marker Lamp1). There, it was still intact and functional (i.e. properly folded) as its red fluorescence was detected. However, a few hours after the uptake, proteolysis started as indicated by the decreasing red fluorescence intensity in the case of HeLa and MC3T3 cells. 12 h after the uptake, the protein was almost completely degraded in HeLa cells and MC3T3 cells. In HEK293T cells and MG-63 cells, no degradation of the protein was observed. In the presence of Bafilomycin A1, an inhibitor of acidification and protein degradation in lysosomes, the fluorescence of R-PE remained intact over the whole observation period in the four cell lines. These results indicate that despite an efficient nanoparticle-mediated uptake of proteins by cells, a rapid endolysosomal degradation may prevent the desired (e.g. therapeutic) effect of a protein inside a cell. © 2017 Kopp et al.This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.view abstract doi: 10.1371/journal.pone.0178260 2017 • 598 Dependence of the optical constants and the performance in the SPREE gas measurement on the thickness of doped tin oxide over coatings
Fischer, D. and Hertwig, A. and Beck, U. and Negendank, D. and Lohse, V. and Kormunda, M. and Esser, N.
Applied Surface Science 421 480-486 (2017)In this study, thickness related changes of the optical properties of doped tin oxide were studied. Two different sets of samples were prepared. The first set was doped with iron or nickel on silicon substrate with thicknesses of 29-56. nm, the second was iron doped on gold/glass substrate with 1.6-6.3. nm. The optical constants were determined by using spectral ellipsometry (SE) followed by modelling of the dielectric function with an oscillator model using Gaussian peaks. The analysis of the optical constants shows a dependence of the refraction and the absorption on the thickness of the doped tin oxide coating. In addition to the tin oxide absorption in the UV, one additional absorption peak was found in the near-IR/red which is related to plasmonic effects due to the doping. This peak shifts from the near-IR to the red part of the visible spectrum and becomes stronger by reducing the thickness, probably due to the formation of metal nanoparticles in this layer. These results were found for two different sets of samples by using the same optical model. Afterwards the second sample set was tested in the Surface Plasmon Resonance Enhanced Ellipsometric (SPREE) gas measurement with CO gas. It was found that the thickness has significant influence on the sensitivity and thus the adsorption of the CO gas. By increasing the thickness from 1.6. nm to 5.1. nm, the sensing ability is enhanced due to a higher coverage of the surface with the over coating. This is explained by the high affinity of CO molecules to the incorporated Fe-nanoparticles in the tin oxide coating. By increasing the thickness further to 6.3. nm, the sensing ability drops because the layer disturbs the SPR sensing effect too much. © 2016.view abstract doi: 10.1016/j.apsusc.2016.11.188 2017 • 597 Direct Integration of Laser-Generated Nanoparticles into Transparent Nail Polish: The Plasmonic "goldfinger"
Lau, M. and Waag, F. and Barcikowski, S.
Industrial and Engineering Chemistry Research 56 3291-3296 (2017)A transparent nail varnish can be colored simply and directly with laser-generated nanoparticles. This does not only enable coloring of the varnish for cosmetic purposes, but also gives direct access to nanodoped varnishes to be used on any solid surface. Therefore, nanoparticle properties such as plasmonic properties or antibacterial effects can be easily adapted to surfaces for medical or optical purposes. The presented method for integration of metal (gold, platinum, silver, and alloy) nanoparticles into varnishes is straightforward and gives access to nanodoped polishes with optical properties, difficult to be achieved by dispersing powder pigments in the high-viscosity liquids. © 2017 American Chemical Society.view abstract doi: 10.1021/acs.iecr.7b00039 2017 • 596 Effect of titania surface modification of mesoporous silica SBA-15 supported Au catalysts: Activity and stability in the CO oxidation reaction
Kučerová, G. and Strunk, J. and Muhler, M. and Behm, R.J.
Journal of Catalysis 356 214-228 (2017)As part of an ongoing effort to understand the deactivation and improve the stability of metal oxide-supported Au catalysts in the low-temperature CO oxidation reaction while maintaining their high activity, we have investigated the influence of a mesoporous silica SBA-15 substrate on the activity and stability of Au/TiO2 catalysts, which consist of a SBA-15 support surface modified by a monolayer of TiOx with Au nanoparticles on top. The extent of the TiOx surface modification was systematically increased, while the Au loading and the Au particle sizes were largely kept constant. Employing kinetic measurements at three different temperatures (30 °C, 80 °C, 180 °C) and a number of ex situ methods as well as in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) for catalyst characterization, we found that the activity of these catalysts increases significantly with the Ti concentration and with reaction temperature. The tendency for deactivation remains essentially unchanged. Detailed in situ DRIFTS measurements reveal that the Au nanoparticles are largely formed on the TiOx surface-modified areas of the SBA-15 support and that the tendency for surface carbonate formation is very low. The observed deactivation may at least partly be related to the accumulation of molecularly adsorbed H2O species, in particular at low temperatures (30 °C). These are likely to be formed from surface hydroxyl groups, they may affect the reaction either by blocking of active sites or by blocking the adsorption of reactants on the substrate. Other effects, such as reaction induced changes in the titania layer, must however, play a role as well, both at 80 °C and in particular at 180 °C, where accumulation of adsorbed species is negligible. The mechanistic ideas are supported by reactivation tests subsequent to calcination at 400 °C, which were found to fully restore the initial activity. © 2017 Elsevier Inc.view abstract doi: 10.1016/j.jcat.2017.09.017 2017 • 595 Efficient Gene Transfection through Inhibition of β-Sheet (Amyloid Fiber) Formation of a Short Amphiphilic Peptide by Gold Nanoparticles
Jana, P. and Samanta, K. and Bäcker, S. and Zellermann, E. and Knauer, S. and Schmuck, C.
Angewandte Chemie - International Edition (2017)The effect of citrate-stabilized gold nanoparticles (AuNPs) on the secondary structure of an artificial β-sheet-forming cationic peptide has been studied. The AuNPs inhibited β-sheet formation and led to fragmented fibrils and spherical oligomers with assembled AuNPs on their surface. Besides this structural change, the functional properties of the peptide are also different. Whereas the peptide was unable to act as a vector for gene delivery, formation of a complex with AuNPs allowed successful gene delivery into cells. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/anie.201700713 2017 • 594 Encapsulation of Bimetallic Metal Nanoparticles into Robust Zirconium-Based Metal-Organic Frameworks: Evaluation of the Catalytic Potential for Size-Selective Hydrogenation
Rösler, C. and Dissegna, S. and Rechac, V.L. and Kauer, M. and Guo, P. and Turner, S. and Ollegott, K. and Kobayashi, H. and Yamamoto, T. and Peeters, D. and Wang, Y. and Matsumura, S. and Van Tendeloo, G. and Kitagawa, H. and Mu...
Chemistry - A European Journal 23 3583-3594 (2017)The realization of metal nanoparticles (NPs) with bimetallic character and distinct composition for specific catalytic applications is an intensively studied field. Due to the synergy between metals, most bimetallic particles exhibit unique properties that are hardly provided by the individual monometallic counterparts. However, as small-sized NPs possess high surface energy, agglomeration during catalytic reactions is favored. Sufficient stabilization can be achieved by confinement of NPs in porous support materials. In this sense, metal-organic frameworks (MOFs) in particular have gained a lot of attention during the last years; however, encapsulation of bimetallic species remains challenging. Herein, the exclusive embedding of preformed core-shell PdPt and RuPt NPs into chemically robust Zr-based MOFs is presented. Microstructural characterization manifests partial retention of the core-shell systems after successful encapsulation without harming the crystallinity of the microporous support. The resulting chemically robust NP@UiO-66 materials exhibit enhanced catalytic activity towards the liquid-phase hydrogenation of nitrobenzene, competitive with commercially used Pt on activated carbon, but with superior size-selectivity for sterically varied substrates. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/chem.201603984 2017 • 593 Enhancement of photocurrent in an ultra-thin perovskite solar cell by Ag nanoparticles deposited at low temperature
Liu, Y. and Lang, F. and Dittrich, T. and Steigert, A. and Fischer, C.-H. and Köhler, T. and Plate, P. and Rappich, J. and Lux-Steiner, M.Ch. and Schmid, M.
RSC Advances 7 1206-1214 (2017)Ultra-thin perovskite absorber layers have attracted increasing interest since they are suitable for application in semi-transparent perovskite and tandem solar cells. In this study, size and density controlled plasmonic silver nanoparticles are successfully incorporated into ultra-thin perovskite solar cells through a low temperature spray chemical vapor deposition method. Incorporation of Ag nanoparticles leads to a significant enhancement of 22.2% for the average short-circuit current density. This resulted in a relative improvement of 22.5% for the average power conversion efficiency. Characterization by surface photovoltage and photoluminescence provides evidence that the implemented silver nanoparticles can enhance the charge separation and the trapping of electrons into the TiO2 layer at the CH3NH3PbI3/TiO2 interface. The application of these silver nanoparticles therefore has promise to enhance the ultra-thin perovskite solar cells. © The Royal Society of Chemistry.view abstract doi: 10.1039/C6RA25149H 2017 • 592 Experimental and numerical study of a HMDSO-seeded premixed laminar low-pressure flame for SiO2 nanoparticle synthesis
Feroughi, O.M. and Deng, L. and Kluge, S. and Dreier, T. and Wiggers, H. and Wlokas, I. and Schulz, C.
Proceedings of the Combustion Institute 36 1045-1053 (2017)Silicon dioxide nanoparticles are generated in a lean hydrogen/oxygen flat flame doped with small amounts of hexamethyldisiloxane (HMDSO) stabilized by a water-cooled sintered bronze matrix. The burner is housed in an optically-accessible low-pressure (3kPa) chamber. Temperature fields were determined via multi-line laser-induced fluorescence (LIF) using added NO as target species. Gas-phase silicon oxide (SiO) was detected via laser-induced fluorescence (LIF) by exciting the weakly temperature-dependent rovibrational Q11(32) transition in the A-X (0,0) vibronic band system at 235.087nm. Semi-quantitative concentration profiles as a function of height-above-burner (HAB) were obtained after exploiting the measured temperature fields and correcting measured LIF intensities for the temperature-dependence of the ground-state population and collisional quenching using measured effective fluorescence lifetimes. Particle sizes were determined as a function of HAB via molecular-beam sampling with subsequent particle mass spectrometry (PMS). The experimental data were used to develop a simple kinetics model of HMDSO combustion and SiO2 particle precursor formation with subsequent nucleation and particle growth in the H2/O2 flame. The model was incorporated in a CFD simulation to account for facility effects that arise from modified flow fields and heat transfer between the flame and the reactor chamber. © 2016 Elsevier Ltd.view abstract doi: 10.1016/j.proci.2016.07.131 2017 • 591 Experimental and Theoretical Understanding of Nitrogen-Doping-Induced Strong Metal-Support Interactions in Pd/TiO2 Catalysts for Nitrobenzene Hydrogenation
Chen, P. and Khetan, A. and Yang, F. and Migunov, V. and Weide, P. and Stürmer, S.P. and Guo, P. and Kähler, K. and Xia, W. and Mayer, J. and Pitsch, H. and Simon, U. and Muhler, M.
ACS Catalysis 7 1197-1206 (2017)By doping the TiO2 support with nitrogen, strong metal-support interactions (SMSI) in Pd/TiO2 catalysts can be tailored to obtain high-performance supported Pd nanoparticles (NPs) in nitrobenzene (NB) hydrogenation catalysis. According to the comparative studies by X-ray diffraction, X-ray photoelectron spectroscopy (XPS), and diffuse reflectance CO FTIR (CO-DRIFTS), N-doping induced a structural promoting effect, which is beneficial for the dispersion of Pd species on TiO2. High-angle annular dark-field scanning transmission electron microscopy study of Pd on N-doped TiO2 confirmed a predominant presence of sub-2 nm Pd NPs, which are stable under the applied hydrogenation conditions. XPS and CO-DRIFTS revealed the formation of strongly coupled Pd-N species in Pd/TiO2 with N-doped TiO2 as support. Density functional theory (DFT) calculations over model systems with Pdn (n = 1, 5, or 10) clusters deposited on TiO2(101) surface were performed to verify and supplement the experimental observations. In hydrogenation catalysis using NB as a model molecule, Pd NPs on N-doped TiO2 outperformed those on N-free TiO2 in terms of both catalytic activity and stability, which can be attributed to the presence of highly dispersed Pd NPs providing more active sites, and to the formation of Pd-N species favoring the dissociative adsorption of the reactant NB and the easier desorption of the product aniline. (Figure Presented). © 2016 American Chemical Society.view abstract doi: 10.1021/acscatal.6b02963 2017 • 590 Experimental identification of unique angular dependent scattering behavior of nanoparticles
Yin, G. and Song, M. and Raja, W. and Andrae, P. and Schmid, M.
Journal of the European Optical Society 13 (2017)Background: Nanoparticles exhibit unique light scattering properties and are applied in many research fields. Methods: In this work, we perform angular resolved scattering measurements to study the scattering behaviour of random and periodic silver (Ag), and periodic polystyrene (PS) nanoparticles. Results: The random Ag nanoparticles, with a wide particle size distribution, are able to broadbandly scatter light into large angles. In contrast, both types of periodic nanoparticles are characterized by a strong scattering zone where scattering angles are increasing as the wavelength increases. Conclusions: Angular resolved scattering measurements enable experimentally revealing the particular scattering properties of different nanostructures. © 2017, The Author(s).view abstract doi: 10.1186/s41476-017-0066-4 2017 • 589 Film forming properties of silicon nanoparticles on SixNy coated substrates during excimer laser annealing
Caninenberg, M. and Kiesler, D. and Benson, N. and Schmechel, R.
Optics and Laser Technology 90 33-39 (2017)In this article we investigate the film forming properties of excimer laser annealed silicon nanoparticles on non-silicon substrates. In contrast to their film forming properties on oxide free silicon substrates, the nanoparticle thin film tends to dewet and form a porous µ-structure on the silicon nitrite covered glass model substrates considered for our investigation. This is quantified using a SEM study in conjunction with image processing software, in order to evaluate the µ-structure size and inter µ-structure distance in dependence of the laser energy density. To generalize our results, the film forming process is described using a COMSOL Multiphysics ® fluid dynamics model, which solves the Navier Stokes equation for incompressible Newtonian fluids. To account for the porous nanoparticle thin film structure in the simulation, an effective medium approach is used by applying a conservative level set one phase method to our mesh. This effort allows us to predict the Si melt film formation ranging from a porous Si µ-structure to a compact 100% density Si thin film in dependence of the substrate / thin film interaction, as well as the laser energy used for the nanoparticle processing. © 2016 Elsevier Ltdview abstract doi: 10.1016/j.optlastec.2016.11.010 2017 • 588 Fluence Threshold Behaviour on Ablation and Bubble Formation in Pulsed Laser Ablation in Liquids
Reich, S. and Schönfeld, P. and Letzel, A. and Kohsakowski, S. and Olbinado, M. and Gökce, B. and Barcikowski, S. and Plech, A.
ChemPhysChem 18 1084-1090 (2017)The ablation yield and bubble-formation process during nanosecond pulsed-laser ablation of silver in water are analysed by stroboscopic videography, time-resolved X-ray radiography and in situ UV/Vis spectroscopy. This process is studied as function of lens–target distance and laser fluence. Both the ablation yield and the bubble-cavitation process exhibit threshold behaviour as a function of fluence, which is linked to the efficiency of coupling of energy at the water/target interface. Although ablation happens below this threshold, quantitative material emission is linked to bubble formation. Above the threshold, both bubble size and ablation show linear behaviour. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/cphc.201601198 2017 • 587 Formation Mechanism of Laser-Synthesized Iron-Manganese Alloy Nanoparticles, Manganese Oxide Nanosheets and Nanofibers
Zhang, D. and Ma, Z. and Spasova, M. and Yelsukova, A.E. and Lu, S. and Farle, M. and Wiedwald, U. and Gökce, B.
Particle and Particle Systems Characterization 34 1600225 (2017)Laser ablation in liquids (LAL) has emerged as a versatile approach for the synthesis of alloy particles and oxide nanomaterials. However, complex chemical reactions often take place during synthesis due to inevitable atomization and ionization of the target materials and decomposition/hydrolysis of solvent/solution molecules, making it difficult to understand the particle formation mechanisms. In this paper, a possible route for the formation of FeMn alloy nanoparticles as well as MnOx nanoparticles, -sheets, and -fibers by LAL is presented. The observed structural, compositional, and morphological variations are clarified by transmission electron microscopy (TEM). The studies suggest that a reaction between Mn atoms and Fe ions followed by surface oxidation result in nonstoichiometric synthesis of Fe-rich FeMn@FeMn2O4 core-shell alloy particles. Interestingly, a phase transformation from Mn3O4 to Mn2O3 and finally to Ramsdellite γ-MnO2 is accompanied by a morphology change from nanosheets to nanofibers in gradually increasing oxidizing environments. High-resolution TEM images reveal that the particle-attachment mechanism dominates the growth of different manganese oxides. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/ppsc.201600225 2017 • 586 High productive and continuous nanoparticle fabrication by laser ablation of a wire-target in a liquid jet
Kohsakowski, S. and Santagata, A. and Dell'Aglio, M. and de Giacomo, A. and Barcikowski, S. and Wagener, P. and Gökce, B.
Applied Surface Science 403 487-499 (2017)To scale-up pulsed laser ablation in liquids for nanoparticle synthesis, we combine two promising approaches, a wire-shaped target and a small liquid layer, in one setup. Using thin liquid layers a significant increase in nanoparticle productivity (up to 5 times) is obtained. This increase is attributed to the dynamics, shape of the cavitation bubble and the spring-board like behavior of the wires in the small liquid filament. It is found that despite the increase in productivity, the particle size is independent of the productivity-related ablation parameters such as repetition rate, liquid layer thickness and wire diameter. In addition to the cavitation bubble, further shielding effects have been related to both, the laser ablated material and the presence of generated small vapor bubbles. The obtained results show that this setup can provide a good strategy to realize a continuous and process-stable (particle size and quality) ablation process without the need of target replacement. © 2017 Elsevier B.V.view abstract doi: 10.1016/j.apsusc.2017.01.077 2017 • 585 High surface area, amorphous titania with reactive Ti3+ through a photo-assisted synthesis method for photocatalytic H2 generation
Zywitzki, D. and Jing, H. and Tüysüz, H. and Chan, C.K.
Journal of Materials Chemistry A 5 10957-10967 (2017)Amorphous titania-based photocatalysts are synthesized using a facile, UV-light mediated method and evaluated as photocatalysts for hydrogen evolution from water/methanol mixtures. The photocatalysts are prepared through the direct injection of a titanium alkoxide precursor into a water/methanol mixture, with subsequent hydrolysis, condensation, and polycondensation to form TiOx(OH)y species under UV-irradiation. The resulting amorphous titania materials exhibit an overall higher hydrogen evolution rate compared to a crystalline TiO2 reference (P25) on a molar basis of the photocatalyst due to their highly porous structure and high surface area (∼500 m2 g-1). The employed titanium alkoxide precursor did not play a major role in affecting the hydrogen evolution rate or the catalyst surface and morphology. A blue coloration, which is associated with the formation of Ti3+ species, was observed in the amorphous titania but not in P25 upon light irradiation and is enabled by the porous and disordered structure of the amorphous photocatalyst. The Ti3+ species are also used to reduce protons to H2 in the absence of light irradiation or reduce Pt2+ to form Pt nanoparticles. These Pt nanoparticles are smaller and better dispersed on the photocatalyst compared to particles prepared using conventional photodeposition, leading to higher H2 evolution rates. The results show that the direct injection method is a facile approach for the preparation of high surface area titania photocatalysts containing Ti3+ species with good photocatalytic activity for the production of H2. © 2017 The Royal Society of Chemistry.view abstract doi: 10.1039/c7ta01614j 2017 • 584 High-Performance Energy Storage and Conversion Materials Derived from a Single Metal-Organic Framework/Graphene Aerogel Composite
Xia, W. and Qu, C. and Liang, Z. and Zhao, B. and Dai, S. and Qiu, B. and Jiao, Y. and Zhang, Q. and Huang, X. and Guo, W. and Dang, D. and Zou, R. and Xia, D. and Xu, Q. and Liu, M.
Nano Letters 17 2788-2795 (2017)Metal oxides and carbon-based materials are the most promising electrode materials for a wide range of low-cost and highly efficient energy storage and conversion devices. Creating unique nanostructures of metal oxides and carbon materials is imperative to the development of a new generation of electrodes with high energy and power density. Here we report our findings in the development of a novel graphene aerogel assisted method for preparation of metal oxide nanoparticles (NPs) derived from bulk MOFs (Co-based MOF, Co(mIM)2 (mIM = 2-methylimidazole). The presence of cobalt oxide (CoOx) hollow NPs with a uniform size of 35 nm monodispersed in N-doped graphene aerogels (NG-A) was confirmed by microscopic analyses. The evolved structure (denoted as CoOx/NG-A) served as a robust Pt-free electrocatalyst with excellent activity for the oxygen reduction reaction (ORR) in an alkaline electrolyte solution. In addition, when Co was removed, the resulting nitrogen-rich porous carbon-graphene composite electrode (denoted as C/NG-A) displayed exceptional capacitance and rate capability in a supercapacitor. Further, this method is readily applicable to creation of functional metal oxide hollow nanoparticles on the surface of other carbon materials such as graphene and carbon nanotubes, providing a good opportunity to tune their physical or chemical activities. © 2017 American Chemical Society.view abstract doi: 10.1021/acs.nanolett.6b05004 2017 • 583 Imaging techniques: Nanoparticle atoms pinpointed
Farle, M.
Nature 542 35-36 (2017)The locations of atoms in a metallic alloy nanoparticle have been determined using a combination of electron microscopy and image simulation, revealing links between the particle's structure and magnetic properties.view abstract doi: 10.1038/542035a 2017 • 582 Improving the zT value of thermoelectrics by nanostructuring: tuning the nanoparticle morphology of Sb2Te3 by using ionic liquids
Schaumann, J. and Loor, M. and Ünal, D. and Mudring, A. and Heimann, S. and Hagemann, U. and Schulz, S. and Maculewicz, F. and Schierning, G.
Dalton Transactions 46 656-668 (2017)A systematic study on the microwave-assisted thermolysis of the single source precursor (Et2Sb)2Te (1) in different asymmetric 1-alkyl-3-methylimidazolium- and symmetric 1,3-dialkylimidazolium-based ionic liquids (ILs) reveals the distinctive role of both the anion and the cation in tuning the morphology and microstructure of the resulting Sb2Te3 nanoparticles as evidenced by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), and X-ray photoelectron spectroscopy (XPS). A comparison of the electrical and thermal conductivities as well as the Seebeck coefficient of the Sb2Te3 nanoparticles obtained from different ILs reveals the strong influence of the specific IL, from which C4mimI was identified as the best solvent, on the thermoelectric properties of as-prepared nanosized Sb2Te3. This work provides design guidelines for ILs, which allow the synthesis of nanostructured thermoelectrics with improved performances. © The Royal Society of Chemistry.view abstract doi: 10.1039/c6dt04323b 2017 • 581 Incorporation of silver nanoparticles into magnetron-sputtered calcium phosphate layers on titanium as an antibacterial coating
Surmeneva, M.A. and Sharonova, A.A. and Chernousova, S. and Prymak, O. and Loza, K. and Tkachev, M.S. and Shulepov, I.A. and Epple, M. and Surmenev, R.A.
Colloids and Surfaces B: Biointerfaces 156 104-113 (2017)A three-layer system of nanocrystalline hydroxyapatite (first layer; 1000 nm thick), silver nanoparticles (second layer; 1.5 μg Ag cm−2) and calcium phosphate (third layer, either 150 or 1000 nm thick) on titanium was prepared by a combination of electrophoretic deposition of silver nanoparticles and the deposition of calcium phosphate by radio frequency magnetron sputtering. Scanning electron microscopy showed that the silver nanoparticles were evenly distributed over the surface. The adhesion of multilayered coating on the substrate was evaluated using the scratch test method. The resistance to cracking and delamination indicated that the multilayered coating has good resistance to contact damage. The release of silver ions from the hydroxyapatite/silver nanoparticle/calcium phosphate system into the phosphate-buffered saline (PBS) solution was measured by atomic absorption spectroscopy (AAS). Approximately one-third of the incorporated silver was released after 3 days immersion into PBS, indicating a total release time of the order of weeks. There were no signs of cracks on the surface of the coating after immersion after various periods, indicating the excellent mechanical stability of the multilayered coating in the physiological environment. An antimicrobial effect against Escherichia coli was found for a 150 nm thick outer layer of the calcium phosphate using a semi-quantitative turbidity test. © 2017 Elsevier B.V.view abstract doi: 10.1016/j.colsurfb.2017.05.016 2017 • 580 Influence of Ni to Co ratio in mixed Co and Ni phosphides on their electrocatalytic oxygen evolution activity
Barwe, S. and Andronescu, C. and Vasile, E. and Masa, J. and Schuhmann, W.
Electrochemistry Communications 79 41-45 (2017)Prompted by the impact of Ni-based support materials on the intrinsic activity of electrocatalysts, we investigated the influence of partial Co substitution by Ni during the reductive thermal synthesis of cobalt-cobalt phosphide nanoparticles from triphenylphosphine complexes. The obtained catalysts were characterised by X-ray diffraction and electrochemistry. Increasing the amount of Ni in the precursor complexes leads to materials with lower overpotential for the OER at low current densities, and lower Tafel slopes. Co nanoparticles, which are only formed in materials with low Ni content, increase the intrinsic material conductivity and reduce the OER overpotential at high current densities. © 2017view abstract doi: 10.1016/j.elecom.2017.04.014 2017 • 579 Influence of Tail Groups during Functionalization of ZnO Nanoparticles on Binding Enthalpies and Photoluminescence
Lin, W. and Schmidt, J. and Mahler, M. and Schindler, T. and Unruh, T. and Meyer, B. and Peukert, W. and Segets, D.
Langmuir 33 13581-13589 (2017)We report on the tailoring of ZnO nanoparticle (NP) surfaces by catechol derivatives (CAT) with different functionalities: tert-butyl group (tertCAT), hydrogen (pyroCAT), aromatic ring (naphCAT), ester group (esterCAT), and nitro group (nitroCAT). The influence of electron-donating/-withdrawing properties on enthalpy of ligand binding (ΔH) was resolved and subsequently linked with optical properties. First, as confirmed by ultraviolet/visible (UV/vis) and Fourier transform infrared (FT-IR) spectroscopy results, all CAT molecules chemisorbed to ZnO NPs, independent of the distinct functionality. Interestingly, the ζ-potentials of ZnO after functionalization shifted to more negative values. Then, isothermal titration calorimetry (ITC) and a mass-based method were applied to resolve the heat release during ligand binding and the adsorption isotherm, respectively. However, both heat- and mass-based approaches alone did not fully resolve the binding enthalpy of each molecule adsorbing to the ZnO surface. This is mainly due to the fact that the Langmuir model oversimplifies the underlying adsorption mechanism, at least for some of the tested CAT molecules. Therefore, a new, fitting-free approach was developed to directly access the adsorption enthalpy per molecule during functionalization by dividing the heat release measured via ITC by the amount of bound molecules determined from the adsorption isotherm. Finally, the efficiency of quenching the visible emission caused by ligand binding was investigated by photoluminescence (PL) spectroscopy, which turned out to follow the same trend as the binding enthalpy. Thus, the functionality of ligand molecules governs the binding enthalpy to the particle surface, which in turn, at least in the current case of ZnO, is an important parameter for the quenching of visible emission. We believe that establishing such correlations is an important step toward a more general way of selecting and designing ligand molecules for surface functionalization. This allows developing strategies for tailored colloidal surfaces beyond empirically driven formulation on a case by case basis. © 2017 American Chemical Society.view abstract doi: 10.1021/acs.langmuir.7b03079 2017 • 578 Large eddy simulation of particle aggregation in turbulent jets
Pesmazoglou, I. and Kempf, A.M. and Navarro-Martinez, S.
Journal of Aerosol Science 111 1-17 (2017)Aggregation is an inter-particle process that involves a multitude of different physical and chemical mechanisms. Aggregation processes often occur within turbulent flows; for example in spray drying, soot formation, or nanoparticle formation. When the concentration of particles is very large, a direct simulation of individual particles is not possible and alternative approaches are needed. The present work follows the stochastic aggregation modelling based on a Lagrangian framework by Pesmazoglou, Kempf, and Navarro-Martinez (2016) and implements it in the Large Eddy Simulation context. The new coupled model is used to investigate particle aggregation in turbulent jets. Two cases are considered: an existent Direct Numerical Simulation of nanoparticle agglomeration in a planar jet and an experimental configuration of SiO2 nanoparticles in a round jet. The results show a good agreement in both cases, demonstrating the advantages of the Lagrangian framework to model agglomeration and it capacity to describe the full particle size distribution. © 2017 Elsevier Ltdview abstract doi: 10.1016/j.jaerosci.2017.06.002 2017 • 577 Large eddy simulations of nanoparticle synthesis from flame spray pyrolysis
Rittler, A. and Deng, L. and Wlokas, I. and Kempf, A.M.
Proceedings of the Combustion Institute 36 1077-1087 (2017)Large eddy simulations of the nanoparticle synthesis from flame spray pyrolysis are presented. A standard reactor is investigated, with ethanol/hexamethyldisiloxane (HMDSO) mixture as spray/precursor composition and oxygen as dispersion gas for the production of silica nanoparticles. Spray evaporation, ignition and stabilisation of the flame are achieved by a premixed methane/oxygen pilot flame. The gas, spray and nanoparticle phases are modelled with Eulerian, Lagrangian and Eulerian approaches, respectively. A modified tabulated chemistry model, adapted from the premixed flamelet generated manifold approach (PFGM) with artificial flame thickening (ATF) is proposed, tested and applied for the system. The control variables are the element mass fractions of hydrogen and carbon together with a joint progress variable. The population balance equation of the nanoparticles is modelled in terms of number, volume and surface area concentration, its subfilter distribution is modelled with a delta function. The combustion of HMDSO and formation of silica particle monomers is described by a two-step global mechanism. The nucleation source term is tabulated as a function of the control variables. The submodels for spray and combustion are validated separately to compensate for the shortage in detailed experimental data for nanoparticle spray flames. Subsequently, simulation results for the particles are presented and discussed, in particular the polydisperse particle size distributions resulting from turbulence. © 2016 The Combustion Institute.view abstract doi: 10.1016/j.proci.2016.08.005 2017 • 576 Laser Synthesis and Processing of Colloids: Fundamentals and Applications
Zhang, D. and Gökce, B. and Barcikowski, S.
Chemical Reviews 117 3990-4103 (2017)Driven by functionality and purity demand for applications of inorganic nanoparticle colloids in optics, biology, and energy, their surface chemistry has become a topic of intensive research interest. Consequently, ligand-free colloids are ideal reference materials for evaluating the effects of surface adsorbates from the initial state for application-oriented nanointegration purposes. After two decades of development, laser synthesis and processing of colloids (LSPC) has emerged as a convenient and scalable technique for the synthesis of ligand-free nanomaterials in sealed environments. In addition to the high-purity surface of LSPC-generated nanoparticles, other strengths of LSPC include its high throughput, convenience for preparing alloys or series of doped nanomaterials, and its continuous operation mode, suitable for downstream processing. Unscreened surface charge of LSPC-synthesized colloids is the key to achieving colloidal stability and high affinity to biomolecules as well as support materials, thereby enabling the fabrication of bioconjugates and heterogeneous catalysts. Accurate size control of LSPC-synthesized materials ranging from quantum dots to submicrometer spheres and recent upscaling advancement toward the multiple-gram scale are helpful for extending the applicability of LSPC-synthesized nanomaterials to various fields. By discussing key reports on both the fundamentals and the applications related to laser ablation, fragmentation, and melting in liquids, this Article presents a timely and critical review of this emerging topic. © 2017 American Chemical Society.view abstract doi: 10.1021/acs.chemrev.6b00468 2017 • 575 Laser synthesis, structure and chemical properties of colloidal nickel-molybdenum nanoparticles for the substitution of noble metals in heterogeneous catalysis
Marzun, G. and Levish, A. and Mackert, V. and Kallio, T. and Barcikowski, S. and Wagener, P.
Journal of Colloid and Interface Science 489 57-67 (2017)Platinum and iridium are rare and expensive noble metals that are used as catalysts for different sectors including in heterogeneous chemical automotive emission catalysis and electrochemical energy conversion. Nickel and its alloys are promising materials to substitute noble metals. Nickel based materials are cost-effective with good availability and show comparable catalytic performances. The nickel-molybdenum system is a very interesting alternative to platinum in water electrolysis. We produced ligand-free nickel-molybdenum nanoparticles by laser ablation in water and acetone. Our results show that segregated particles were formed in water due to the oxidation of the metals. X-ray diffraction shows a significant change in the lattice parameter due to a diffusion of molybdenum atoms into the nickel lattice with increasing activity in the electrochemical oxygen evolution reaction. Even though the solubility of molecular oxygen in acetone is higher than in water, there were no oxides and a more homogeneous metal distribution in the particles in acetone as seen by TEM-EDX. This showed that dissolved molecular oxygen does not control oxide formation. Overall, the laser ablation of pressed micro particulate mixtures in liquids offers a combinational synthesis approach that allows the screening of alloy nanoparticles for catalytic testing and can convert micro-mixtures into nano-alloys. © 2016 Elsevier Inc.view abstract doi: 10.1016/j.jcis.2016.09.014 2017 • 574 Laser-induced atomic emission of silicon nanoparticles during laser-induced heating
Menser, J. and Daun, K. and Dreier, T. and Schulz, C.
Applied Optics 56 E50-E57 (2017)The temporal luminescence behavior of silicon atoms during and after laser-heating of gas-borne silicon nano-particles was investigated. Silicon nanoparticles were formed in the exhaust stream of a microwave plasma reactor at 100 mbar. The observed prompt atomic line intensities correspond with thermal excitation of the evaporated species. A prompt signal at 251.61 and 288.15 nm originating from the 3s23p2 → 3s23p4s transitions showed a lifetime of 16 ns that matches the documented excited-state lifetime for the respective transitions. A secondary delayed signal contribution with similar peak intensities was observed commencing approximately 100-300 ns after the laser pulse and persisting for hundreds of nanoseconds. This signal contribution is attributed to electron impact excitation or recombination after electron impact ionization of the silicon evaporated as a consequence of the laser heating of the plasma leading to non-thermal population of electronically excited silicon. The observations support a nanoparticle evaporation model that can be used to recover nanoparticle sizes from time-resolved LII data. © 2017 Optical Society of America.view abstract doi: 10.1364/AO.56.000E50 2017 • 573 Laser-induced growth of YVO4:Eu3+ nanoparticles from sequential flowing aqueous suspension
Wang, H. and Lau, M. and Sannomiya, T. and Gökce, B. and Barcikowski, S. and Odawara, O. and Wada, H.
RSC Advances 7 9002-9008 (2017)Ligand-free lanthanide ion-doped oxide nanoparticles have critical biological applications. An environmentally friendly and chemically green synthesis of YVO4:Eu3+ nanoparticles with high crystallinity is achieved using a physical method, laser irradiation from sequential flowing aqueous suspension in a free liquid reactor. The fabricated nanoparticles have an ovoid or spindle shape depending on the number of laser irradiation cycles. A transmission electron microscopy study showed that spindle-like particles are single-crystalline with high crystallinity, which is beneficial for high luminescence efficiency. Strong light emission even from a single particle was confirmed by cathodoluminescence mapping. A possible mechanism of nanoparticle formation was proposed as follows. Primary nanocrystals were produced from the plasma plume and self-assembled into ovoid-like nanoparticles via oriented attachment. After several cycles of laser irradiation, we observed spindle-like nanoparticles that were much longer than the ovoid-like particles. The spindle-like nanoparticles grew as a result of the diffusion and coalescence of the ovoid-like nanoparticles during repetitive laser irradiation. These findings provide useful information for the formation of ligand-free luminescent nanoparticles with different sizes based on YVO4. © The Royal Society of Chemistry.view abstract doi: 10.1039/c6ra28118d 2017 • 572 Liquid filtration of nanoparticles through track-etched membrane filters under unfavorable and different ionic strength conditions: Experiments and modeling
Lee, H. and Segets, D. and Süß, S. and Peukert, W. and Chen, S.-C. and Pui, D.Y.H.
Journal of Membrane Science 524 682-690 (2017)Nanoparticle deposition experiments under unfavorable conditions were conducted experimentally and theoretically. The 0.2 and 0.4 µm rated track-etched membrane filters were challenged with 60, 100, 147, 220, 350 and 494 nm polystyrene latex (PSL) particles with different ionic strengths ranging from 0.005 to 0.05 M. The capillary tube model, with replacing the viscosity of air to water, was used to estimate the initial efficiency, or the transport efficiency of the particles to the filter surface, which was corrected in a second step by allowing the detachment of the nanoparticles according to the sum of adhesive and hydrodynamic torques. The adhesive torques were derived from surface interactions accessed by the extended DLVO theory. Calculation results showed that the adhesive torque of a particle located in the calculated primary minimum was slightly larger than the hydrodynamic torque, resulting in particle deposition. However, experimental data clearly indicated that detachment occurred. This could only be explained by the presence of additional hydration forces, leading to a larger separation which became relevant at high ionic strengths. By including hydration into our theoretical framework, experiment and theory were in very good agreement under all different ionic strength conditions. The findings allow a basic understanding of surface interactions between nanoparticles and membranes in micro- and ultra-filtration applications for drinking water production, wastewater treatment and particle free water production in industries. © 2016 Elsevier B.V.view abstract doi: 10.1016/j.memsci.2016.11.023 2017 • 571 Local characterization of light trapping effects of metallic and dielectric nanoparticles in ultra-thin Cu(In,Ga)Se2 solar cells via scanning near-field optical microscopy
Song, M. and Yin, G. and Fumagalli, P. and Schmid, M.
Proceedings of SPIE - The International Society for Optical Engineering 10114 (2017)Plasmonic and photonic nanoparticles have proven beneficial for solar cells in the aspect of light management. For improved exploitation of nanoparticles in solar cells, it is necessary to reveal the absorption enhancement mechanism from the nanoparticles. In this study, we investigated the nanoparticle-enhanced solar cells in near-field regime with optic and opto-electric scanning near-field optical microscopy (SNOM). The near-field distribution of regularly arranged silver and polystyrene nanoparticles produced by nanosphere lithography on Cu(In,Ga)Se2 (CIGSe) solar cells is characterized using a custom-built SNOM, which gives insight into the optical mechanism of light trapping from nanoparticles to solar cells. On the other hand, the photocurrent of CIGSe solar cells with and without nanoparticles is studied with an opto-electric SNOM by recording the photocurrent during surface scanning, further revealing the opto-electrical influences of the nanoparticles. In addition, finite element method simulations have been performed and agree with the results from SNOM. We found the dielectric polystyrene spheres are able to enhance the absorption and benefit the generation of charge carriers in the solar cells. Copyright © 2017 SPIE.view abstract doi: 10.1117/12.2253223 2017 • 570 Local delivery of siRNA-loaded calcium phosphate nanoparticles abates pulmonary inflammation
Frede, A. and Neuhaus, B. and Knuschke, T. and Wadwa, M. and Kollenda, S. and Klopfleisch, R. and Hansen, W. and Buer, J. and Bruder, D. and Epple, M. and Westendorf, A.M.
Nanomedicine: Nanotechnology, Biology, and Medicine 13 2395-2403 (2017)The local interference of cytokine signaling mediated by siRNA-loaded nanoparticles might be a promising new therapeutic approach to dampen inflammation during pulmonary diseases. For the local therapeutic treatment of pulmonary inflammation, we produced multi-shell nanoparticles consisting of a calcium phosphate core, coated with siRNAs directed against pro-inflammatory mediators, encapsulated into poly(lactic-co-glycolic acid), and coated with a final outer layer of polyethylenimine. Nasal instillation of nanoparticles loaded with a mixture of siRNAs directed against different cytokines to mice suffering from TH1 cell-mediated lung inflammation, or of siRNA directed against NS-1 in an influenza infection model led to a significant reduction of target gene expression which was accompanied by distinct amelioration of lung inflammation in both models. Thus, this study provides strong evidence that the specific and local modulation of the inflammatory response by CaP/PLGA nanoparticle-mediated siRNA delivery could be a promising approach for the treatment of inflammatory disorders of the lung. © 2017 Elsevier Inc.view abstract doi: 10.1016/j.nano.2017.08.001 2017 • 569 Long-term thermal stability of nanoclusters in ODS-Eurofer steel: An atom probe tomography study
Zilnyk, K.D. and Pradeep, K.G. and Choi, P. and Sandim, H.R.Z. and Raabe, D.
Journal of Nuclear Materials 492 142-147 (2017)Oxide-dispersion strengthened materials are important candidates for several high-temperature structural applications in advanced nuclear power plants. Most of the desirable mechanical properties presented by these materials are due to the dispersion of stable nanoparticles in the matrix. Samples of ODS-Eurofer steel were annealed for 4320 h (6 months) at 800 °C. The material was characterized using atom probe tomography in both conditions (prior and after heat treatment). The particles number density, size distribution, and chemical compositions were determined. No significant changes were observed between the two conditions indicating a high thermal stability of the Y-rich nanoparticles at 800 °C. © 2017 Elsevier B.V.view abstract doi: 10.1016/j.jnucmat.2017.05.027 2017 • 568 Mass spectrometric analysis of clusters and nanoparticles during the gas-phase synthesis of tungsten oxide
Kluge, S. and Wiggers, H. and Schulz, C.
Proceedings of the Combustion Institute 36 1037-1044 (2017)The combustion synthesis of nanoscale tungsten-oxide particles from tungsten hexafluoride is investigated in a low-pressure hydrogen/oxygen flat flame. The reactor is equipped with molecular-beam sampling of post-flame gases at variable height above burner (HAB). Main species of the flame, intermediate tungsten species, and tungsten-oxide clusters are studied with time-of-flight mass spectrometry (TOF-MS) as a function of HAB. Various WO x (OH) y are identified within the flame front. With increasing HAB, (WO3) n clusters with increasing cluster size appear in the burnt gases at the expense of the concentration of W1 species. Clusters with n =3-7 arise at 70mm HAB, followed by larger clusters at even larger heights. Clusters up to (WO3)38 were identified. The subsequent formation of nanoparticles is detected with particle mass spectrometry (PMS) and a quartz crystal microbalance (QCM) from 120mm HAB and the increasing particle size and mass flux have been determined. © 2016.view abstract doi: 10.1016/j.proci.2016.06.165 2017 • 567 Massive nanoprecipitation in an Fe-19Ni-xAl maraging steel triggered by the intrinsic heat treatment during laser metal deposition
Kürnsteiner, P. and Wilms, M.B. and Weisheit, A. and Barriobero-Vila, P. and Jägle, E.A. and Raabe, D.
Acta Materialia 129 52-60 (2017)Due to the layer-by-layer build-up of additively manufactured parts, the deposited material experiences a cyclic re-heating in the form of a sequence of temperature pulses. In the current work, this “intrinsic heat treatment (IHT)” was exploited to induce the precipitation of NiAl nanoparticles in an Fe-19Ni-xAl (at%) model maraging steel, a system known for rapid clustering. We used Laser Metal Deposition (LMD) to synthesize compositionally graded specimens. This allowed for the efficient screening of effects associated with varying Al contents ranging from 0 to 25 at% and for identifying promising concentrations for further studies. Based on the existence of the desired martensitic matrix, an upper bound for the Al concentration of 15 at% was defined. Owing to the presence of NiAl precipitates as observed by Atom Probe Tomography (APT), a lower bound of 3–5 at% Al was established. Within this concentration window, increasing the Al concentration gave rise to an increase in hardness by 225 HV due to an exceptionally high number density of 1025 NiAl precipitates per m3, as measured by APT. This work demonstrates the possibility of exploiting the IHT of the LMD process for the production of samples that are precipitation strengthened during the additive manufacturing process without need for any further heat treatment. © 2017view abstract doi: 10.1016/j.actamat.2017.02.069 2017 • 566 Metal–Organic Framework Derived Carbon Nanotube Grafted Cobalt/Carbon Polyhedra Grown on Nickel Foam: An Efficient 3D Electrode for Full Water Splitting
Aijaz, A. and Masa, J. and Rösler, C. and Xia, W. and Weide, P. and Fischer, R.A. and Schuhmann, W. and Muhler, M.
ChemElectroChem 4 188-193 (2017)The growth of metal–organic framework (ZIF-67) nanocrystals on nickel foam (NF), followed by carbonization in diluted H2, leads to a nitrogen-doped carbon-nanotube-grafted cobalt/carbon polyhedra film on NF. The obtained material serves as a highly active binder-free electrocatalyst for both the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER), enabling high-performance alkaline (0.1 m KOH) water electrolysis with potentials of 1.62 and 0.24 V, respectively, at OER and HER current densities of 10 mA cm−2. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/celc.201600452 2017 • 565 Microstructure and thermoelectric properties of Si-WSi2 nanocomposites
Stoetzel, J. and Schneider, T. and Mueller, M.M. and Kleebe, H.-J. and Wiggers, H. and Schierning, G. and Schmechel, R.
Acta Materialia 125 321-326 (2017)Nanocomposites of n-doped Si/WSi2 were prepared and morphologically and thermoelectrically investigated. The composites were densified by spark-plasma-sintering of doped Si nanoparticles with WSi2 nanoinclusions. The nanoparticles were synthesized in a gas-phase process. The microstructure of the bulk nanocomposite shows an inhomogeneous distribution of the WSi2 nanoinclusions in form of WSi2-rich and -depleted regions. This inhomogeneity is not present in the starting material and is assigned to a self-organizing process during sintering. The inhomogeneities are in the micrometer range and may act as scattering centers for long-wavelength phonons. The WSi2 nanoinclusions grow during sintering from originally 3–7 nm up to 30–143 nm depending on the total W content and might act as scattering centers for the medium wavelength range of phonons. Further, the growth of Si grains is suppressed by the WSi2 inclusions, which leads to an enhanced grain boundary density. Adding 1 at% W reduces lattice thermal conductivity by almost 35% within the temperature range from 300 K to 1250 K compared to pure, nanocrystalline silicon (doped). By addition of 6 at% W a reduction of 54% in lattice thermal conductivity is achieved. Although little amounts of W slightly reduce the power factor an enhancement of the thermoelectric figure of merit of 50% at 1250 K compared to a tungsten-free reference was realized. © 2016view abstract doi: 10.1016/j.actamat.2016.11.069 2017 • 564 Mobility investigations of magnetic nanoparticles in biocomposites
Müller, R. and Zhou, M. and Liebert, T. and Landers, J. and Salamon, S. and Webers, S. and Dellith, A. and Borin, D. and Heinze, T. and Wende, H.
Materials Chemistry and Physics 193 364-370 (2017)Biocompatible composites are presented, consisting of magnetite nanoparticles embedded into a matrix of meltable dextran ester, which can be softened under an induced alternating magnetic field and may thereby allow magnetically controlled release applications. Temperature dependent mobility investigations of magnetic nanoparticles in the molten composites were carried out by optical microscopy, magnetometry, AC susceptibility and Mössbauer spectroscopy measurements. Optical microscopy shows a movement of agglomerates and texturing in the micrometer scale, whereas AC-susceptometry and Mössbauer spectroscopy investigations reveal that the particles perform diffusive Brownian motion in the liquid polymer melt as separated particles rather than as large agglomerates. © 2017 Elsevier B.V.view abstract doi: 10.1016/j.matchemphys.2017.02.046 2017 • 563 MOF-Templated Assembly Approach for Fe3C Nanoparticles Encapsulated in Bamboo-Like N-Doped CNTs: Highly Efficient Oxygen Reduction under Acidic and Basic Conditions
Aijaz, A. and Masa, J. and Rösler, C. and Antoni, H. and Fischer, R.A. and Schuhmann, W. and Muhler, M.
Chemistry - A European Journal (2017)Developing high-performance non-precious metal catalysts (NPMCs) for the oxygen-reduction reaction (ORR) is of critical importance for sustainable energy conversion. We report a novel NPMC consisting of iron carbide (Fe3C) nanoparticles encapsulated in N-doped bamboo-like carbon nanotubes (b-NCNTs), synthesized by a new metal-organic framework (MOF)-templated assembly approach. The electrocatalyst exhibits excellent ORR activity in 0.1m KOH (0.89V at -1mAcm-2) and in 0.5m H2SO4 (0.73V at -1mAcm-2) with a hydrogen peroxide yield of below 1% in both electrolytes. Due to encapsulation of the Fe3C nanoparticles inside porous b-NCNTs, the reported NPMC retains its high ORR activity after around 70hours in both alkaline and acidic media. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/chem.201701389 2017 • 562 Nano-sized metal organic framework to improve the structural properties and desalination performance of thin film composite forward osmosis membrane
Zirehpour, A. and Rahimpour, A. and Ulbricht, M.
Journal of Membrane Science 531 59-67 (2017)In the present study, nano-sized metal-organic framework (MOF) particles consisting of silver (I) and 1,3,5-benzene tricarboxylic acid were synthesized and applied to improve the structural properties as well as desalination performance of thin-film composite (TFC) forward osmosis (FO) membranes. The MOF nanocrystals were incorporated into the polyamide layer of membranes through interfacial polymerization. Characterizations by Field emission scanning electron microscopy and X-ray photoelectron spectroscopy enabled the detection of MOF nanocrystals within the selective layer of the resultant membranes. The MOF incorporation led to changes of the membrane active layer in terms of hydrophilicity and transport properties, without detrimental effects on the layer selectivity. These features enhanced pure water permeability of the membranes to 129%, which was provided through 0.04% MOF loading of the organic phase during interfacial polymerization. As a result, the modified membrane exhibited an enhanced FO seawater desalination performance in comparison with the control membrane. The performance stability of TFC membrane was also improved by presence of MOF in active layer (as seen by a water flux decline of about 7% for modified membrane against about 18% for unmodified membrane when tested with real seawater). This study demonstrates the potential of MOF particles to enhance desalination performance of TFC membranes in FO systems. © 2017 Elsevier B.V.view abstract doi: 10.1016/j.memsci.2017.02.049 2017 • 561 Nanoparticle atoms pinpointed
Farle, M.
Nature 542 35-36 (2017)doi: 10.1038/542035a 2017 • 560 Nanoparticle-based B-cell targeting vaccines: Tailoring of humoral immune responses by functionalization with different TLR-ligands
Zilker, C. and Kozlova, D. and Sokolova, V. and Yan, H. and Epple, M. and Überla, K. and Temchura, V.
Nanomedicine: Nanotechnology, Biology, and Medicine 13 173-182 (2017)Induction of an appropriate type of humoral immune response during vaccination is essential for protection against viral and bacterial infections. We recently observed that biodegradable calcium phosphate (CaP) nanoparticles coated with proteins efficiently targeted and activated naïve antigen-specific B-cells in vitro. We now compared different administration routes for CaP-nanoparticles and demonstrated that intramuscular immunization with such CaP-nanoparticles induced stronger immune responses than immunization with monovalent antigen. Additional functionalization of the CaP-nanoparticles with TRL-ligands allowed modulating the IgG subtype response and the level of mucosal IgA antibodies. CpG-containing CaP-nanoparticles were as immunogenic as a virus-like particle vaccine. Functionalization of CaP-nanoparticles with T-helper cell epitopes or CpG also allowed overcoming lack of T-cell help. Thus, our results indicate that CaP-nanoparticle-based B-cell targeting vaccines functionalized with TLR-ligands can serve as a versatile platform for efficient induction and modulation of humoral immune responses in vivo. © 2016 Elsevier Inc.view abstract doi: 10.1016/j.nano.2016.08.028 2017 • 559 Nanoparticulate versus ionic silver: Behavior in the tank water, bioaccumulation, elimination and subcellular distribution in the freshwater mussel Dreissena polymorpha
Zimmermann, S. and Ruchter, N. and Loza, K. and Epple, M. and Sures, B.
Environmental Pollution 222 251-260 (2017)Zebra mussels (Dreissena polymorpha) were exposed to polyvinylpyrrolidone (PVP)-coated silver nanoparticles (AgNP; hydrodynamic diameter 80 nm; solid diameter 50 nm) to investigate the behavior of Ag in the tank water with respect to its uptake, bioaccumulation, elimination and subcellular distribution in the mussel soft tissue. Parallel experiments were performed with ionic Ag (AgNO3) to unravel possible differences between the metal forms. The recovery of the applied Ag concentration (500 μg/L) in the tank water was clearly affected by the metal source (AgNP < AgNO3) and water type (reconstituted water < tap water). Filtration (< 0.45 μm) of water samples showed different effects on the quantified metal concentration depending on the water type and Ag form. Ag accumulation in the mussel soft tissue was neither influenced by the metal source nor by the water type. Ag concentrations in the mussel soft tissue did not decrease during 14 days of depuration. For both metal forms the Ag distribution within different subcellular fractions, i.e. metal-rich granules (MRG), cellular debris, organelles, heat-sensitive proteins (HSP) and metallothionein-like proteins (MTLP), revealed time-dependent changes which can be referred to intracellular Ag translocation processes. The results provide clear evidence for the uptake of Ag by the mussel soft tissue in nanoparticulate as well as in ionic form. Thus, zebra mussels could be used as effective accumulation indicators for environmental monitoring of both Ag forms. © 2016 Elsevier Ltd.view abstract doi: 10.1016/j.envpol.2016.12.048 2017 • 558 Nanophase Segregation of Self-Assembled Monolayers on Gold Nanoparticles
Meena, S.K. and Goldmann, C. and Nassoko, D. and Seydou, M. and Marchandier, T. and Moldovan, S. and Ersen, O. and Ribot, F. and Chanéac, C. and Sanchez, C. and Portehault, D. and Tielens, F. and Sulpizi, M.
ACS Nano 11 7371-7381 (2017)Nanophase segregation of a bicomponent thiol self-assembled monolayer is predicted using atomistic molecular dynamics simulations and experimentally confirmed. The simulations suggest the formation of domains rich in acid-terminated chains, on one hand, and of domains rich in amide-functionalized ethylene glycol oligomers, on the other hand. In particular, within the amide-ethylene glycol oligomers region, a key role is played by the formation of interchain hydrogen bonds. The predicted phase segregation is experimentally confirmed by the synthesis of 35 and 15 nm gold nanoparticles functionalized with several binary mixtures of ligands. An extensive study by transmission electron microscopy and electron tomography, using silica selective heterogeneous nucleation on acid-rich domains to provide electron contrast, supports simulations and highlights patchy nanoparticles with a trend toward Janus nano-objects depending on the nature of the ligands and the particle size. These results validate our computational platform as an effective tool to predict nanophase separation in organic mixtures on a surface and drive further exploration of advanced nanoparticle functionalization. © 2017 American Chemical Society.view abstract doi: 10.1021/acsnano.7b03616 2017 • 557 On the bifunctional nature of Cu/ZrO2 catalysts applied in the hydrogenation of ethyl acetate
Schittkowski, J. and Tölle, K. and Anke, S. and Stürmer, S. and Muhler, M.
Journal of Catalysis 352 120-129 (2017)The catalytic hydrogenation of ethyl acetate to ethanol was studied at ambient pressure in the temperature range from 463 K to 513 K using Cu/ZrO2 catalysts obtained by co-precipitation as a function of the Cu loading. The hydrogenation was established as a reproducible probe reaction by determining optimal reaction parameters without deactivation or thermodynamic limitations. Power-law kinetics were determined yielding an apparent activation energy of 74 kJ mol−1 and reaction orders of 0.1–0.3 for H2 and −0.4 to 0.1 for ethyl acetate in the temperature range from 473 K to 503 K. Metallic Cu was found to be essential for the hydrogenation, but the catalytic activity was not proportional to the Cu surface area derived from N2O decomposition and temperature-programmed H2 desorption experiments identifying Cu/ZrO2 as bifunctional catalyst. The acidic sites of the ZrO2 matrix were probed by temperature-programmed experiments with ethyl acetate and NH3. Cu0 is assumed to provide atomic hydrogen by dissociative adsorption and spillover, but the reaction rate is more affected by the tight contact between the embedded Cu nanoparticles and the X-ray amorphous ZrO2 matrix. © 2017 Elsevier Inc.view abstract doi: 10.1016/j.jcat.2017.05.009 2017 • 556 Parasitic Reactions in Nanosized Silicon Anodes for Lithium-Ion Batteries
Gao, H. and Xiao, L. and Plümel, I. and Xu, G.-L. and Ren, Y. and Zuo, X. and Liu, Y. and Schulz, C. and Wiggers, H. and Amine, K. and Chen, Z.
Nano Letters 17 1512-1519 (2017)When designing nano-Si electrodes for lithium-ion batteries, the detrimental effect of the c-Li15Si4 phase formed upon full lithiation is often a concern. In this study, Si nanoparticles with controlled particle sizes and morphology were synthesized, and parasitic reactions of the metastable c-Li15Si4 phase with the nonaqueous electrolyte was investigated. The use of smaller Si nanoparticles (∼60 nm) and the addition of fluoroethylene carbonate additive played decisive roles in the parasitic reactions such that the c-Li15Si4 phase could disappear at the end of lithiation. This suppression of c-Li15Si4 improved the cycle life of the nano-Si electrodes but with a little loss of specific capacity. In addition, the characteristic c-Li15Si4 peak in the differential capacity (dQ/dV) plots can be used as an early-stage indicator of cell capacity fade during cycling. Our findings can contribute to the design guidelines of Si electrodes and allow us to quantify another factor to the performance of the Si electrodes. © 2017 American Chemical Society.view abstract doi: 10.1021/acs.nanolett.6b04551 2017 • 555 Peptide Cross-linkers: Immobilization of Platinum Nanoparticles Highly Dispersed on Graphene Oxide Nanosheets with Enhanced Photocatalytic Activities
Mizutaru, T. and Marzun, G. and Kohsakowski, S. and Barcikowski, S. and Hong, D. and Kotani, H. and Kojima, T. and Kondo, T. and Nakamura, J. and Yamamoto, Y.
ACS Applied Materials and Interfaces 9 9996-10002 (2017)For exerting potential catalytic and photocatalytic activities of metal nanoparticles (MNPs), immobilization of MNPs on a support medium in highly dispersed state is desired. In this Research Article, we demonstrated that surfactant-free platinum nanoparticles (PtNPs) were efficiently immobilized on graphene oxide (GO) nanosheets in a highly dispersed state by utilizing oligopeptide β-sheets as a cross-linker. The fluorenyl-substituted peptides were designed to form β-sheets, where metal-binding thiol groups and protonated and positively charged amino groups are integrated on the opposite sides of the surface of a β-sheet, which efficiently bridge PtNPs and GO nanosheet. In comparison to PtNP/GO composite without the peptide linker, the PtNP/peptide/GO ternary complex exhibited excellent photocatalytic dye degradation activity via electron transfer from GO to PtNP and simultaneous hole transfer from oxidized GO to the dye. Furthermore, the ternary complex showed photoinduced hydrogen evolution upon visible light irradiation using a hole scavenger. This research provides a new methodology for the development of photocatalytic materials by a bottom-up strategy on the basis of self-assembling features of biomolecules. © 2017 American Chemical Society.view abstract doi: 10.1021/acsami.6b16765 2017 • 554 Perspective of laser-prototyping nanoparticle-polymer composites
Zhang, D. and Gökce, B.
Applied Surface Science 392 991-1003 (2017)Nanoparticle synthesis by laser ablation in liquids has attracted attention from researchers worldwide the past few years and the integration of these nanoparticles in functional materials such as nanoparticle-polymer composites, represents a natural next step. Such “nanointegration” into polymers can be achieved by the ex situ dispersion of laser-synthesized inorganic nanoparticles in polymer matrices and the in situ encapsulation/grafting of nanoparticles with polymers/monomers during synthesis. Because the nanoparticle shell and the polymer matrix may be identical, this method often does not require the use of dispersants or matrix binders and constitutes a new avenue for direct particle-polymer coupling. In this perspective review, we summarize the methodologies for in situ and ex situ laser prototyping of nanoparticle-polymer composites (LaNPC) and downstream bulk-processing techniques. The determinants of polymer-solvent-laser parametrization for aimed physical and chemical properties of the composites are discussed. By highlighting representative works related to a variety of promising applications, the advantageous features of this technique are demonstrated. Finally, the challenges and prospects of LaNPC are outlined and a perspective is given regarding how the recent research findings reviewed changed the research direction in the field. © 2016view abstract doi: 10.1016/j.apsusc.2016.09.150 2017 • 553 Photocatalytic and Magnetic Porous Cellulose-Based Nanocomposite Films Prepared by a Green Method
Wittmar, A. and Fu, Q. and Ulbricht, M.
ACS Sustainable Chemistry and Engineering 5 9858-9868 (2017)The present work expands our previous studies related to cellulose processing with room-temperature ionic liquids and simultaneous integration of functional nanoparticles toward photocatalytically active and easily recyclable nanocomposite porous films based on a renewable matrix material. Porosity can be tuned by the selection of phase separation conditions for the films obtained from the casting solutions of cellulose in ionic liquids or their mixture with an organic co-solvent. TiO2 nanoparticles confer to the nanocomposite photocatalytic activity, while Fe3O4 nanoparticles make it magnetically active. The photocatalytic activity of the cellulose film containing 10 mg of TiO2 was 1 order of magnitude lower than that of the same amount of pure TiO2 nanopowder, due to the reduction of the active catalytic surface which can be reached by UV irradiation after embedment in the polymer matrix. However, this fixation in a solid polymer support allows facile recovery of the catalyst after use. The rate constant when using the cellulose nanocomposite doped with TiO2 and Fe3O4 (k ≈ 0.0019 min-1) is very close to that for the corresponding composite containing only TiO2 (k ≈ 0.0017 min-1), suggesting that co-doping with Fe3O4 nanoparticles did not diminish the photocatalytic activity of the final composite, which can be easily separated from solution with a magnet. Additionally, by Fe3O4 doping, the composite material's temperature can be homogeneously increased by ∼12 K via exposure to a high-frequency alternating magnetic field (AMF) for 5 min. For an optimal thermal response to AMF, the magnetite nanoparticles have to be homogeneously dispersed within the polymer matrix. The preparation method for the casting solution has been found to play an essential role for the one-step fabrication of multifunctional cellulose-based nanocomposite materials. © 2017 American Chemical Society.view abstract doi: 10.1021/acssuschemeng.7b01830 2017 • 552 Probing Oxide Reduction and Phase Transformations at the Au-TiO2 Interface by Vibrational Spectroscopy
Pougin, A. and Lüken, A. and Klinkhammer, C. and Hiltrop, D. and Kauer, M. and Tölle, K. and Havenith-Newen, M. and Morgenstern, K. and Grünert, W. and Muhler, M. and Strunk, J.
Topics in Catalysis 60 1744-1753 (2017)By a combination of FT-NIR Raman spectroscopy, infrared spectroscopy of CO adsorption under ultrahigh vacuum conditions (UHV-IR) and Raman spectroscopy in the line scanning mode the formation of a reduced titania phase in a commercial Au/TiO2 catalyst and in freshly prepared Au/anatase catalysts was detected. The reduced phase, formed at the Au-TiO2 interface, can serve as nucleation point for the formation of stoichiometric rutile. TinO2n−1 Magnéli phases, structurally resembling the rutile phase, might be involved in this process. The formation of the reduced phase and the rutilization process is clearly linked to the presence of gold nanoparticles and it does not proceed under similar conditions with the pure titania sample. Phase transformations might be both thermally or light induced, however, the colloidal deposition synthesis of the Au/TiO2 catalysts is clearly ruled out as cause for the formation of the reduced phase. © 2017, The Author(s).view abstract doi: 10.1007/s11244-017-0851-8 2017 • 551 Process Chain for the Fabrication of Nanoparticle Polymer Composites by Laser Ablation Synthesis
Maurer, E. and Barcikowski, S. and Gökce, B.
Chemical Engineering and Technology 40 1535-1543 (2017)Nanoparticle polymer composites are of growing interest due to their unique properties. However, conventional composite synthesis methods usually require several process steps including steps for cleaning and improving the particle-matrix dispersion. As an alternative, laser ablation synthesis can be used to prepare tunable composite materials. This method enables an easy process chain, without the need of additional steps. In this status report, the process chain of laser-based pre-series fabrication of nanocomposites is visualized, and the increase of the method's technology readiness level is demonstrated. The process steps are demonstrated from the synthesis of the colloid to applicable functional products. The advantages of using laser ablation for nanocomposite synthesis are highlighted. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/ceat.201600506 2017 • 550 Promoting Photocatalytic Overall Water Splitting by Controlled Magnesium Incorporation in SrTiO3 Photocatalysts
Han, K. and Lin, Y.-C. and Yang, C.-M. and Jong, R. and Mul, G. and Mei, B.
ChemSusChem 10 4510-4516 (2017)SrTiO3 is a well-known photocatalyst inducing overall water splitting when exposed to UV irradiation of wavelengths <370 nm. However, the apparent quantum efficiency of SrTiO3 is typically low, even when functionalized with nanoparticles of Pt or Ni@NiO. Here, we introduce a simple solid-state preparation method to control the incorporation of magnesium into the perovskite structure of SrTiO3. After deposition of Pt or Ni@NiO, the photocatalytic water-splitting efficiency of the Mg:SrTiOx composites is up to 20 times higher compared to SrTiO3 containing similar catalytic nanoparticles, and an apparent quantum yield (AQY) of 10 % can be obtained in the wavelength range of 300–400 nm. Detailed characterization of the Mg:SrTiOx composites revealed that Mg is likely substituting the tetravalent Ti ion, leading to a favorable surface–space–charge layer. This originates from tuning of the donor density in the cubic SrTiO3 structure by Mg incorporation and enables high oxygen-evolution rates. Nevertheless, interfacing with an appropriate hydrogen evolution catalyst is mandatory and non-trivial to obtain high-performance in water splitting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/cssc.201701794 2017 • 549 Rock Salt Ni/Co Oxides with Unusual Nanoscale-Stabilized Composition as Water Splitting Electrocatalysts
Fominykh, K. and Tok, G.C. and Zeller, P. and Hajiyani, H. and Miller, T. and Döblinger, M. and Pentcheva, R. and Bein, T. and Fattakhova-Rohlfing, D.
Advanced Functional Materials 27 (2017)The influence of nanoscale on the formation of metastable phases is an important aspect of nanostructuring that can lead to the discovery of unusual material compositions. Here, the synthesis, structural characterization, and electrochemical performance of Ni/Co mixed oxide nanocrystals in the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is reported and the influence of nanoscaling on their composition and solubility range is investigated. Using a solvothermal synthesis in tert-butanol ultrasmall crystalline and highly dispersible Ni x Co1− x O nanoparticles with rock salt type structure are obtained. The mixed oxides feature non-equilibrium phases with unusual miscibility in the whole composition range, which is attributed to a stabilizing effect of the nanoscale combined with kinetic control of particle formation. Substitutional incorporation of Co and Ni atoms into the rock salt lattice has a remarkable effect on the formal potentials of NiO oxidation that shift continuously to lower values with increasing Co content. This can be related to a monotonic reduction of the work function of (001) and (111)-oriented surfaces with an increase in Co content, as obtained from density functional theory (DFT+U) calculations. Furthermore, the electrocatalytic performance of the Ni x Co1− x O nanoparticles in water splitting changes significantly. OER activity continuously increases with increasing Ni contents, while HER activity shows an opposite trend, increasing for higher Co contents. The high electrocatalytic activity and tunable performance of the nonequilibrium Ni x Co1− x O nanoparticles in HER and OER demonstrate great potential in the design of electrocatalysts for overall water splitting. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/adfm.201605121 2017 • 548 Role of Composition and Size of Cobalt Ferrite Nanocrystals in the Oxygen Evolution Reaction
Chakrapani, K. and Bendt, G. and Hajiyani, H. and Schwarzrock, I. and Lunkenbein, T. and Salamon, S. and Landers, J. and Wende, H. and Schlögl, R. and Pentcheva, R. and Behrens, M. and Schulz, S.
ChemCatChem 9 2988-2995 (2017)Sub-10 nm CoFe2O4 nanoparticles with different sizes and various compositions obtained by (partial) substitution of Co with Ni cations have been synthesized by using a one-pot method from organic solutions by the decomposition of metal acetylacetonates in the presence of oleylamine. The electrocatalytic activity of CoFe2O4 towards the oxygen evolution reaction (OER) is clearly enhanced with a smaller size (3.1 nm) of the CoFe2O4 nanoparticles (compared with 4.5 and 5.9 nm). In addition, the catalytic activity is improved by partial substitution of Co with Ni, which also leads to a higher degree of inversion of the spinel structure. Theoretical calculations attribute the positive catalytic effect of Ni owing to the lower binding energy differences between adsorbed O and OH compared with pure cobalt or nickel ferrites, resulting in higher OER activity. Co0.5Ni0.5Fe2O4 exhibited a low overpotential of approximately 340 mV at 10 mA cm−2, a smaller Tafel slope of 51 mV dec−1, and stability over 30 h. The unique tunability of these CoFe2O4 nanocrystals provides great potential for their application as an efficient and competitive anode material in the field of electrochemical water splitting as well as for systematic fundamental studies aiming at understanding the correlation of composition and structure with performance in electrocatalysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/cctc.201700376 2017 • 547 SiO multi-line laser-induced fluorescence for quantitative temperature imaging in flame-synthesis of nanoparticles
Chrystie, R.S.M. and Feroughi, O.M. and Dreier, T. and Schulz, C.
Applied Physics B: Lasers and Optics 123 (2017)Silicon monoxide (SiO) is an intermediate in the gas-phase synthesis of SiO2 nanoparticles and coatings. We demonstrate a method for in situ imaging the gas-phase temperature via multi-line laser-induced fluorescence (LIF) using excitation in the A1Π–X1Σ+(0,0) band near 235 nm. A low-pressure lean (3 kPa, φ = 0.39) premixed hydrogen/oxygen flame was seeded with 210 ppm hexamethyldisiloxane (HMDSO) to produce SiO2 nanoparticles. Spectral regions with no interference from other species in the flame were located, and the excitation-spectral range that provides the best temperature sensitivity was determined from numerical experiments. Quenching rates of the selected transitions were also determined from fluorescence lifetime measurements, and found to be independent of the excited rotational state. Upon laser light-sheet excitation, images of fluorescence were recorded for a sequence of excitation wavelengths and pixel-wise multi-line fitting of the spectra yields temperature images. The results were compared against multi-line NO-LIF temperature imaging measurements using the A2Σ+–X2Π(0,0) band near 225 nm from 500 ppm NO added to the gas flow as a thermometry target. Both methods show good qualitative agreement with each other and demonstrate that temperature can be evaluated from the zone in the reactor where SiO is naturally present without adding tracers. SiO LIF exhibited high signal-to-noise ratios of the order of ten times that of NO LIF. © 2017, Springer-Verlag Berlin Heidelberg.view abstract doi: 10.1007/s00340-017-6692-0 2017 • 546 Site-Specific SERS Assay for Survivin Protein Dimer: From Ensemble Experiments to Correlative Single-Particle Imaging
Wissler, J. and Bäcker, S. and Feis, A. and Knauer, S.K. and Schlücker, S.
Small 13 (2017)An assay for Survivin, a small dimeric protein which functions as modulator of apoptosis and cell division and serves as a promising diagnostic biomarker for different types of cancer, is presented. The assay is based on switching on surface-enhanced Raman scattering (SERS) upon incubation of the Survivin protein dimer with Raman reporter-labeled gold nanoparticles (AuNP). Site-specificity is achieved by complexation of nickel-chelated N-nitrilo-triacetic acid (Ni-NTA) anchors on the particle surface by multiple histidines (His6-tag) attached to each C-terminus of the centrosymmetric protein dimer. Correlative single-particle analysis using light sheet laser microscopy enables the simultaneous observation of both elastic and inelastic light scattering from the same sample volume. Thereby, the SERS-inactive AuNP-protein monomers can be directly discriminated from the SERS-active AuNP-protein dimers/oligomers. This information, i.e. the percentage of SERS-active AuNP in colloidal suspension, is not accessible from conventional SERS experiments due to ensemble averaging. The presented correlative single-particle approach paves the way for quantitative site-specific SERS assays in which site-specific protein recognition by small chemical and in particular supramolecular ligands can be tested. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/smll.201700802 2017 • 545 Size Quenching during Laser Synthesis of Colloids Happens Already in the Vapor Phase of the Cavitation Bubble
Letzel, A. and Gökce, B. and Wagener, P. and Ibrahimkutty, S. and Menzel, A. and Plech, A. and Barcikowski, S.
Journal of Physical Chemistry C 121 5356-5365 (2017)Although nanoparticle synthesis by pulsed laser ablation in liquids (PLAL) is gaining wide applicability, the mechanism of particle formation, in particular size-quenching effects by dissolved anions, is not fully understood yet. It is well-known that the size of small primary particles (d ≤ 10 nm), secondary particles (spherical particles d > 10 nm), and agglomerates observed ex situ is effectively reduced by the addition of small amounts of monovalent electrolyte to the liquid prior to laser ablation. In this study, we focus on the particle formation and evolution inside the vapor filled cavitation bubble. This vapor phase is enriched with ions from the afore added electrolyte. By probing the cavitation bubbles' interior by means of small-angle X-ray scattering (SAXS), we are able to examine whether the size quenching reaction between nanoparticles and ions starts already during cavitation bubble confinement or if these reactions are subjected to the liquid phase. We find that particle size quenching occurs already within the first bubble oscillation (approximately 100 μs after laser impact), still inside the vapor phase. Thereby we demonstrate that nanoparticle-ion interactions during PLAL are in fact a gas phase phenomenon. These interactions include size reduction of both primary and secondary particles and a decreased abundance of the latter as shown by in situ SAXS and confirmed by ex situ particle analysis (e.g., static SAXS and TEM). (Figure Presented). © 2017 American Chemical Society.view abstract doi: 10.1021/acs.jpcc.6b12554 2017 • 544 Size- and density-controlled deposition of Ag nanoparticle films by a novel low-temperature spray chemical vapour deposition method—research into mechanism, particle growth and optical simulation
Liu, Y. and Plate, P. and Hinrichs, V. and Köhler, T. and Song, M. and Manley, P. and Schmid, M. and Bartsch, P. and Fiechter, S. and Lux-Steiner, M.C. and Fischer, C.-H.
Journal of Nanoparticle Research 19 (2017)Ag nanoparticles have attracted interest for plasmonic absorption enhancement of solar cells. For this purpose, well-defined particle sizes and densities as well as very low deposition temperatures are required. Thus, we report here a new spray chemical vapour deposition method for producing Ag NP films with independent size and density control at substrate temperatures even below 100 °C, which is much lower than for many other techniques. This method can be used on different substrates to deposit Ag NP films. It is a reproducible, low-cost process which uses trimethylphosphine (hexafluoroacetylacetonato) silver as a precursor in alcoholic solution. By systematic variation of deposition parameters and classic experiments, mechanisms of particle growth and of deposition processes as well as the low decomposition temperature of the precursor could be explained. Using the 3D finite element method, absorption spectra of selected samples were simulated, which fitted well with the measured results. Hence, further applications of such Ag NP films for generating plasmonic near field can be predicted by the simulation. © 2017, Springer Science+Business Media Dordrecht.view abstract doi: 10.1007/s11051-017-3834-6 2017 • 543 Size-dependent reactivity of gold-copper bimetallic nanoparticles during CO2 electroreduction
Mistry, H. and Reske, R. and Strasser, P. and Roldan Cuenya, B.
Catalysis Today 288 30-36 (2017)New catalysts are needed to achieve lower overpotentials and higher faradaic efficiency for desirable products during the electroreduction of CO2. In this study, we explore the size-dependence of monodisperse gold-copper alloy nanoparticles (NPs) synthesized by inverse micelle encapsulation as catalysts for CO2 electroreduction. X-ray spectroscopy revealed that gold-copper alloys were formed and were heavily oxidized in their initial as prepared state. Current density was found to increase significantly for smaller NPs due to the increasing population of strongly binding low coordinated sites on NPs below 5nm. Product analysis showed formation of H2, CO, and CH4, with faradaic selectivity showing a minor dependence on size. The selectivity trends observed are assigned to reaction-induced segregation of gold atoms to the particle surface and altered electronic or geometric properties due to alloying. © 2016.view abstract doi: 10.1016/j.cattod.2016.09.017 2017 • 542 Solar biosupercapacitor
González-Arribas, E. and Aleksejeva, O. and Bobrowski, T. and Toscano, M.D. and Gorton, L. and Schuhmann, W. and Shleev, S.
Electrochemistry Communications 74 9-13 (2017)Here we report on an entirely new kind of bioelectronic device – a solar biosupercapacitor, which is built from a dual-feature photobioanode combined with a double-function enzymatic cathode. The self-charging biodevice, based on transparent nanostructured indium tin oxide electrodes modified with biological catalysts, i.e. thylakoid membranes and bilirubin oxidase, is able to capacitively store electricity produced by direct conversion of radiant energy into electric energy. When self-charged during 10 min, using ambient light only, the biosupercapacitor provided a maximum of 6 mW m− 2 at 0.20 V. © 2016 Elsevier B.V.view abstract doi: 10.1016/j.elecom.2016.11.009 2017 • 541 Spectroscopic models for laser-heated silicon and copper nanoparticles
Daun, K. and Menser, J. and Mansmann, R. and Moghaddam, S.T. and Dreier, T. and Schulz, C.
Journal of Quantitative Spectroscopy and Radiative Transfer 197 3-11 (2017)Interpreting laser-induced incandescence (LII) measurements on aerosolized nanoparticles requires a spectroscopic model that relates the measured spectral incandescence to the temperature of the nanoparticles. We present spectroscopic models for molten silicon and copper nanoparticles, which are evaluated through extinction and incandescence measurements on nanoaerosols. Measurements on molten silicon nanoparticles are consistent with the Drude theory in the Rayleigh limit of Mie theory. The copper nanoparticles were initially assumed to coalesce into spheres, but the observed spectral incandescence does not show a surface plasmon polariton (SPP) peak in the vicinity of 600. nm expected of spheres. A simulation based on the discrete dipole approximation (DDA) suggests that this effect could be explained by the structure of the copper aggregates. © 2016.view abstract doi: 10.1016/j.jqsrt.2016.10.006 2017 • 540 Surface-Enhanced Raman Spectroscopy and Density Functional Theory Calculations of a Rationally Designed Rhodamine with Thiol Groups at the Xanthene Ring
Brem, S. and Schlücker, S.
Journal of Physical Chemistry C 121 15310-15317 (2017)Rhodamines are widely used dyes in fluorescence and surface-enhanced Raman spectroscopy (SERS). The latter requires adsorption of the dye onto the surface of plasmonic nanostructures, a process which requires attractive molecule-surface interactions. Here, we report an experimental SERS and computational density functional theory (DFT) study investigating the role of thiol functionalization at the xanthene ring of the rhodamine in the adsorption onto gold nanoparticles. For this purpose, a new bisthiolated rhodamine derivative was rationally designed and synthesized via a PPh3/I2 reduction route. The introduction of two thiol moieties directly at the xanthene ring provides the shortest possible distance between the molecular π-system and the metal surface for maximum SERS enhancement combined with the strong Au-S interaction for chemisorption. The comparison of experimental SERS spectra obtained from gold nanostars and a film of gold nanoparticles with results from DFT calculations (molecular electrostatic potential, normal modes) suggests adsorption via the thiol groups at the xanthene moiety. © 2017 American Chemical Society.view abstract doi: 10.1021/acs.jpcc.7b01504 2017 • 539 Synergistic effect of potassium hydroxide and steam co-treatment on the functionalization of carbon nanotubes applied as basic support in the Pd-catalyzed liquid-phase oxidation of ethanol
Dong, W. and Xia, W. and Xie, K. and Peng, B. and Muhler, M.
Carbon 121 452-462 (2017)Surface functionalization of carbon nanotubes (CNTs) was achieved by a thermal treatment in the presence of pre-adsorbed potassium hydroxide and steam at 350–550 °C. The generated oxygen-containing functional groups were more basic and thermally stable compared with conventional acid-generated groups. The influence of the KOH-steam co-treatment conditions on the functionalization of CNTs was systematically investigated. Residual K species were found to intercalate in the inner graphene layers of the CNTs providing additional Brønsted basicity. Owing to the favorable basic properties and high thermal stability of the generated functional groups, Pd nanoparticles supported on the co-treated CNTs were found to be strongly anchored leading to a high degree of Pd dispersion and a high resistance to sintering. The Pd nanoparticles on the co-treated CNT support produced at 450 °C and 550 °C showed the highest activity and yields of acetic acid in the aerobic oxidation of aqueous ethanol reaching almost full conversion after 5 h in the absence of additional base. In addition, the KOH-steam co-treatment was found to enhance the recyclability of the Pd/CNT catalysts. © 2017 Elsevier Ltdview abstract doi: 10.1016/j.carbon.2017.06.019 2017 • 538 The Production of Cu Nanoparticles on Large Area Graphene by Sputtering and in-Flight Sintering
Ünlü, C.G. and Acet, M. and Tekgül, A. and Farle, M. and Atakan, Ş. and Lindner, J.
Crystal Research and Technology 52 (2017)We have developed a simple method to synthesize Cu nanoparticles on graphene, which is a composite that is currently investigated for use as biosensors. Firstly, large area graphene (2 × 2 cm2) was prepared by chemical vapor deposition on Cu foils and then transferred onto SiO2 substrates by a transfer process. The Cu nanoparticles were collected on graphene/SiO2 by magnetron sputtering. The presence of graphene was verified by optical microscopy and Raman spectroscopy. The structure of graphene decorated with Cu nanoparticles was determined by scanning and transmission electron microscopy. The results show that the Cu nanoparticles acquire a cubic structure on graphene. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/crat.201700149 2017 • 537 Time-resolved impact electrochemistry for quantitative measurement of single-nanoparticle reaction kinetics
Saw, E.N. and Kratz, M. and Tschulik, K.
Nano Research 1-10 (2017)Single-nanoparticle electrochemistry has been established as a tool to characterize various nanomaterials based on the charge passed during their random impact at an electrode. Here it is demonstrated that the duration and shape of the resulting current peak can be used to quantify the reaction kinetics on a single-particle basis. Both the chemical rate constant and reaction mechanism for oxidation of single nanoparticles in different electrolytes can be determined directly from the duration of the current signal recorded in high-speed, highsensitivity current measurements. Using 29-nm-sized Ag particles in four different electrolytes as a proof of concept for this general approach, hitherto inaccessible insights into single-particle reactivity are provided. While comparable rate constants were measured for the four electrolytes at low overpotentials, transport-limited impacts at high overpotentials were found to depend strongly on the type and quantity of anions present in solution. [Figure not available: see fulltext.] © 2017 Tsinghua University Press and Springer-Verlag GmbH Germanyview abstract doi: 10.1007/s12274-017-1578-3 2017 • 536 Transparent, mediator- and membrane-free enzymatic fuel cell based on nanostructured chemically modified indium tin oxide electrodes
González-Arribas, E. and Bobrowski, T. and Di Bari, C. and Sliozberg, K. and Ludwig, R. and Toscano, M.D. and De Lacey, A.L. and Pita, M. and Schuhmann, W. and Shleev, S.
Biosensors and Bioelectronics 97 46-52 (2017)We detail a mediator- and membrane-free enzymatic glucose/oxygen biofuel cell based on transparent and nanostructured conducting supports. Chemically modified indium tin oxide nanoparticle modified electrodes were used to substantially increase the active surface area without significantly compromising transparency. Two different procedures for surface nanostructuring were employed, viz. spray-coating and drop-coating. The spray-coated biodevice showed superior characteristics as compared to the drop-coated enzymatic fuel cell, as a result of the higher nanostructured surface area as confirmed by electrochemical characterisation, as well as scanning electron and atomic force microscopy. Subsequent chemical modification with silanes, followed by the immobilisation of either cellobiose dehydrogenase from Corynascus thermophiles or bilirubin oxidase from Myrothecium verrucaria, were performed to obtain the bioanodes and biocathodes, respectively. The optimised biodevice exhibited an OCV of 0.67 V and power output of up to 1.4 µW/cm2 at an operating voltage of 0.35 V. This is considered a significant step forward in the field of glucose/oxygen membrane- and mediator-free, transparent enzymatic fuel cells. © 2017 Elsevier B.V.view abstract doi: 10.1016/j.bios.2017.05.040 2017 • 535 Upconversion Nanoparticles Synthesized by Ultrashort Pulsed Laser Ablation in Liquid: Effect of the Stabilizing Environment
Gemini, L. and Schmitz, T. and Kling, R. and Barcikowski, S. and Gökce, B.
ChemPhysChem 18 1210-1216 (2017)The distinctive feature of upconverting compounds to absorb and emit light in the near-infrared region has made upconverting nanoparticles of great interest in various application fields. Nevertheless, these colloids show a highly hydrophobic behavior, and therefore, the use of a proper stabilizing agent is necessary in most cases. Although few chemical techniques for colloid stabilization are available, it is still difficult to achieve a fully reproducible synthesis method for stable upconverting nanoparticle colloids. In this work, upconversion 18 %Yb:1 %Er:NaYF4 nanoparticles were produced by ultrafast pulsed laser ablation in a water and 2-[2-(2-methoxyethoxy)- ethoxy]acetic acid (MEEAA) environment to assess the stabilization effect of the surfactant on the nanoparticle colloid properties. The effects of the laser fluence and MEEAA concentration on the nanoparticles′ properties were investigated by TEM, EDS, and emission spectra analyses. The results show that ultrashort pulsed laser ablation in liquid allows generating highly spherical nanoparticles with conserved stoichiometry and optical properties. Moreover, it is possible to obtain colloids with significantly higher stability and preserved optical properties by one-step PLAL processes directly in the MEEAA environment. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/cphc.201601266 2017 • 534 Uptake of the proteins HTRA1 and HTRA2 by cells mediated by calcium phosphate nanoparticles
Rotan, O. and Severin, K.N. and Pöpsel, S. and Peetsch, A. and Merdanovic, M. and Ehrmann, M. and Epple, M.
Beilstein Journal of Nanotechnology 8 381-393 (2017)The efficient intracellular delivery of (bio)molecules into living cells remains a challenge in biomedicine. Many biomolecules and synthetic drugs are not able to cross the cell membrane, which is a problem if an intracellular mode of action is desired, for example, with a nuclear receptor. Calcium phosphate nanoparticles can serve as carriers for small and large biomolecules as well as for synthetic compounds. The nanoparticles were prepared and colloidally stabilized with either polyethyleneimine (PEI; cationic nanoparticles) or carboxymethyl cellulose (CMC; anionic nanoparticles) and loaded with defined amounts of the fluorescently labelled proteins HTRA1, HTRA2, and BSA. The nanoparticles were purified by ultracentrifugation and characterized by dynamic light scattering and scanning electron microscopy. Various cell types (HeLa, MG-63, THP-1, and hMSC) were incubated with fluorescently labelled proteins alone or with protein-loaded cationic and anionic nanoparticles. The cellular uptake was followed by light and fluorescence microscopy, confocal laser scanning microscopy (CLSM), and flow cytometry. All proteins were readily transported into the cells by cationic calcium phosphate nanoparticles. Notably, only HTRA1 was able to penetrate the cell membrane of MG-63 cells in dissolved form. However, the application of endocytosis inhibitors revealed that the uptake pathway was different for dissolved HTRA1 and HTRA1-loaded nanoparticles. © 2017 Rotan et al.view abstract doi: 10.3762/bjnano.8.40 2017 • 533 Water-free synthesis of ZnO quantum dots for application as an electron injection layer in light-emitting electrochemical cells
Daumann, S. and Andrzejewski, D. and Di Marcantonio, M. and Hagemann, U. and Wepfer, S. and Vollkommer, F. and Bacher, G. and Epple, M. and Nannen, E.
Journal of Materials Chemistry C 5 2344-2351 (2017)Large-area light emitters like organic (OLEDs) or quantum dot light-emitting devices (QLEDs) and light-emitting electrochemical cells (LECs) have gained increasing interest due to their cost-effective fabrication on various even flexible substrates. The implementation of ZnO nanoparticles as an electron injection layer in large-area emitters leads to efficient solution-based devices. However, ZnO support layers are frequently in direct contact with water-sensitive emitter materials, which requires ZnO nanoparticles with minimum water content. A water-free synthesis route (except for the small amount of water formed during the synthesis) of ligand-free ZnO nanoparticles is presented. The spherical ZnO nanoparticles have a diameter of 3.4 nm, possess a high crystallinity, and form stable dispersions in ethanol or 1-hexanol. Their application together with a transition metal complex (iTMC)-LEC as an additional electron injection layer resulted in an increase of the device efficiency from 1.6 to 2.4 lm W−1 as well as the reduction of the run-up time to one fifth, compared to the same system without ZnO nanoparticles. © The Royal Society of Chemistry.view abstract doi: 10.1039/c6tc05571k 2016 • 532 A novel magnetically-separable porous iron-oxide nanocomposite as an adsorbent for methylene blue (MB) dye
Sehlleier, Y.H. and Hardt, S. and Schulz, C. and Wiggers, H.
Journal of Environmental Chemical Engineering 4 3779-3787 (2016)In this study, efficient and magnetically separable adsorbents for the removal of organic pollutants from water are developed, which are both, environmental friendly and cheap to produce. A new type of porous iron-oxide/polymer nanocomposite was synthesized by a two-step process utilizing surface modification of gas-phase synthesized iron-oxide nanoparticles and a subsequent polymerization process. The potential of iron-oxide/polymer composite adsorbents with a large surface area for the removal of organic components was studied using methylene blue (MB) as a test substance. Adsorption isotherms fitted well with the Langmuir isotherm model and the adsorption capacity of MB on this adsorbent was found to be as high as 298 mg/g which is several times higher than the adsorption capacity of a number of recently reported potential adsorbents. Owing to its magnetic properties, the polluted adsorbent can be easily separated from aqueous solutions. © 2016 Elsevier B.V. All rights reserved.view abstract doi: 10.1016/j.jece.2016.08.018 2016 • 531 A versatile large-scale and green process for synthesizing magnetic nanoparticles with tunable magnetic hyperthermia features
Simeonidis, K. and Liébana-Viñas, S. and Wiedwald, U. and Ma, Z. and Li, Z.-A. and Spasova, M. and Patsia, O. and Myrovali, E. and Makridis, A. and Sakellari, D. and Tsiaoussis, I. and Vourlias, G. and Farle, M. and Angelakeris, M.
RSC Advances 6 53107-53117 (2016)This work proposes a large-scale synthesis methodology for engineered and functional magnetic nanoparticles (i.e. ferrites, sulfides) designed towards the principles of green and sustainable production combined with biomedical applicability. The experimental setup consists of a two-stage continuous-flow reactor in which single-crystalline nanoparticles are formed by the coprecipitation of metal salts in an aqueous environment. A series of optimized iron-based nanocrystals (Fe3O4, Fe3S4, CoFe2O4 and MnFe2O4) with diameters between 18 and 38 nm has been obtained. The samples were validated as potential magnetic hyperthermia agents by their heating efficiency as determined by specific loss power (SLP) in calorimetric experiments. In an effort to enhance colloidal stability and surface functionality, nanoparticles were coated by typical molecules of biomedical interest in a single step process. Finally, two-phase particle systems have been produced by a two-stage procedure to enhance the heating rate by the effective combination of different magnetic features. Results indicate relatively high SLP values for uncoated nanoparticles (420 W g-1 for Fe3O4) and a reduction of 20-60% in the heat dissipation rate upon covering by functional groups. Eventually, such effect was more than counterbalanced by the magnetic coupling of different phases in binary systems, since SLP was multiplied up to ∼1700 W g-1 for MnFe2O4/Fe3O4 suggesting a novel route to tune the efficiency of magnetic hyperthermia agents. © 2016 The Royal Society of Chemistry.view abstract doi: 10.1039/c6ra09362k 2016 • 530 Alternative Precursors for the Synthesis of Binary Sb2E3and Bi2E3(E = S, Se, Te) Nanoparticles by the Hot Injection Method
Rusek, M. and Bendt, G. and Wölper, C. and Schulz, S.
European Journal of Inorganic Chemistry 2016 3673-3679 (2016)Intramolecularly stabilized Sb(OCH2CH2NMe2)3(1) and Bi(OCH2CH2NMe2)3(2) readily react with (Me3Si)2S and (Et3Si)2E (E = Se, Te) at moderate temperatures (hot injection method) with elimination of the corresponding silyl ether and subsequent formation of the group 15 chalcogenides Sb2E3and Bi2E3, which were characterized by XRD, SEM, and energy-dispersive X-ray spectroscopy (EDX). In addition, the solid-state structure of 1 was determined by single-crystal XRD. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/ejic.201600490 2016 • 529 Atomic layer deposition and high-resolution electron microscopy characterization of nickel nanoparticles for catalyst applications
Dashjav, E. and Lipińska-Chwałek, M. and Grüner, D. and Mauer, G. and Luysberg, M. and Tietz, F.
Surface and Coatings Technology 307 428-435 (2016)Ni nanoparticles (diameter < 10 nm) are deposited on Si and ceramic substrates of porous lanthanum-substituted strontium titanate/yttrium-stabilized zirconia (LST/YSZ) composites by a two-step process. First, NiO films are produced by atomic layer deposition at 200 °C using bis(methylcyclopentadienyl)nickel(II) (Ni(MeCp)2) and H2O as precursors. In the second step, the NiO films are reduced in H2 atmosphere at 400–800 °C. The size of the resulting Ni nanoparticles is controlled by the temperature. The largest particles with a diameter of about 7 nm are obtained at 800 °C. NiO film and Ni nanoparticles deposited on Si substrates are characterized by high-resolution electron microscopy. It was found that the Ni(MeCp)2 precursor reacts with the substrate, leading to the formation of NiSi2 precipitates beneath the surface of the Si wafer and amorphization of the surrounding area, resulting in a 10 nm thick top layer of the Si wafer. After reductive annealing, NiSi2 precipitates are preserved but Si recrystallizes and the amorphous NiO film transforms into crystalline Ni nanoparticles well distributed on the wafer surface. Process parameters were optimized for Si substrates and transfer of the process to ceramic LST/YSZ substrates is possible in principle. However, a much higher number of ALD cycles (1200 compared to 100 for Si) are necessary to obtain Ni nanoparticles of similar size and the number density of particles is lower than observed for Si substrates. © 2016 Elsevier B.V.view abstract doi: 10.1016/j.surfcoat.2016.08.074 2016 • 528 Barium sulfate micro- and nanoparticles as bioinert reference material in particle toxicology
Loza, K. and Föhring, I. and Bünger, J. and Westphal, G.A. and Köller, M. and Epple, M. and Sengstock, C.
Nanotoxicology 10 1492-1502 (2016)The inhalation of particles and their exposure to the bronchi and alveoli constitute a major public health risk. Chemical as well as particle-related properties are important factors for the biological response but are difficult to separate from each other. Barium sulfate is a completely inert chemical compound, therefore it is ideally suited to separate these two factors. The biological response of rat alveolar macrophages (NR8383) was analyzed after exposure to barium sulfate particles with three different diameters (40 nm, 270 nm, and 1.3 μm, respectively) for 24 h in vitro (particle concentrations from 12.5 to 200 μg mL− 1). The particles were colloidally stabilized as well as fluorescently-labeled by carboxymethylcellulose, conjugated with 6-aminofluorescein. All kinds of barium sulfate particles were efficiently taken up by NR8383 cells and found inside endo-lysosomes, but never in the cell nucleus. Neither an inflammatory nor a cytotoxic response was detected by the ability of dHL-60 and NR8383 cells to migrate towards a chemotactic gradient (conditioned media of NR8383 cells) and by the release of inflammatory mediators (CCL2, TNF-α, IL-6). The particles neither caused apoptosis (up to 200 μg mL− 1) nor necrosis (up to 100 μg mL− 1). As only adverse reaction, necrosis was found at a concentration of 200 μg mL− 1 of the largest barium sulfate particles (1.3 μm). Barium sulfate particles are ideally suited as bioinert control to study size-dependent effects such as uptake mechanisms of intracellular distributions of pure particles, especially in nanotoxicology. © 2016 Informa UK Limited, trading as Taylor & Francis Group.view abstract doi: 10.1080/17435390.2016.1235740 2016 • 527 Barrierless growth of precursor-free, ultrafast laser-fragmented noble metal nanoparticles by colloidal atom clusters - A kinetic in situ study
Jendrzej, S. and Gökce, B. and Amendola, V. and Barcikowski, S.
Journal of Colloid and Interface Science 463 299-307 (2016)Unintended post-synthesis growth of noble metal colloids caused by excess amounts of reactants or highly reactive atom clusters represents a fundamental problem in colloidal chemistry, affecting product stability or purity. Hence, quantified kinetics could allow defining nanoparticle size determination in dependence of the time. Here, we investigate in situ the growth kinetics of ps pulsed laser-fragmented platinum nanoparticles in presence of naked atom clusters in water without any influence of reducing agents or surfactants. The nanoparticle growth is investigated for platinum covering a time scale of minutes to 50 days after nanoparticle generation, it is also supplemented by results obtained from gold and palladium. Since a minimum atom cluster concentration is exceeded, a significant growth is determined by time resolved UV/Vis spectroscopy, analytical disc centrifugation, zeta potential measurement and transmission electron microscopy. We suggest a decrease of atom cluster concentration over time, since nanoparticles grow at the expense of atom clusters. The growth mechanism during early phase (<1. day) of laser-synthesized colloid is kinetically modeled by rapid barrierless coalescence. The prolonged slow nanoparticle growth is kinetically modeled by a combination of coalescence and Lifshitz-Slyozov-Wagner kinetic for Ostwald ripening, validated experimentally by the temperature dependence of Pt nanoparticle size and growth quenching by Iodide anions. © 2015.view abstract doi: 10.1016/j.jcis.2015.10.032 2016 • 526 Characterization of the oleic acid/iron oxide nanoparticle interface by magnetic resonance
Masur, S. and Zingsem, B. and Marzi, T. and Meckenstock, R. and Farle, M.
Journal of Magnetism and Magnetic Materials 415 8-12 (2016)The synthesis of colloidal nanoparticles involves surfactant molecules, which bind to the particle surface and stabilize nanoparticles against aggregation. In many cases these protecting shells also can be used for further functionalization. In this study, we investigated monodisperse single crystalline iron oxide core/shell nanoparticles (FexOy-NPs) in situ covered with an oleic acid layer which showed two electron spin resonance (ESR) signals. The nanoparticles with the ligands attached were characterized by transmission electron microscopy (TEM) and ferro- and paramagnetic resonance (FMR, EPR). Infrared spectroscopy confirmed the presence of the functional groups and revealed that the oleic acid (OA) is chemisorbed as a carboxylate on the iron oxide and is coordinated symmetrically to the oxide atoms. We show that the EPR signal of the OA ligand molecule can be used as a local probe to determine the temperature changes at the surface of the nanoparticle. © 2016 Published by Elsevier B.V.view abstract doi: 10.1016/j.jmmm.2016.03.045 2016 • 525 Characterizing the Effect of Multivalent Conjugates Composed of Aβ-Specific Ligands and Metal Nanoparticles on Neurotoxic Fibrillar Aggregation
Streich, C. and Akkari, L. and Decker, C. and Bormann, J. and Rehbock, C. and Müller-Schiffmann, A. and Niemeyer, F.C. and Nagel-Steger, L. and Willbold, D. and Saccà, B. and Korth, C. and Schrader, T. and Barcikowski, S.
ACS Nano 10 7582-7597 (2016)Therapeutically active small molecules represent promising nonimmunogenic alternatives to antibodies for specifically targeting disease-relevant receptors. However, a potential drawback compared to antibody-antigen interactions may be the lower affinity of small molecules toward receptors. Here, we overcome this low-affinity problem by coating the surface of nanoparticles (NPs) with multiple ligands. Specifically, we explored the use of gold and platinum nanoparticles to increase the binding affinity of Aβ-specific small molecules to inhibit Aβ peptide aggregation into fibrils in vitro. The interactions of bare NPs, free ligands, and NP-bound ligands with Aβ are comprehensively studied via physicochemical methods (spectroscopy, microscopy, immunologic tests) and cell assays. Reduction of thioflavin T fluorescence, as an indicator for β-sheet content, and inhibition of cellular Aβ excretion are even more effective with NP-bound ligands than with the free ligands. The results from this study may have implications in the development of therapeutics for treating Alzheimer's disease. © 2016 American Chemical Society.view abstract doi: 10.1021/acsnano.6b02627 2016 • 524 Co3O4 Nanoparticles Supported on Mesoporous Carbon for Selective Transfer Hydrogenation of α,β-Unsaturated Aldehydes
Wang, G.-H. and Deng, X. and Gu, D. and Chen, K. and Tüysüz, H. and Spliethoff, B. and Bongard, H.-J. and Weidenthaler, C. and Schmidt, W. and Schüth, F.
Angewandte Chemie - International Edition 55 11101-11105 (2016)A simple and scalable method for synthesizing Co3O4nanoparticles supported on the framework of mesoporous carbon (MC) was developed. Benefiting from an ion-exchange process during the preparation, the cobalt precursor is introduced into a mesostructured polymer framework that results in Co3O4nanoparticles (ca. 3 nm) supported on MC (Co3O4/MC) with narrow particle size distribution and homogeneous dispersion after simple reduction/pyrolysis and mild oxidation steps. The as-obtained Co3O4/MC is a highly efficient catalyst for transfer hydrogenation of α,β-unsaturated aldehydes. Selectivities towards unsaturated alcohols are always higher than 95 % at full conversion. In addition, the Co3O4/MC shows high stability under the reaction conditions, it can be recycled at least six times without loss of activity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/anie.201604673 2016 • 523 Co@Co3O4 Encapsulated in Carbon Nanotube-Grafted Nitrogen-Doped Carbon Polyhedra as an Advanced Bifunctional Oxygen Electrode
Aijaz, A. and Masa, J. and Rösler, C. and Xia, W. and Weide, P. and Botz, A.J.R. and Fischer, R.A. and Schuhmann, W. and Muhler, M.
Angewandte Chemie - International Edition 55 4087-4091 (2016)Efficient reversible oxygen electrodes for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are vitally important for various energy conversion devices, such as regenerative fuel cells and metal-air batteries. However, realization of such electrodes is impeded by insufficient activity and instability of electrocatalysts for both water splitting and oxygen reduction. We report highly active bifunctional electrocatalysts for oxygen electrodes comprising core-shell Co@Co3O4 nanoparticles embedded in CNT-grafted N-doped carbon-polyhedra obtained by the pyrolysis of cobalt metal-organic framework (ZIF-67) in a reductive H2 atmosphere and subsequent controlled oxidative calcination. The catalysts afford 0.85 V reversible overvoltage in 0.1 m KOH, surpassing Pt/C, IrO2, and RuO2 and thus ranking them among one of the best non-precious-metal electrocatalysts for reversible oxygen electrodes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/anie.201509382 2016 • 522 Colonic gene silencing using siRNA-loaded calcium phosphate/PLGA nanoparticles ameliorates intestinal inflammation in vivo
Frede, A. and Neuhaus, B. and Klopfleisch, R. and Walker, C. and Buer, J. and Müller, W. and Epple, M. and Westendorf, A.M.
Journal of Controlled Release 222 86-96 (2016)Cytokines and chemokines are predominant players in the progression of inflammatory bowel diseases. While systemic neutralization of these players with antibodies works well in some patients, serious contraindications and side effects have been reported. Therefore, the local interference of cytokine signaling mediated by siRNA-loaded nanoparticles might be a promising new therapeutic approach. In this study, we produced multi-shell nanoparticles consisting of a calcium phosphate (CaP) core coated with siRNA directed against pro-inflammatory mediators, encapsulated into poly(d,l-lactide-co-glycolide acid) (PLGA), and coated with a final outer layer of polyethyleneimine (PEI), for the local therapeutic treatment of colonic inflammation. In cell culture, siRNA-loaded CaP/PLGA nanoparticles exhibited a rapid cellular uptake, almost no toxicity, and an excellent in vitro gene silencing efficiency. Importantly, intrarectal application of these nanoparticles loaded with siRNA directed against TNF-α, KC or IP-10 to mice suffering from dextran sulfate sodium (DSS)-induced colonic inflammation led to a significant decrease of the target genes in colonic biopsies and mesenteric lymph nodes which was accompanied with a distinct amelioration of intestinal inflammation. Thus, this study provides evidence that the specific and local modulation of the inflammatory response by CaP/PLGA nanoparticle-mediated siRNA delivery could be a promising approach for the treatment of intestinal inflammation. © 2015 Elsevier B.V. All rights reserved.view abstract doi: 10.1016/j.jconrel.2015.12.021 2016 • 521 Combination of nanoparticle-based therapeutic vaccination and transient ablation of regulatory T cells enhances anti-viral immunity during chronic retroviral infection
Knuschke, T. and Rotan, O. and Bayer, W. and Sokolova, V. and Hansen, W. and Sparwasser, T. and Dittmer, U. and Epple, M. and Buer, J. and Westendorf, A.M.
Retrovirology 13 (2016)Background: Regulatory T cells (Tregs) have been shown to limit anti-viral immunity during chronic retroviral infection and to restrict vaccine-induced T cell responses. The objective of the study was to assess whether a combinational therapy of nanoparticle-based therapeutic vaccination and concomitant transient ablation of Tregs augments anti-viral immunity and improves virus control in chronically retrovirus-infected mice. Therefore, chronically Friend retrovirus (FV)-infected mice were immunized with calcium phosphate (CaP) nanoparticles functionalized with TLR9 ligand CpG and CD8+ or CD4+ T cell epitope peptides (GagL85-93 or Env gp70123-141) of FV. In addition, Tregs were ablated during the immunization process. Reactivation of CD4+ and CD8+ effector T cells was analysed and the viral loads were determined. Results: Therapeutic vaccination of chronically FV-infected mice with functionalized CaP nanoparticles transiently reactivated cytotoxic CD8+ T cells and significantly reduced the viral loads. Transient ablation of Tregs during nanoparticle-based therapeutic vaccination strongly enhanced anti-viral immunity and further decreased viral burden. Conclusion: Our data illustrate a crucial role for CD4+ Foxp3+ Tregs in the suppression of anti-viral T cell responses during therapeutic vaccination against chronic retroviral infection. Thus, the combination of transient Treg ablation and therapeutic nanoparticle-based vaccination confers robust and sustained anti-viral immunity. © 2016 Knuschke et al.view abstract doi: 10.1186/s12977-016-0258-9 2016 • 520 Concentrating light in Cu(In,Ga)Se2 solar cells
Schmid, M. and Yin, G. and Song, M. and Duan, S. and Heidmann, B. and Sancho-Martinez, D. and Kämmer, S. and Köhler, T. and Manley, P. and Lux-Steiner, M.C.
Proceedings of SPIE - The International Society for Optical Engineering 9937 (2016)Light concentration has proven beneficial for solar cells, most notably for highly efficient but expensive absorber materials using high concentrations and large scale optics. Here we investigate light concentration for cost efficient thinfilm solar cells which show nano-or microtextured absorbers. Our absorber material of choice is Cu(In,Ga)Se2 (CIGSe) which has a proven stabilized record efficiency of 22.6% and which-despite being a polycrystalline thin-film material-is very tolerant to environmental influences. Taking a nanoscale approach, we concentrate light in the CIGSe absorber layer by integrating photonic nanostructures made from dielectric materials. The dielectric nanostructures give rise to resonant modes and field localization in their vicinity. Thus when inserted inside or adjacent to the absorber layer, absorption and efficiency enhancement are observed. In contrast to this internal absorption enhancement, external enhancement is exploited in the microscale approach: mm-sized lenses can be used to concentrate light onto CIGSe solar cells with lateral dimensions reduced down to the micrometer range. These micro solar cells come with the benefit of improved heat dissipation compared to the large scale concentrators and promise compact high efficiency devices. Both approaches of light concentration allow for reduction in material consumption by restricting the absorber dimension either vertically (ultra-thin absorbers for dielectric nanostructures) or horizontally (micro absorbers for concentrating lenses) and have significant potential for efficiency enhancement. © 2016 SPIE.view abstract doi: 10.1117/12.2238056 2016 • 519 Conjugation of thiol-terminated molecules to ultrasmall 2 nm-gold nanoparticles leads to remarkably complex 1H-NMR spectra
Schuetze, B. and Mayer, C. and Loza, K. and Gocyla, M. and Heggen, M. and Epple, M.
Journal of Materials Chemistry B 4 2179-2189 (2016)Gold nanoparticles, functionalized by aliphatic and aromatic mercapto-functionalized carboxylic acids and by two small peptides (CG and CGGRGD), respectively, were synthesized by the reduction of HAuCl4 with NaBH4 in the presence of the above ligands. After purification by centrifugation or filtration and redispersion, the dispersed nanoparticles were analysed by differential centrifugal sedimentation (DCS), high-resolution transmission electron microscopy (HRTEM), and a variety of NMR spectroscopic techniques: 1H-NMR, 1H,1H-COSY and 1H-DOSY. The hydrodynamic diameter of the particles was between 1.8 and 4.4 nm, as determined by DOSY, in good agreement with the DCS and HRTEM results. Diffusion ordered spectroscopy (DOSY) turned out to be a valuable and non-destructive tool to determine the hydrodynamic diameter of dispersed nanoparticles and to control the purity of the final particles. The coordination of the organic molecules to the gold nanoparticles resulted in distinct and complex changes in the 1H-NMR spectra. These were only partially explainable but clearly caused by the vicinity of the molecules to the gold nanoparticle. © The Royal Society of Chemistry 2016.view abstract doi: 10.1039/c5tb02443a 2016 • 518 Continuous multigram nanoparticle synthesis by high-power, high-repetition-rate ultrafast laser ablation in liquids
Streubel, R. and Barcikowski, S. and Gökce, B.
Optics Letters 41 1486-1489 (2016)Utilizing a novel laser system consisting of a 500 W, 10 MHz, 3 ps laser source which is fully synchronized with a polygon scanner reaching scanning speeds up to 500 m/s, we explore the possibilities to increase the productivity of nanoparticle synthesis by laser ablation in liquids. By exploiting the high scanning speed, laser-induced cavitation bubbles are spatially bypassed at high repetition rates and continuous multigram ablation rates up to 4 g/h are demonstrated for platinum, gold, silver, aluminum, copper, and titanium. Furthermore, the applicable, ablation-effective repetition rate is increased by two orders ofmagnitude.The ultrafast ablation mechanisms are investigated for different laser fluences, repetition rates, interpulse distances, and ablation times, while the resulting trends are successfully described by validating a model developed for ultrafast laser ablation in air to hold in liquids as well. © 2016 Optical Society of America.view abstract doi: 10.1364/OL.41.001486 2016 • 517 Controlling the Photocorrosion of Zinc Sulfide Nanoparticles in Water by Doping with Chloride and Cobalt Ions
Weide, P. and Schulz, K. and Kaluza, S. and Rohe, M. and Beranek, R. and Muhler, M.
Langmuir 32 12641-12649 (2016)Photodegradation under UV light irradiation is a major drawback in photocatalytic applications of sulfide semiconductors. ZnS nanoparticles were doped with very low amounts of chloride or cobalt ions in the ppm range and codoped with chloride and cobalt ions during their synthesis by precipitation in aqueous solution followed by calcination. The high-temperature wurtzite phase annealed at 800 °C had a high susceptibility to UV irradiation in water, while the low-temperature zincblende phase annealed at 400 °C was found to be stable. Chlorine doping increased the rate of photocorrosion in water, whereas cobalt doping led to a stabilization of the ZnS nanoparticles. Based on photochemical and spectroscopic investigations applying UV/vis, X-ray photoelectron, and photoluminescence spectroscopy, the increased susceptibility of Cl-doped ZnS is ascribed to a higher number of surface point defects, whereas the stabilization by Co2+ is caused by additional recombination pathways for the charge carriers in the bulk, thus avoiding photocorrosion processes at the surface. Additional doping of Cl-doped ZnS with cobalt ions was found to counteract the detrimental effect of the chloride ions efficiently. © 2016 American Chemical Society.view abstract doi: 10.1021/acs.langmuir.6b03385 2016 • 516 Controlling the shape of Janus nanostructures through supramolecular modification of ABC terpolymer bulk morphologies
Hiekkataipale, P. and Löbling, T.I. and Poutanen, M. and Priimagi, A. and Abetz, V. and Ikkala, O. and Gröschel, A.H.
Polymer (United Kingdom) 107 456-465 (2016)Block copolymers microphase separate into a variety of bulk morphologies that serve as scaffolds, templates, masks and source for polymeric nano-particles. While supramolecular additives are common to complex within diblock copolymers to modify the morphology, the subtle effects of complexation on ABC triblock terpolymer morphologies are less explored. Here, we describe the manipulation of polystyrene-block-poly(4-vinylpyridine)-block-poly(tert-butyl methacrylate) (PS-b-P4VP-b-PT or S4VT) triblock terpolymer bulk morphologies through supramolecular complexation with rod-like 4-(4-pentylphenylazo)phenol (5PAP). The 5PAP molecule hydrogen bonds by phenolic groups to the 4VP repeating units and with increasing molar fraction of 5PAP, initially observed P4VP cylinders flatten into elliptic cylinders until a morphological transition occurs into a third (P4VP/5PAP) lamella. At sufficient 5PAP loadings, the cylinders can even merge into a perforated P4VP lamella located at the PS/PT interface. Quaternization of the P4VP phase and re-dispersion in organic solvent allows liberating S4VT Janus nanostructures from the bulk, including Janus cylinders, nanoporous Janus membranes and Janus sheets. The manipulation of “sandwiched” microphases through supramolecular binding motifs could allow the preparation of previously inaccessible terpolymer bulk morphologies and, in case of cross-linkable phases, lead to a larger library of Janus nano-objects. © 2016 Elsevier Ltdview abstract doi: 10.1016/j.polymer.2016.05.076 2016 • 515 Cr2O3 Nanoparticles on Ba5Ta4O15 as a Noble-Metal-Free Oxygen Evolution Co-Catalyst for Photocatalytic Overall Water Splitting
Soldat, J. and Busser, G.W. and Muhler, M. and Wark, M.
ChemCatChem 8 153-156 (2016)The (1 1 1)-layered perovskite material Ba5Ta4O15 represents a suitable photoabsorber with remarkable photocatalytic activity in overall water splitting. We are the first to demonstrate overall water splitting without the presence of a noble-metal-based co-catalyst over this catalyst. The photocatalytic activity of Ba5Ta4O15 was investigated by overall water splitting after reductive photodeposition of amorphous Cr2O3. The formation of Cr2O3 nanoparticles for water splitting was evidenced by X-ray photoelectron spectroscopy and transmission electron microscopy. The reductive photodeposition of very low amounts of Cr2O3 on Ba5Ta4O15 induces stable rates in overall water splitting up to 465 μmol h-1 H2 and 228 μmol h-1 O2. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/cctc.201500977 2016 • 514 Deagglomeration testing of airborne nanoparticle agglomerates: Stability analysis under varied aerodynamic shear and relative humidity conditions
Ding, Y. and Stahlmecke, B. and Kaminski, H. and Jiang, Y. and Kuhlbusch, T.A.J. and Riediker, M.
Aerosol Science and Technology 50 1253-1263 (2016)Occupational exposure to nanomaterial aerosols poses potential health risks to workers at nanotechnology workplaces. Understanding the mechanical stability of airborne nanoparticle agglomerates under varied mechanical forces and environmental conditions is important for estimating their emission potential and the released particle size distributions, which in consequence alters their transport and human uptake probability. In this study, two aerosolization and deagglomeration systems were used to investigate the potential for deagglomeration of nanopowder aerosols with different surface hydrophilicity under a range of shear forces and relative humidity conditions. Critical orifices were employed to subject airborne agglomerates to the shear forces induced by a pressure drop. Increasing applied pressure drop was found to be associated with decreased mean particle size and increased particle number concentrations. Rising humidity decreased the deagglomeration tendency as expressed by larger modal particle sizes and lower number concentrations compared to dry conditions. Hydrophilic aerosols exhibited higher sensitivities to changes in humidity than hydrophobic particles. However, the test systems themselves also differed in generated particle number concentrations and size distributions, which in turn altered the responses of created aerosols to humidity changes. The results of the present study clearly demonstrate that (a) humidity control is essential for dustiness and deagglomeration testing, (b) that (industrial) deagglomeration, for example, for preparation of aerosol suspensions, can be manipulated by subjecting airborne particles to external energies, and (c) that the humidity of workplace air may be relevant when assessing occupational exposure to nanomaterial aerosols. Copyright © 2016 American Association for Aerosol Research © 2016 American Association for Aerosol Research.view abstract doi: 10.1080/02786826.2016.1216072 2016 • 513 Detection of individual nanoparticle impacts using etched carbon nanoelectrodes
Clausmeyer, J. and Wilde, P. and Löffler, T. and Ventosa, E. and Tschulik, K. and Schuhmann, W.
Electrochemistry Communications 73 67-70 (2016)A rapid and reliable nanofabrication route produces electrodes with beneficial properties for electrochemistry based on stochastic nanoparticle collision events. Carbon nanoelectrodes are etched to expose conical carbon tips which present an increased surface area for the detection of nanoparticle impacts. The tuneable electrode size as well as the conical geometry allow to increase the observed particle impact frequency while maintaining low background noise. Moreover, anodic particle coulometry for the sizing of silver nanoparticles shows that the detected impacts are representative of the polydisperse particle population. © 2016view abstract doi: 10.1016/j.elecom.2016.11.003 2016 • 512 Effect of pH on the spontaneous synthesis of palladium nanoparticles on reduced graphene oxide
Zhang, X. and Ooki, W. and Kosaka, Y.R. and Okonogi, A. and Marzun, G. and Wagener, P. and Barcikowski, S. and Kondo, T. and Nakamura, J.
Applied Surface Science 389 911-915 (2016)Palladium (Pd) nanoparticles were spontaneously deposited on reduced graphene oxide (rGO) without any external reducing agents. The prepared Pd/rGO composites were then characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Spontaneous deposition occurred because of a redox reaction between the Pd precursor and rGO, which involved reduction of bivalent Pd to metallic Pd0 and oxidation of the sp2 carbon of rGO to oxygen-containing functional groups. The amount of Pd deposited on rGO varied with pH, and this was attributed to electrostatic interactions between the Pd precursor and rGO based on the results of zeta potential measurements. The importance of the redox reaction in the spontaneous deposition was demonstrated in the experiment with Zn, Ni, Cu, Ag, Pt, Pd, and Au. © 2016 Elsevier B.V.view abstract doi: 10.1016/j.apsusc.2016.08.014 2016 • 511 Efficient synthesis of polyoxazoline-silica hybrid nanoparticles by using the "grafting-onto" approach
Bissadi, G. and Weberskirch, R.
Polymer Chemistry 7 1271-1280 (2016)Well-defined silica poly(2-methyl-2-oxazoline) nanoparticles were prepared via the "grafting to" method employing either click chemistry or silane coupling using different reaction conditions. In the first approach, alkyne-functionalized poly(2-methyl-2-oxazoline), P1, was prepared by ring opening cationic polymerization and clicked on azide-functionalized silica nanoparticles (SNPs), which led to the fabrication of hybrid nanoparticles. In the second approach, trimethoxysilane-functionalized poly(2-methyl-2-oxazoline), P2, was prepared similar to P1 and grafted on the surface of SNPs using coupling reactions between trimethoxysilane and hydroxyl groups of the silica nanoparticle. Hybrid particles were characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), and elemental analysis (EA). The grafting density ranged from 0.183 chains per nm2 for the click chemistry approach up to 0.45 chains per nm2 when using trimethoxysilane-functionalized P2 in acetonitrile at 80 °C. The water-in-oil microemulsion approach resulted still in a relatively high grafting density of 0.353 chains per nm2 and has the advantage of a one-step process and mild reaction conditions. © The Royal Society of Chemistry 2016.view abstract doi: 10.1039/c5py01775k 2016 • 510 Electrophoretic deposition of ligand-free platinum nanoparticles on neural electrodes affects their impedance in vitro and in vivo with no negative effect on reactive gliosis
Angelov, S.D. and Koenen, S. and Jakobi, J. and Heissler, H.E. and Alam, M. and Schwabe, K. and Barcikowski, S. and Krauss, J.K.
Journal of Nanobiotechnology 14 (2016)Background: Electrodes for neural stimulation and recording are used for the treatment of neurological disorders. Their features critically depend on impedance and interaction with brain tissue. The effect of surface modification on electrode impedance was examined in vitro and in vivo after intracranial implantation in rats. Electrodes coated by electrophoretic deposition with platinum nanoparticles (NP; <10 and 50 nm) as well as uncoated references were implanted into the rat's subthalamic nucleus. After postoperative recovery, rats were electrostimulated for 3 weeks. Impedance was measured before implantation, after recovery and then weekly during stimulation. Finally, local field potential was recorded and tissue-to-implant reaction was immunohistochemically studied. Results: Coating with NP significantly increased electrode's impedance in vitro. Postoperatively, the impedance of all electrodes was temporarily further increased. This effect was lowest for the electrodes coated with particles <10 nm, which also showed the most stable impedance dynamics during stimulation for 3 weeks and the lowest total power of local field potential during neuronal activity recording. Histological analysis revealed that NP-coating did not affect glial reactions or neural cell-count. Conclusions: Coating with NP <10 nm may improve electrode's impedance stability without affecting biocompatibility. Increased impedance after NP-coating may improve neural recording due to better signal-to-noise ratio. © 2016 Angelov et al.view abstract doi: 10.1186/s12951-015-0154-9 2016 • 509 Exploring the mineral-water interface: Reduction and reaction kinetics of single hematite (α-Fe2O3) nanoparticles
Shimizu, K. and Tschulik, K. and Compton, R.G.
Chemical Science 7 1408-1414 (2016)In spite of their natural and technological importance, the intrinsic electrochemical properties of hematite (α-Fe2O3) nanoparticles are not well understood. In particular, particle agglomeration, the presence of surface impurities, and/or inadequate proton concentrations are major obstacles to uncover the fundamental redox activities of minerals in solution. These are particularly problematic when samples are characterized in common electrochemical analyses such as cyclic voltammetry in which nanoparticles are immobilized on a stationary electrode. In this work, the intrinsic reaction kinetics and thermodynamics of individual hematite nanoparticles are investigated by particle impact chronoamperometry. The particle radius derived from the integrated area of spikes recorded in a chronoamperogram is in excellent agreement with electron microscopy results, indicating that the method provides a quantitative analysis of the reduction of the nanoparticles to the ferrous ion. A key finding is that the suspended individual nanoparticles undergo electrochemical reduction at potentials much more positive than those immobilized on a stationary electrode. The critical importance of the solid/water interface on nanoparticle activity is further illustrated by a kinetic model. It is found that the first electron transfer process is the rate determining step of the reductive dissolution of hematite nanoparticles, while the overall process is strongly affected by the interfacial proton concentration. This article highlights the effects of the interfacial proton and ferrous ion concentrations on the reductive dissolution of hematite nanoparticles and provides a highly effective method that can be readily applied to study a wide range of other mineral nanoparticles. © 2016 The Royal Society of Chemistry.view abstract doi: 10.1039/c5sc03678j 2016 • 508 Formation of polyoxazoline-silica nanoparticles: Via the surface-initiated cationic polymerization of 2-methyl-2-oxazoline
Bissadi, G. and Weberskirch, R.
Polymer Chemistry 7 5157-5168 (2016)Well-defined polyoxazoline-silica hybrid nanoparticles were prepared by coating silica nanoparticles (SNPs) with poly(2-methyl-2-oxazoline) using a surface-initiated cationic ring-opening polymerization process. First, reverse microemulsion was used to synthesize monodisperse SNPs followed by immobilizing (chloromethyl)phenylethyl)trimethoxysilane on the surface of the nanoparticles acting as an initiator. The grafting density of the polymeric shell was controlled by varying the polymerization time, PSNPs-A, and the monomer/initiator ratio concentration, PSNPs-B. Hybrid nanoparticles were characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and transmission electron microscopy (TEM). The molecular weight and polydispersity indices of the polymer chains were determined by size exclusion chromatography (SEC) after etching the silica core. The hybrid nanoparticles were further functionalized with fluorescein isothiocyanate (FITC) and folic acid (FA) as a fluorescence imaging molecule and a cancer-targeting ligand, respectively. Moreover, hybrid nanoparticles with Rubpy as a fluorophore encapsulated in the silica core and the poly(2-methyl-2-oxazoline) shell were prepared. © 2016 The Royal Society of Chemistry.view abstract doi: 10.1039/c6py01034b 2016 • 507 Formation of Well-Defined Polymer Particles in the Sub-100 nm Size Range by Using Amphiphilic Block Copolymer Surfactants and a Microemulsion Approach
Kampmann, A.-L. and Luksin, M. and Pretzer, I. and Weberskirch, R.
Macromolecular Chemistry and Physics 217 1704-1711 (2016)Here, the formation of nanoparticles based on a microemulsion approach and the use of polymer surfactants are described. Therefore, two amphiphilic poly(2-oxazoline) block copolymers P1 and P2 with alkyne groups in their hydrophobic block have been synthesized by ring-opening, cationic polymerization. The polymers P1 and P2 are employed in a microemulsion process to stabilize the particle core by core cross-linking of 1,6-hexanediol diacrylate (HDDA) using either AIBN as azo-initiator or 2-propanethiol as a photo-initiator for the polymerization reaction. The results show that particle size can be controlled by sonication time, the hydrophilic–hydrophobic balance of the polymer surfactant, and the ratio of polymer surfactant versus HDDA giving access to water-soluble nanoparticles in a size range of 10–70 nm. (Figure presented.). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/macp.201600108 2016 • 506 From Gold Nanoseeds to Nanorods: The Microscopic Origin of the Anisotropic Growth
Meena, S.K. and Sulpizi, M.
Angewandte Chemie - International Edition 55 11960-11964 (2016)Directly manipulating and controlling the size and shape of metal nanoparticles is a key step for their tailored applications. In this work, molecular dynamics simulations were applied to understand the microscopic origin of the asymmetric growth mechanism in gold nanorods. Different factors influencing the growth were selectively included in the models to unravel the role of the surfactants and ions. In the early stage of the growth, when the seed is only a few nanometers large, a dramatic symmetry breaking occurs as the surfactant layer preferentially covers the (100) and (110) facets, leaving the (111) facets unprotected. This anisotropic surfactant layer in turn promotes anisotropic growth with the less protected tips growing faster. When silver salt is added to the growth solution, the asymmetry of the facets is preserved, but the Br−concentration at the interface increases, resulting in increased surface passivation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/anie.201604594 2016 • 505 Gas-phase synthesis of Fe-Bi metastable and dumbbell particles
Ünlü, C.G. and Li, Z.-A. and Acet, M. and Farle, M.
Crystal Research and Technology 51 333-336 (2016)Fe-Bi nanoparticles were prepared in the gas-phase by DC magnetron sputtering and in-fight annealing. The morphological, structural and compositional properties were investigated by High-resolution transmission electron microscopy, energy dispersive X-ray spectroscopy and scanning transmission electron microscopy. High-resolution microscopy studies show that primary particles produced without in-flight annealing are spherical with a diameter of about 50 nm. Particles sintered at 773 K acquire a dumbbell structure with Fe-FeO and Bi sections. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/crat.201500329 2016 • 504 Gold on Different Manganese Oxides: Ultra-Low-Temperature CO Oxidation over Colloidal Gold Supported on Bulk-MnO2 Nanomaterials
Gu, D. and Tseng, J.-C. and Weidenthaler, C. and Bongard, H.-J. and Spliethoff, B. and Schmidt, W. and Soulimani, F. and Weckhuysen, B.M. and Schüth, F.
Journal of the American Chemical Society 138 9572-9580 (2016)Nanoscopic gold particles have gained very high interest because of their promising catalytic activity for various chemicals reactions. Among these reactions, low-temperature CO oxidation is the most extensively studied one due to its practical relevance in environmental applications and the fundamental problems associated with its very high activity at low temperatures. Gold nanoparticles supported on manganese oxide belong to the most active gold catalysts for CO oxidation. Among a variety of manganese oxides, Mn2O3 is considered to be the most favorable support for gold nanoparticles with respect to catalytic activity. Gold on MnO2 has been shown to be significantly less active than gold on Mn2O3 in previous work. In contrast to these previous studies, in a comprehensive study of gold nanoparticles on different manganese oxides, we developed a gold catalyst on MnO2 nanostructures with extremely high activity. Nanosized gold particles (2-3 nm) were supported on α-MnO2 nanowires and mesoporous β-MnO2 nanowire arrays. The materials were extremely active at very low temperature (-80 °C) and also highly stable at 25 °C (70 h) under normal conditions for CO oxidation. The specific reaction rate of 2.8 molCO·h-1·gAu -1 at a temperature as low as -85 °C is almost 30 times higher than that of the most active Au/Mn2O3 catalyst. © 2016 American Chemical Society.view abstract doi: 10.1021/jacs.6b04251 2016 • 503 High temperature stability study of carbon supported high surface area catalysts—Expanding the boundaries of ex-situ diagnostics
Polymeros, G. and Baldizzone, C. and Geiger, S. and Grote, J.P. and Knossalla, J. and Mezzavilla, S. and Keeley, G.P. and Cherevko, S. and Zeradjanin, A.R. and Schüth, F. and Mayrhofer, K.J.J.
Electrochimica Acta 211 744-753 (2016)The performance of proton-exchange membrane fuel cells (PEMFCs) is defined by the equally important parameters of the intrinsic activity and stability of the electrocatalysts. This work focuses on the stability of carbon supported high surface area oxygen reduction reaction catalysts at potentials and temperatures similar to the operating conditions of PEMFCs. The catalysts used for this investigation consist of Pt nanoparticles of the same particle size supported on two types of carbon support having different textural properties, i.e., Vulcan and Hollow Graphitic Spheres (HGS). A broad toolbox of characterization techniques is utilized at 60 °C in order to resolve the contribution of the different degradation mechanisms, namely nanoparticle coalescence, metal dissolution and the corrosion of carbon support, to the total active surface area loss. The results obtained by investigating the impact of temperature, potential treatment and catalyst layer morphology on the aging behavior lead to a deeper understanding of the aging mechanisms and their interrelation at application-relevant conditions. Moreover, the previously reported improved performance of the Pt/HGS catalyst is confirmed also under higher temperatures. The experimental approach introduced in this work, highlights new challenges for high-temperature degradation investigations with supported PEMFC catalyst. © 2016 Elsevier Ltdview abstract doi: 10.1016/j.electacta.2016.06.105 2016 • 502 High-Temperature Stable Ni Nanoparticles for the Dry Reforming of Methane
Mette, K. and Kühl, S. and Tarasov, A. and Willinger, M.G. and Kröhnert, J. and Wrabetz, S. and Trunschke, A. and Scherzer, M. and Girgsdies, F. and Düdder, H. and Kähler, K. and Ortega, K.F. and Muhler, M. and Schlögl, R. an...
ACS Catalysis 6 7238-7248 (2016)Dry reforming of methane (DRM) has been studied for many years as an attractive option to produce synthesis gas. However, catalyst deactivation by coking over nonprecious-metal catalysts still remains unresolved. Here, we study the influence of structural and compositional properties of nickel catalysts on the catalytic performance and coking propensity in the DRM. A series of bulk catalysts with different Ni contents was synthesized by calcination of hydrotalcite-like precursors NixMg0.67-xAl0.33(OH)2(CO3)0.17·mH2O prepared by constant-pH coprecipitation. The obtained Ni/MgAl oxide catalysts contain Ni nanoparticles with diameters between 7 and 20 nm. High-resolution transmission electron microscopy (HR-TEM) revealed a nickel aluminate overgrowth on the Ni particles, which could be confirmed by Fourier transform infrared (FTIR) spectroscopy. In particular, catalysts with low Ni contents (5 mol %) exhibit predominantly oxidic surfaces dominated by Ni2+ and additionally some isolated Ni0 sites. These properties, which are determined by the overgrowth, effectively diminish the formation of coke during the DRM, while the activity is preserved. A large (TEM) and dynamic (microcalorimetry) metallic Ni surface at high Ni contents (50 mol %) causes significant coke formation during the DRM. © 2016 American Chemical Society.view abstract doi: 10.1021/acscatal.6b01683 2016 • 501 High-yield and scalable synthesis of a Silicon/Aminosilane-functionalized Carbon NanoTubes/Carbon (Si/A-CNT/C) composite as a high-capacity anode for lithium-ion batteries
Sehlleier, Y.H. and Dobrowolny, S. and Plümel, I. and Xiao, L. and Mahlendorf, F. and Heinzel, A. and Schulz, C. and Wiggers, H.
Journal of Applied Electrochemistry 46 229-239 (2016)In this study, we present a novel anode architecture for high-performance lithium-ion batteries based on a Silicon/3-aminosilane-functionalized CNT/Carbon (Si/A-CNT/C) composite. A high-yield, low-cost approach has been developed to stabilize and support silicon as an active anode material. Silicon (Si) nanoparticles synthesized in a hot-wall reactor and aminosilane-functionalized carbon nanotubes (A-CNT) were dispersed in styrene and divinylbenzene (DVB) and subsequently polymerized forming a porous Si/A-CNT/C composite. Transmission electron microscopy showed that this method enables the interconnection and a uniform encapsulation of Si nanoparticles within a porous carbon matrix especially using aminosilane-functionalized CNT (A-CNT). Electrochemical characterization shows that this material can deliver a delithiation capacity of 2293 mAh g−1 with a capacity retention of more than 90 % after 200 cycles at lithiation and delithiation rate of 0.5 C. We conclude that the porous Si/A-CNT/C composite material can accommodate sufficient space for Si volume expansion and extraction and improve the electronic and ionic conduction. Excellent electrochemical performance during repeated cycling can thus be achieved. © 2015, Springer Science+Business Media Dordrecht.view abstract doi: 10.1007/s10800-015-0897-x 2016 • 500 Hollow Zn/Co Zeolitic Imidazolate Framework (ZIF) and Yolk-Shell Metal@Zn/Co ZIF Nanostructures
Rösler, C. and Aijaz, A. and Turner, S. and Filippousi, M. and Shahabi, A. and Xia, W. and Van Tendeloo, G. and Muhler, M. and Fischer, R.A.
Chemistry - A European Journal 22 3304-3311 (2016)Metal-organic frameworks (MOFs) feature a great possibility for a broad spectrum of applications. Hollow MOF structures with tunable porosity and multifunctionality at the nanoscale with beneficial properties are desired as hosts for catalytically active species. Herein, we demonstrate the formation of well-defined hollow Zn/Co-based zeolitic imidazolate frameworks (ZIFs) by use of epitaxial growth of Zn-MOF (ZIF-8) on preformed Co-MOF (ZIF-67) nanocrystals that involve in situ self-sacrifice/excavation of the Co-MOF. Moreover, any type of metal nanoparticles can be accommodated in Zn/Co-ZIF shells to generate yolk-shell metal@ZIF structures. Transmission electron microscopy and tomography studies revealed the inclusion of these nanoparticles within hollow Zn/Co-ZIF with dominance of the Zn-MOF as shell. Our findings lead to a generalization of such hollow systems that are working effectively to other types of ZIFs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/chem.201503619 2016 • 499 Improved photoelectrochemical performance of electrodeposited metal-doped BiVO4 on Pt-nanoparticle modified FTO surfaces
Gutkowski, R. and Peeters, D. and Schuhmann, W.
Journal of Materials Chemistry A 4 7875-7882 (2016)The recombination of photogenerated electron-hole pairs is one of the main limiting factors of photoelectrocatalysts absorbing in the visible part of the solar spectrum. Especially for BiVO4 the slow electron transport to the back contact facilitates charge recombination. Hence, thin layers have to be used to obtain higher photocurrents which are concomitantly only allow low absorption of the incident light. To address this limitation we have modified FTO substrates with Pt-nanoparticles before electrodepositing BiVO4. The Pt-nanoparticles decrease the overpotential for the electrodeposition of BiVO4, but more importantly they provide the basis for decreased charge recombination. Electrodeposited Mo-doped BiVO4 on Pt-nanoparticle modified FTO exhibits a substantially decreased recombination of photogenerated charge carriers during frontside illumination. Simultaneous co-doping of BiVO4 with two different metals leads to a substantial enhancement of the incident-photon-to-current efficiency (IPCE) during light driven oxygen evolution reaction. Highest IPCE (>30% at 1.2 V vs. RHE) values were obtained for Mo/Zn- and Mo/B-doped BiVO4. © 2016 The Royal Society of Chemistry.view abstract doi: 10.1039/c6ta01340f 2016 • 498 In Situ Investigations of Laser-Generated Ligand-Free Platinum Nanoparticles by X-ray Absorption Spectroscopy: How Does the Immediate Environment Influence the Particle Surface?
Fischer, M. and Hormes, J. and Marzun, G. and Wagener, P. and Hagemann, U. and Barcikowski, S.
Langmuir 32 8793-8802 (2016)Pulsed laser ablation in liquid (PLAL) has proven its usefulness as a nanoparticle (NP) synthesis method alternative to traditional chemical reduction methods, where the absence of any molecular ligands or residual reactants makes laser-generated nanoparticles ideal reference materials for charge-transfer experiments. We synthesized additive-free platinum nanoparticles by PLAL and in-situ characterized their interaction with H2O, sodium phosphate buffer, and sodium citrate as well as a TiO2 support by X-ray absorption fine structure (XAFS), i.e., X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). Differences in the white-line intensity among the colloidal particles in the three liquids indicate that the respective NP-solvent interaction varies in strength. The ions added ex situ diffuse through the particles' electric double layer and interact electrostatically with the Stern plane. Consequently, these ions weaken the interaction of the functional OH groups that are bound to the partially oxidized platinum surfaces and cause their partial reduction. Comparing XAFS spectra of laser-generated Pt NPs in citrate with wet-chemically synthesized ones (both ligand-covered) indicates different types of Pt-O bonds: a Pt(IV)O2 type in the case of wet-chemical NPs and a Pt(II)O type in the case of laser-generated NPs. A comparison of unsupported laser-generated platinum NPs in H2O with TiO2-supported ones shows no white-line intensity differences and also an identical number of Pt-O bonds in both cases. This suggests that in the deposition process at least part of the double-layer coating stays intact and that the ligand-free Pt particle properties are preserved in the TiO2-supported Pt particles, relevant for heterogeneous catalysis. © 2016 American Chemical Society.view abstract doi: 10.1021/acs.langmuir.6b00685 2016 • 497 Influence of agglomeration and specific lung lining lipid/protein interaction on short-term inhalation toxicity
Wohlleben, W. and Driessen, M.D. and Raesch, S. and Schaefer, U.F. and Schulze, C. and Vacano, B.V. and Vennemann, A. and Wiemann, M. and Ruge, C.A. and Platsch, H. and Mues, S. and Ossig, R. and Tomm, J.M. and Schnekenburger, J. ...
Nanotoxicology 10 970-980 (2016)Abstract: Lung lining fluid is the first biological barrier nanoparticles (NPs) encounter during inhalation. As previous inhalation studies revealed considerable differences between surface functionalized NPs with respect to deposition and toxicity, our aim was to investigate the influence of lipid and/or protein binding on these processes. Thus, we analyzed a set of surface functionalized NPs including different SiO2 and ZrO2 in pure phospholipids, CuroSurfTM and purified native porcine pulmonary surfactant (nS). Lipid binding was surprisingly low for pure phospholipids and only few NPs attracted a minimal lipid corona. Additional presence of hydrophobic surfactant protein (SP) B in CuroSurfTM promoted lipid binding to NPs functionalized with Amino or PEG residues. The presence of the hydrophilic SP A in nS facilitated lipid binding to all NPs. In line with this the degree of lipid and protein affinities for different surface functionalized SiO2 NPs in nS followed the same order (SiO2 Phosphate ∼ unmodified SiO2 < SiO2 PEG < SiO2 Amino NPs). Agglomeration and biomolecule interaction of NPs in nS was mainly influenced by surface charge and hydrophobicity. Toxicological differences as observed in short-term inhalation studies (STIS) were mainly influenced by the core composition and/or surface reactivity of NPs. However, agglomeration in lipid media and lipid/protein affinity appeared to play a modulatory role on short-term inhalation toxicity. For instance, lipophilic NPs like ZrO2, which are interacting with nS to a higher extent, exhibited a far higher lung burden than their hydrophilic counterparts, which deserves further attention to predict or model effects of respirable NPs. © 2016 Informa UK Limited, trading as Taylor & Francis Group.view abstract doi: 10.3109/17435390.2016.1155671 2016 • 496 Influence of the liquid on femtosecond laser ablation of iron
Kanitz, A. and Hoppius, J.S. and Gurevich, E.L. and Ostendorf, A.
Physics Procedia 83 114-122 (2016)Ultrashort pulse laser ablation has become a very important industrial method for highly precise material removal ranging from sensitive thin film processing to drilling and cutting of metals. Over the last decade, a new method to produce pure nanoparticles emerged from this technique: Pulsed Laser Ablation in Liquids (PLAL). By this method, the ablation of material by a laser beam is used to generate a metal vapor within the liquid in order to obtain nanoparticles from its recondensation process. It is well known that the liquid significantly alters the ablation properties of the substrate, in our case iron. For example, the ablation rate and crater morphology differ depending on the used liquid. We present our studies on the efficiency and quality of ablated grooves in water, methanol, acetone, ethanol and toluene. The produced grooves are investigated by means of white-light interferometry, EDX and SEM. © 2016 The Authors.view abstract doi: 10.1016/j.phpro.2016.08.022 2016 • 495 Kinetics of chemotaxis, cytokine, and chemokine release of NR8383 macrophages after exposure to inflammatory and inert granular insoluble particles
Schremmer, I. and Brik, A. and Weber, D.G. and Rosenkranz, N. and Rostek, A. and Loza, K. and Brüning, T. and Johnen, G. and Epple, M. and Bünger, J. and Westphal, G.A.
Toxicology Letters 263 68-75 (2016)Accumulation of macrophages and neutrophil granulocytes in the lung are key events in the inflammatory response to inhaled particles. The present study aims at the time course of chemotaxis in vitro in response to the challenge of various biopersistent particles and its functional relation to the transcription of inflammatory mediators. NR8383 rat alveolar macrophages were challenged with particles of coarse quartz, barium sulfate, and nanosized silica for one, four, and 16 h and with coarse and nanosized titanium dioxide particles (rutile and anatase) for 16 h only. The cell supernatants were used to investigate the chemotaxis of unexposed NR8383 macrophages. The transcription of inflammatory mediators in cells exposed to quartz, silica, and barium sulfate was analyzed by quantitative real-time PCR. Challenge with quartz, silica, and rutile particles induced significant chemotaxis of unexposed NR8383 macrophages. Chemotaxis caused by quartz and silica was accompanied by an elevated transcription of CCL3, CCL4, CXCL1, CXCL3, and TNFα. Quartz exposure showed an earlier onset of both effects compared to the nanosized silica. The strength of this response roughly paralleled the cytotoxic effects. Barium sulfate and anatase did not induce chemotaxis and barium sulfate as well caused no elevated transcription. In conclusion, NR8383 macrophages respond to the challenge with inflammatory particles with the release of chemotactic compounds that act on unexposed macrophages. The kinetics of the response differs between the various particles. © 2016 Elsevier Ireland Ltdview abstract doi: 10.1016/j.toxlet.2016.08.014 2016 • 494 Laser-based diagnostics in the gas-phase synthesis of inorganic nanoparticles
Dreier, T. and Schulz, C.
Powder Technology 287 226-238 (2016)As gas-phase methods for the synthesis of tailored nanomaterials become increasingly sophisticated, the need for in situ diagnostics of reaction conditions and particle properties grows correspondingly. Laser-based methods provide a wide range of capabilities which are reviewed in this article. © 2015.view abstract doi: 10.1016/j.powtec.2015.10.015 2016 • 493 Laser-based in situ embedding of metal nanoparticles into bioextruded alginate hydrogel tubes enhances human endothelial cell adhesion
Blaeser, A. and Million, N. and Campos, D.F.D. and Gamrad, L. and Köpf, M. and Rehbock, C. and Nachev, M. and Sures, B. and Barcikowski, S. and Fischer, H.
Nano Research 9 3407-3427 (2016)Alginate is a widely used hydrogel in tissue engineering owing to its simple and non-cytotoxic gelation process, ease of use, and abundance. However, unlike hydrogels derived from mammalian sources such as collagen, alginate does not contain cell adhesion ligands. Here, we present a novel laser ablation technique for the in situ embedding of gold and iron nanoparticles into hydrogels. We hypothesized that integration of metal nanoparticles in alginate could serve as an alternative material because of its chemical biofunctionalization ability (coupling of RGD ligands) to favor cell adhesion. Cytocompatibility and biofunctionality of the gels were assessed by cell culture experiments using fibroblasts and endothelial cells. Nanoparticles with an average particle size of 3 nm (gold) and 6 nm (iron) were generated and stably maintained in alginate for up to 6 months. Using an extrusion system, several centimeter-long alginate tubes with an outer diameter of approximately 3 mm and a wall thickness of approximately 150 μm were manufactured. Confocal microscopy revealed homogeneously distributed nanoparticle agglomerates over the entire tube volume. Endothelial cells seeded on iron-loaded gels showed significantly higher viability and an increased degree of spreading, and the number of attached cells was also elevated in comparison to the control and gold-loaded alginates. We conclude that laser-based in situ integration of iron nanoparticles (≤ 0.01 wt.%) in alginate is a straightforward method to generate composite materials that favor the adhesion of endothelial cells. In addition, we show that nanoparticle integration does not impair the alginate’s gelation and 3D biofabrication properties. [Figure not available: see fulltext.] © 2016, Tsinghua University Press and Springer-Verlag Berlin Heidelberg.view abstract doi: 10.1007/s12274-016-1218-3 2016 • 492 Laser-induced incandescence from laser-heated silicon nanoparticles
Menser, J. and Daun, K. and Dreier, T. and Schulz, C.
Applied Physics B: Lasers and Optics 122 (2016)This work describes the application of temporally and spectrally resolved laser-induced incandescence to silicon nanoparticles synthesized in a microwave plasma reactor. Optical properties for bulk silicon presented in the literature were extended for nanostructured particles analyzed in this paper. Uncertainties of parameters in the evaporation submodel, as well as measurement noise, are incorporated into the inference process by Bayesian statistics. The inferred nanoparticle sizes agree with results from transmission electron microscopy, and the determined accommodation coefficient matches the values of the preceding study. © 2016, Springer-Verlag Berlin Heidelberg.view abstract doi: 10.1007/s00340-016-6551-4 2016 • 491 Laser-synthesized ligand-free Au nanoparticles for contrast agent applications in computed tomography and magnetic resonance imaging
Simão, T. and Chevallier, P. and Lagueux, J. and Côté, M.-F. and Rehbock, C. and Barcikowski, S. and Fortin, M.-A. and Guay, D.
Journal of Materials Chemistry B 4 6413-6427 (2016)In recent years, pulsed laser ablation in liquids (PLAL) has emerged as a new green chemistry method to produce different types of nanoparticles (NPs). It does not require the use of reducing or stabilizing agents, therefore enabling the synthesis of NPs with highly-pure surfaces. In this study, pure Au NPs were produced by PLAL in aqueous solutions, sterically stabilized using minimal PEG excess, and functionalized with manganese chelates to produce a dual CT/MRI contrast agent. The small hydrodynamic size (36.5 nm), low polydispersity (0.2) and colloidal stability of Au NPs@PEG-Mn2+ were demonstrated by DLS. The particles were further characterized by TEM, XPS, FTIR and 1H NMR to confirm the purity of the Au surfaces (i.e. free from the common residual chemicals found after NP synthesis) and the presence of the different surface molecules. The potential of these particles as contrast agents for CT/MRI was assessed in vivo (e.g. chicken embryo). Au NPs@PEG-Mn2+ also demonstrated strong blood retention for at least 90 minutes following intravenous injection in mouse models. The promising performance of PEGylated PLAL-synthesized Au NPs containing manganese chelates could open new possibilities for the production of purer dual imaging contrast agents based on Au colloids. © 2016 The Royal Society of Chemistry.view abstract doi: 10.1039/c6tb01162d 2016 • 490 Magnetic Mesoporous Photonic Cellulose Films
Giese, M. and Blusch, L.K. and Schlesinger, M. and Meseck, G.R. and Hamad, W.Y. and Arjmand, M. and Sundararaj, U. and MacLachlan, M.J.
Langmuir 32 9329-9334 (2016)Novel hybrid materials of cellulose and magnetic nanoparticles (NPs) were synthesized and characterized. The materials combine the chiral nematic structural features of mesoporous photonic cellulose (MPC) with the magnetic properties of cobalt ferrite (CoFe2O4). The photonic, magnetic, and dielectric properties of the hybrid materials were investigated during the dynamic swelling and deswelling of the MPC films. It was observed that the dielectric properties of the generated MPC films increased tremendously following swelling in water, endorsing efficient swelling ability of the generated mesoporous films. The high magnetic permeability of the developed MPC films in conjunction with their superior dielectric properties, predominantly in the swollen state, makes them interesting for electromagnetic interference shielding applications. © 2016 American Chemical Society.view abstract doi: 10.1021/acs.langmuir.6b02974 2016 • 489 Magnetoresponsive Poly(ether sulfone)-Based Iron Oxide cum Hydrogel Mixed Matrix Composite Membranes for Switchable Molecular Sieving
Lin, X. and Nguyen Quoc, B. and Ulbricht, M.
ACS Applied Materials and Interfaces 8 29001-29014 (2016)Stimuli-responsive membranes that can adjust mass transfer and interfacial properties "on demand" have drawn large interest over the last few decades. Here, we designed and prepared a novel magnetoresponsive separation membrane with remote switchable molecular sieving effect by simple one-step and scalable nonsolvent induced phase separation (NIPS) process. Specifically, poly(ether sulfone) (PES) as matrix for an anisotropic membrane, prefabricated poly(N-isopropylacrylamide) (PNIPAAm) nanogel (NG) particles as functional gates, and iron oxide magnetic nanoparticles (MNP) as localized heaters were combined in a synergistic way. Before membrane casting, the properties of the building blocks, including swelling property and size distribution for NG, and magnetic property and heating efficiency for MNP, were investigated. Further, to identify optimal film casting conditions for membrane preparation by NIPS, in-depth rheological study of the effects of composition and temperature on blend dope solutions was performed. At last, a composite membrane with 10% MNP and 10% NG blended in a porous PES matrix was obtained, which showed a large, reversible, and stable magneto-responsivity. It had 9 times higher water permeability at the "on" state of alternating magnetic field (AMF) than at the "off"-state. Moreover, the molecular weight cutoff of such membrane could be reversibly shifted from ∼70 to 1750 kDa by switching off or on the external AMF, as demonstrated in dextran ultrafiltration tests. Overall, it has been proved that the molecular sieving performance of the novel mixed matrix composite membrane can be controlled by the swollen/shrunken state of PNIPAAm NG embedded in the nanoporous barrier layer of a PES-based anisotropic porous matrix, via the heat generation of nearby MNP. And the structure of such membrane can be tailored by the NIPS process conditions. Such membrane has potential as enabling material for remote-controlled drug release systems or devices for tunable fractionations of biomacromolecule/-particle mixtures. © 2016 American Chemical Society.view abstract doi: 10.1021/acsami.6b09369 2016 • 488 Membrane-based purification of proteins from nanoparticle dispersions: Influences of membrane type and ultrafiltration conditions
Alele, N. and Ulbricht, M.
Separation and Purification Technology 158 171-182 (2016)The combination of nanoparticles with proteins to form functional hybrid systems is receiving undiminished attention because of its many biotechnological and medical applications. The separation of these hybrid materials from unbound free biomolecules has posed difficult challenges to fractionation and purification. Here, a model study has been carried out by removing proteins (bovine serum albumin (BSA) or lysozyme (LYS)) from the dispersion mixtures with silica nanoparticles (nominal size 20 nm) using ultrafiltration (UF) membranes. Regenerated cellulose (RC) and polyethersulfone (PES) membranes with nominal molecular weight cut-off (NMWCO) of 100 kDa, and a PES UF membrane (NMWCO 300 kDa) functionalized with UV-grafted amphoteric polymer hydrogel layer consisting of N-[3-(dimethylamino)propyl]-acrylamide (DMAPAA) and 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and having an experimentally determined cut-off of 180 kDa (identical with the experimental data for PES 100 kDa) were studied. Membrane properties and filtration conditions, in particular pH value and flux, were selected or adapted based on data for single component feeds to achieve maximum protein transmission, complete silica retention and, hence, maximum silica/protein selectivity. Batch dead-end and continuous diafiltration processes were used for fractionation and purification. Overall, the performance of PES UF membranes was inferior compared to the other membranes because of too strong fouling. With membrane RC 100, the transmission data of LYS and BSA from the mixture with silica were 80% and 30%, respectively. With the hydrogel-functionalized PES membrane, the respective transmissions from the mixture were ∼35% and ∼15% for LYS and BSA, respectively. In both cases, quantitative rejection of silica could be achieved. Using continuous diafiltration, membrane RC 100 had better purification efficiency, removing a total of 91% of LYS using 6 diavolumes (DV) in 2.4 h and 84% of BSA using 10 DV in 5.5 h. With the hydrogel-functionalized PES membrane, 82% of LYS and 74% of BSA were removed using 6 and 10 DV within larger time, i.e. 4.0 and 6.8 h, respectively. Importantly, the retained silica nanoparticles remained stable in the dispersion, without any indication of aggregation. Overall, this study will add valuable knowledge to the most efficient use of ultrafiltration sieving properties for the removal or purification of proteins from systems comprising other colloidal particles having a size which is larger by a factor of only 3-10. © 2015 Published by Elsevier B.V.view abstract doi: 10.1016/j.seppur.2015.11.031 2016 • 487 Metal-semiconductor pair nanoparticles by a physical route based on bipolar mixing
Kala, S. and Theissmann, R. and Rouenhoff, M. and Kruis, F.E.
Nanotechnology 27 (2016)In this report a methodology is described and demonstrated for preparing Au-Ge pair nanoparticles with known compositions by extending and modifying the basic steps normally used to synthesize nanoparticles in carrier gas. For the formation of pair nanoparticles by bipolar mixing, two oppositely charged aerosols of nanoparticles having the desired size are produced with the help of two differential mobility analyzers. Then both are allowed to pass through a tube, which provides sufficient residence time to result in nanoparticle pair formation due to Brownian collisions influenced by Coulomb forces. The effect of residence time on the formation of nanoparticle pairs as well as the influence of diffusion and discharging is described. Subsequently, necessary modifications to the experimental setup are demonstrated systematically. The kinetics of nanoparticles pair formation in a carrier gas is also calculated and compared with measurements made with the help of an online aerosol size analysis technique. This synthesis of nanoparticle pairs can be seen as a possible route towards Janus-type nanoparticles. © 2016 IOP Publishing Ltd.view abstract doi: 10.1088/0957-4484/27/12/125604 2016 • 486 Nanoelectrodes: Applications in electrocatalysis, single-cell analysis and high-resolution electrochemical imaging
Clausmeyer, J. and Schuhmann, W.
TrAC - Trends in Analytical Chemistry 79 46-59 (2016)High sensitivity and high spatial resolution in localized electrochemical measurements are the key advantages of electroanalysis using nanometer-sized electrodes. Due to recent progress in nanoelectrode fabrication and electrochemical instrument development, nanoelectrochemical methods are becoming more widespread. We summarize different protocols for the fabrication of needle-type nanoelectrodes and discuss their properties with regard to various applications. We discuss the limits of conventional theory to describe electrochemistry at the nanoscale and point out technical aspects for characterization and handling of nanometric electrodes. Different applications are highlighted: i) Nanoelectrodes are powerful tools for non-ensemble studies of electrocatalysis at single nanoparticles at high mass transport rates. ii) Electrochemical nanosensors are employed for highly localized non-invasive analysis of single living cells and intracellular detection of neurotransmitters and metabolites. iii) Used in scanning electrochemical probe techniques, nanoprobes afford topographical and truly chemical imaging of samples with high spatial resolution. © 2016 Published by Elsevier B.V.view abstract doi: 10.1016/j.trac.2016.01.018 2016 • 485 Nanoparticles as transfection agents: A comprehensive study with ten different cell lines
Neuhaus, B. and Tosun, B. and Rotan, O. and Frede, A. and Westendorf, A.M. and Epple, M.
RSC Advances 6 18102-18112 (2016)The performance of transfection agents to deliver nucleic acids into cells strongly depends on the cell type. In a comprehensive study, nine different cell lines and primary human mesenchymal stem cells were transfected with DNA encoding for enhanced green fluorescent protein (eGFP). As transfection agents, two kinds of cationic multi-shell calcium phosphate nanoparticles and the commercially available transfection agent Lipofectamine were used. The transfection efficiency was measured by fluorescence microscopy by counting the percentage of green fluorescent cells which expressed eGFP as well as qPCR. Furthermore, the uptake of fluorescent calcium phosphate nanoparticles was measured by fluorescence microscopy. The cell viability was measured by the MTT test after incubation with nanoparticles and Lipofectamine. All cell types took up nanoparticles (with different efficiency), but the expression of eGFP was strongly different, demonstrating that the uptake not necessarily leads to processing of a gene. A clear correlation was found between the transfection efficiency and the cell viability that was independent on the transfection agent: a high transfection efficiency was clearly correlated with a low cell viability and vice versa. © The Royal Society of Chemistry 2016.view abstract doi: 10.1039/c5ra25333k 2016 • 484 Nanoparticles for light management in ultrathin chalcopyrite solar cells
Schmid, M. and Manley, P. and Ott, A. and Song, M. and Yin, G.
Journal of Materials Research 31 3273-3289 (2016)We evaluate the potential of inserting metallic, metal-dielectric core-shell, and fully dielectric nanoparticles in ultrathin chalcopyrite solar cells to enhance absorption which experiences a significant drop for absorber thicknesses below 500 nm. For different integration positions at the front or at the rear of the solar cell structure theoretical expectations and potential benefits originating from light scattering, near-field enhancement and coupling into waveguide modes by the nanoparticles are presented. These benefits are always balanced against experimental challenges arising for particular geometries due to the very specific fabrication processes of chalcopyrite solar cells. In particular high absorber deposition temperatures as well as contact layers that are relatively thick compared to other devices need to be considered. Based on this, we will need to go beyond some geometries that have proven beneficial for other types of solar cells and identify the most promising configurations for chalcopyrite-based devices. © 2016 Materials Research Society.view abstract doi: 10.1557/jmr.2016.382 2016 • 483 Nitrogen-Doped Ordered Mesoporous Carbon Supported Bimetallic PtCo Nanoparticles for Upgrading of Biophenolics
Wang, G.-H. and Cao, Z. and Gu, D. and Pfänder, N. and Swertz, A.-C. and Spliethoff, B. and Bongard, H.-J. and Weidenthaler, C. and Schmidt, W. and Rinaldi, R. and Schüth, F.
Angewandte Chemie - International Edition 55 8850-8855 (2016)Hydrodeoxygenation (HDO) is an attractive route for the upgrading of bio-oils produced from lignocellulose. Current catalysts require harsh conditions to effect HDO, decreasing the process efficiency in terms of energy and carbon balance. Herein we report a novel and facile method for synthesizing bimetallic PtCo nanoparticle catalysts (ca. 1.5 nm) highly dispersed in the framework of nitrogen-doped ordered mesoporous carbon (NOMC) for this reaction. We demonstrate that NOMC with either 2D hexagonal (p6m) or 3D cubic (Im3m) structure can be easily synthesized by simply adjusting the polymerization temperature. We also demonstrate that PtCo/NOMC (metal loading: Pt 9.90 wt %; Co 3.31 wt %) is a highly effective catalyst for HDO of phenolic compounds and “real-world” biomass-derived phenolic streams. In the presence of PtCo/NOMC, full deoxygenation of phenolic compounds and a biomass-derived phenolic stream is achieved under conditions of low severity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/anie.201511558 2016 • 482 Novel back-reflector architecture with nanoparticle based buried light-scattering microstructures for improved solar cell performance
Desta, D. and Ram, S.K. and Rizzoli, R. and Bellettato, M. and Summonte, C. and Jeppesen, B.R. and Jensen, P.B. and Tsao, Y.-C. and Wiggers, H. and Pereira, R.N. and Balling, P. and Larsen, A.N.
Nanoscale 8 12035-12046 (2016)A new back-reflector architecture for light-management in thin-film solar cells is proposed that includes a morphologically smooth top surface with light-scattering microstructures buried within. The microstructures are pyramid shaped, fabricated on a planar reflector using TiO2 nanoparticles and subsequently covered with a layer of Si nanoparticles to obtain a flattened top surface, thus enabling growth of good quality thin-film solar cells. The optical properties of this back-reflector show high broadband haze parameter and wide angular distribution of diffuse light-scattering. The n-i-p amorphous silicon thin-film solar cells grown on such a back-reflector show enhanced light absorption resulting in improved external quantum efficiency. The benefit of the light trapping in those solar cells is evidenced by the gains in short-circuit current density and efficiency up to 15.6% and 19.3% respectively, compared to the reference flat solar cells. This improvement in the current generation in the solar cells grown on the flat-topped (buried pyramid) back-reflector is observed even when the irradiation takes place at large oblique angles of incidence. Finite-difference-time-domain simulation results of optical absorption and ideal short-circuit current density values agree well with the experimental findings. The proposed approach uses a low cost and simple fabrication technique and allows effective light manipulation by utilizing the optical properties of micro-scale structures and nanoscale constituent particles. © 2016 The Royal Society of Chemistry.view abstract doi: 10.1039/c6nr00259e 2016 • 481 Novel magneto-responsive membrane for remote control switchable molecular sieving
Lin, X. and Huang, R. and Ulbricht, M.
Journal of Materials Chemistry B 4 867-879 (2016)Stimuli-responsive separation membranes with tunable molecular scale pore size, which are desirable for on-demand sieving of targeted macromolecules, have attracted increasing attention in recent years. In this study, novel magneto-hydrogel pore-filled composite membranes with excellent magneto-responsivity and tunability for molecular sieving have been developed. Such membranes comprising magnetic nanoparticles (MNPs) as localized heater which can be excited by high frequency alternating magnetic field (AMF), poly(N-isopropylacrylamide) (PNIPAAm) hydrogel network as the sieving medium and actuator, and polyethylene terephthalate (PET) track-etched membrane as robust support, have been prepared via in situ reactive pore-filling functionalization. Rheological study has been carried out first to investigate the influence of MNPs and initiation methods on gelation kinetics and microstructure of the MNP-PNIPAAm composite hydrogels, and to identify proper conditions for further pore-filling functionalization. Then AMF distribution of chosen field condition and its heating effectiveness for MNPs and MNP-PNIPAMm composite hydrogel were studied. Pre-functionalization of the PET membranes with linear polymer chains with different composition were compared with respect to their effects for achieving desired MNP loading and fixation of the hydrogel network in the pores. At last, in situ reactive pore-filling functionalization was carried out to immobilize robust magneto-hydrogel in the pores of the membranes. Conditions were investigated and optimized to obtain functionalized membranes with high MNP loading and suited PNIPAM network properties, i.e. good stimuli-responsivity and sieving in the ultrafiltration range. The excellent thermo- and magneto-responsivity of obtained pore-filled membranes was proved by its large and reversible change of water permeability in response to switching on and off the AMF. Finally, it was demonstrated by filtration of dextrans with different molecular weights that the membranes had ultrafiltration properties and that large changes of their molecular sieving performance could be obtained by "remote control" with the external AMF. © 2016 The Royal Society of Chemistry.view abstract doi: 10.1039/c5tb02368h 2016 • 480 On Local Phase Equilibria and the Appearance of Nanoparticles in the Microstructure of Single-Crystal Ni-Base Superalloys
Yardley, V. and Povstugar, I. and Choi, P.-P. and Raabe, D. and Parsa, A.B. and Kostka, A. and Somsen, C. and Dlouhy, A. and Neuking, K. and George, E.P. and Eggeler, G.
Advanced Engineering Materials 18 1556-1567 (2016)High-resolution characterization techniques are combined with thermodynamic calculations (CALPHAD) to rationalize microstructural features of single crystal Ni-base superalloys. Considering the chemical compositions of dendritic and interdendritic regions one can explain differences in γ′-volume fractions. Using thermodynamic calculations one can explain, why γ-nanoparticles are observed in the central regions of large cuboidal γ′-particles and why tertiary γ′-nanoparticles form in the γ-channels. The chemical compositions of the γ-channels and of the newly formed γ-particles differ because of the Gibbs–Thomson pressure which acts on the small particles. With increasing size of secondary γ′-particles, their shape changes from spherical to cuboidal. Some general thermodynamic aspects including the temperature dependencies of the Gibbs free energy G, the enthalpy H, and the entropy S and site occupancies in the ordered L12 (γ′) phase are considered. The importance of cooling rate after homogenization is discussed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/adem.201600237 2016 • 479 On the Crystallography of Silver Nanoparticles with Different Shapes
Helmlinger, J. and Prymak, O. and Loza, K. and Gocyla, M. and Heggen, M. and Epple, M.
Crystal Growth and Design 16 3677-3687 (2016)The crystallographic properties of silver nanoparticles with different morphologies (two different kinds of spheres, cubes, platelets, and rods) were derived from X-ray powder diffraction and electron microscopy. The size of the metallic particle core was determined by scanning electron microscopy, and the colloidal stability and the hydrodynamic particle diameter were analyzed by dynamic light scattering. The preferred crystallographic orientation (texture) as obtained by X-ray powder diffraction, including pole figure analysis, and high resolution transmission electron microscopy showed the crystallographic nature of the spheres (almost no texture), the cubes (terminated by {100} faces), the platelets (terminated by {111} faces), and the rods (grown from pentagonal twins along [110] and terminated by {100} faces). The crystallite size was determined by Rietveld refinement of X-ray powder diffraction data and agreed well with the transmission electron microscopic data. © 2016 American Chemical Society.view abstract doi: 10.1021/acs.cgd.6b00178 2016 • 478 On the role of the stability of functional groups in multi-walled carbon nanotubes applied as support in iron-based high-temperature Fischer-Tropsch synthesis
Chew, L.M. and Xia, W. and Düdder, H. and Weide, P. and Ruland, H. and Muhler, M.
Catalysis Today 270 85-92 (2016)The role of the stability of surface functional groups in oxygen- and nitrogen-functionalized multi-walled carbon nanotubes (CNTs) applied as support for iron catalysts in high-temperature Fischer-Tropsch synthesis was studied in a fixed-bed U-tube reactor at 340°C and 25 bar with a H2:CO ratio of 1. Iron oxide nanoparticles supported on untreated oxygen-functionalized CNTs (OCNTs) and nitrogen-functionalized CNTs (NCNTs) as well as thermally treated OCNTs were synthesized by the dry impregnation method using ammonium ferric citrate as iron precursor. The properties of all catalysts were examined using X-ray diffraction, temperature-programmed reduction in H2, X-ray photoelectron spectroscopy and temperature-programmed oxidation in O2. The activity loss for iron nanoparticles supported on untreated OCNTs was found to originate from severe sintering and carbon encapsulation of the iron carbide nanoparticles under reaction conditions. Conversely, the sintering of the iron carbide nanoparticles on thermally treated OCNTs and untreated NCNTs during reaction was far less pronounced. The presence of more stable surface functional groups in both thermally treated OCNTs and untreated NCNTs is assumed to be responsible for the less severe sintering of the iron carbide nanoparticles during reaction. As a result, no activity loss for iron nanoparticles supported on thermally treated OCNTs and untreated NCNTs was observed, which even became gradually more active under reaction conditions. © 2015 Published by Elsevier B.V.view abstract doi: 10.1016/j.cattod.2015.09.023 2016 • 477 Optical and electron microscopy study of laser-based intracellular molecule delivery using peptide-conjugated photodispersible gold nanoparticle agglomerates
Krawinkel, J. and Richter, U. and Torres-Mapa, M.L. and Westermann, M. and Gamrad, L. and Rehbock, C. and Barcikowski, S. and Heisterkamp, A.
Journal of Nanobiotechnology 14 (2016)Background: Cell-penetrating peptides (CPPs) can act as carriers for therapeutic molecules such as drugs and genetic constructs for medical applications. The triggered release of the molecule into the cytoplasm can be crucial to its effective delivery. Hence, we implemented and characterized laser interaction with defined gold nanoparticle agglomerates conjugated to CPPs which enables efficient endosomal rupture and intracellular release of molecules transported. Results: Gold nanoparticles generated by pulsed laser ablation in liquid were conjugated with CPPs forming agglomerates and the intracellular release of molecules was triggered via pulsed laser irradiation (λ = 532 nm, τpulse = 1 ns). The CPPs enhance the uptake of the agglomerates along with the cargo which can be co-incubated with the agglomerates. The interaction of incident laser light with gold nanoparticle agglomerates leads to heat deposition and field enhancement in the vicinity of the particles. This highly precise effect deagglomerates the nanoparticles and disrupts the enclosing endosomal membrane. Transmission electron microscopy images confirmed this rupture for radiant exposures of 25 mJ/cm2 and above. Successful intracellular release was shown using the fluorescent dye calcein. For a radiant exposure of 35 mJ/cm2 we found calcein delivery in 81 % of the treated cells while maintaining a high percentage of cell viability. Furthermore, cell proliferation and metabolic activity were not reduced 72 h after the treatment. Conclusion: CPPs trigger the uptake of the gold nanoparticle agglomerates via endocytosis and co-resident molecules in the endosomes are released by applying laser irradiation, preventing their intraendosomal degradation. Due to the highly localized effect, the cell membrane integrity is not affected. Therefore, this technique can be an efficient tool for spatially and temporally confined intracellular release. The utilization of specifically designed photodispersible gold nanoparticle agglomerates (65 nm) can open novel avenues in imaging and molecule delivery. Due to the induced deagglomeration the primary, small particles (~5 nm) are more likely to be removed from the body. © 2016 Krawinkel et al.view abstract doi: 10.1186/s12951-015-0155-8 2016 • 476 Optimization of a transferred arc reactor for metal nanoparticle synthesis
Stein, M. and Kruis, F.E.
Journal of Nanoparticle Research 18 (2016)The demand for metal nanoparticles is increasing strongly. Transferred arc synthesis is a promising process in this respect, as it shows high production rates, good quality particles and the ability of up-scaling. The influence of several process parameters on the performance of the process in terms of production rate and particle size is investigated. These parameters are the electrode design and adjustment, the gas flow rate and power input. A novel feeding mechanism allows process operation over an extended time period. It is shown that the process is capable of producing pure metal nanoparticles with variable primary particle sizes and comparatively high production rates. Optimal process conditions for a single transferred arc electrode pair are found, which allow further scale-up by numbering up. © 2016, The Author(s).view abstract doi: 10.1007/s11051-016-3559-y 2016 • 475 Optimum nanoscale design in ferrite based nanoparticles for magnetic particle hyperthermia
Liébana-Viñas, S. and Simeonidis, K. and Wiedwald, U. and Li, Z.-A. and Ma, Zh. and Myrovali, E. and Makridis, A. and Sakellari, D. and Vourlias, G. and Spasova, M. and Farle, M. and Angelakeris, M.
RSC Advances 6 72918-72925 (2016)The study demonstrates the multiplex enhancement of the magnetic hyperthermia response in ferrites by nanoscale design and tuning without sparing the biocompatibility of iron-oxide. We propose core/shell nanoparticles with a 7-9 nm ferrite core, either magnetically soft MnFe2O4 or hard CoFe2O4, encapsulated by a 2-3 nm Fe3O4 shell providing a core/shell interface. In this case, the exchange interaction between core and shell dramatically affects the macroscopic magnetic behavior and, at the same time, a biocompatible shell prevents interactions of the toxic cores with their environment. The tunable, yet superior, magnetic hyperthermia response is proven by an increase of the specific loss power by a factor of 24 for CoFe2O4-Fe3O4 core/shell particles. This gain is directly connected with the magnetic coupling strength at the core/shell interface and opens the possibility of further optimization. © 2016 The Royal Society of Chemistry.view abstract doi: 10.1039/c6ra17892h 2016 • 474 Orientation of FePt nanoparticles on top of a-SiO2/Si(001), MgO(001) and sapphire(0001): Effect of thermal treatments and influence of substrate and particle size
Schilling, M. and Ziemann, P. and Zhang, Z. and Biskupek, J. and Kaiser, U. and Wiedwald, U.
Beilstein Journal of Nanotechnology 7 591-604 (2016)Texture formation and epitaxy of thin metal films and oriented growth of nanoparticles (NPs) on single crystal supports are of general interest for improved physical and chemical properties especially of anisotropic materials. In the case of FePt, the main focus lies on its highly anisotropic magnetic behavior and its catalytic activity, both due to the chemically ordered face-centered tetragonal (fct) L10 phase. If the c-axis of the tetragonal system can be aligned normal to the substrate plane, perpendicular magnetic recording could be achieved. Here, we study the orientation of FePt NPs and films on a-SiO2/Si(001), i.e., Si(001) with an amorphous (a-) native oxide layer on top, on MgO(001), and on sapphire(0001) substrates. For the NPs of an approximately equiatomic composition, two different sizes were chosen: "small" NPs with diameters in the range of 2-3 nm and "large" ones in the range of 5-8 nm. The 3 nm thick FePt films, deposited by pulsed laser deposition (PLD), served as reference samples. The structural properties were probed in situ, particularly texture formation and epitaxy of the specimens by reflection high-energy electron diffraction (RHEED) and, in case of 3 nm nanoparticles, additionally by high-resolution transmission electron microscopy (HRTEM) after different annealing steps between 200 and 650 °C. The L10 phase is obtained at annealing temperatures above 550 °C for films and 600 °C for nanoparticles in accordance with previous reports. On the amorphous surface of a-SiO2/Si substrates we find no preferential orientation neither for FePt films nor nanoparticles even after annealing at 630 °C. On sapphire(0001) supports, however, FePt nanoparticles exhibit a clearly preferred (111) orientation even in the as-prepared state, which can be slightly improved by annealing at 600-650 °C. This improvement depends on the size of NPs: Only the smaller NPs approach a fully developed (111) orientation. On top of MgO(001) the effect of annealing on particle orientation was found to be strongest. From a random orientation in the as-prepared state observed for both, small and large FePt NPs, annealing at 650 °C for 30 min reorients the small particles towards a cube-on-cube epitaxial orientation with a minor fraction of (111)-oriented particles. In contrast, large FePt NPs keep their as-prepared random orientation even after doubling the annealing period at 650 °C to 60 min. © 2016 Schilling et al.view abstract doi: 10.3762/bjnano.7.52 2016 • 473 Palladium Nanoparticles Supported on Nitrogen-Doped Carbon Nanotubes as a Release-and-Catch Catalytic System in Aerobic Liquid-Phase Ethanol Oxidation
Dong, W. and Chen, P. and Xia, W. and Weide, P. and Ruland, H. and Kostka, A. and Köhler, K. and Muhler, M.
ChemCatChem 8 1269-1273 (2016)Pd nanoparticles supported on carbon nanotubes were applied in the selective oxidation of ethanol in the liquid phase. The characterization of the surface and bulk properties combined with the catalytic tests indicated the dissolution and redeposition of Pd under the reaction conditions. A dynamic interplay within the Pd life cycle was identified to be responsible for the overall reactivity. Nitrogen-doped carbon nanotubes were found to act as an excellent support for the Pd catalyst system by efficiently stabilizing and recapturing the Pd species, which resulted in high activity and selectivity to acetic acid. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/cctc.201501379 2016 • 472 Pd deposited on functionalized carbon nanotubes for the electrooxidation of ethanol in alkaline media
Hiltrop, D. and Masa, J. and Maljusch, A. and Xia, W. and Schuhmann, W. and Muhler, M.
Electrochemistry Communications 63 30-33 (2016)Large scale commercialization of direct ethanol fuel cells is hampered by the high cost and scarcity of noble metal electrocatalysts employed at both the anode and cathode. We demonstrate improved utilization of palladium as anode catalyst for ethanol oxidation by exploiting the strong interaction between Pd nanoparticles and nitrogen-doped carbon nanotubes (NCNTs) as support. 0.85 wt% Pd supported on NCNTs achieved a specific current density of 517 A gPd - 1 compared with 421 A gPd - 1 for 0.86 wt% Pd on oxygen-functionalized carbon nanotubes. The electrocatalytic performance deteriorated only gradually and catalysis was sustained for at least 80 h. © 2015 Elsevier B.V. All rights reserved.view abstract doi: 10.1016/j.elecom.2015.11.010 2016 • 471 Pilot-scale synthesis of metal nanoparticles by high-speed pulsed laser ablation in liquids
Streubel, R. and Bendt, G. and Gökce, B.
Nanotechnology 27 (2016)The synthesis of catalysis-relevant nanoparticles such as platinum and gold is demonstrated with productivities of 4 g h-1 for pulsed laser ablation in liquids (PLAL). The major drawback of low productivity of PLAL is overcome by utilizing a novel ultrafast high-repetition rate laser system combined with a polygon scanner that reaches scanning speeds up to 500 m s-1. This high scanning speed is exploited to spatially bypass the laser-induced cavitation bubbles at MHz-repetition rates resulting in an increase of the applicable, ablation-effective, repetition rate for PLAL by two orders of magnitude. The particle size, morphology and oxidation state of fully automated synthesized colloids are analyzed while the ablation mechanisms are studied for different laser fluences, repetition rates, interpulse distances, ablation times, volumetric flow rates and focus positions. It is found that at high scanning speeds and high repetition rate PLAL the ablation process is stable in crystallite size and decoupled from shielding and liquid effects that conventionally occur during low-speed PLAL. © 2016 IOP Publishing Ltd.view abstract doi: 10.1088/0957-4484/27/20/205602 2016 • 470 Plasmon assisted 3D microstructuring of gold nanoparticle-doped polymers
Jonušauskas, L. and Lau, M. and Gruber, P. and Gökce, B. and Barcikowski, S. and Malinauskas, M. and Ovsianikov, A.
Nanotechnology 27 (2016)3D laser lithography of a negative photopolymer (zirconium/silicon hybrid solgel SZ2080) doped with gold nanoparticles (Au NPs) is performed with a 515 nm and 300 fs laser system and the effect of doping is explored. By varying the laser-generated Au NP doping concentration from 4.8 • 10-6 wt% to 9.8 • 10-3 wt% we find that the fabricated line widths are enlarged by up to 14.8% compared to structures achieved in pure SZ2080. While implicating a positive effect on the photosensitivity, the doping has no adverse impact on the mechanical quality of intricate 3D microstructures produced from the doped nanocompound. Additionally, we found that SZ2080 increases the long term (∼months) colloidal stability of Au NPs in isopropanol. By discussing the nanoparticle-light interaction in the 3D polymer structures we provide implications that our findings might have on other fields, such as biomedicine and photonics. © 2016 IOP Publishing Ltd.view abstract doi: 10.1088/0957-4484/27/15/154001 2016 • 469 Plasmonic Au/TiO2 nanostructures for glycerol oxidation
Dodekatos, G. and Tüysüz, H.
Catalysis Science and Technology 6 7307-7315 (2016)Au nanoparticles supported on P25 TiO2 (Au/TiO2) were prepared by a facile deposition-precipitation method with urea and investigated for surface plasmon-assisted glycerol oxidation under base-free conditions. Au/TiO2 samples were characterized in detail by X-ray diffraction, UV-vis spectroscopy, transmission electron microscopy and energy-dispersive X-ray spectroscopy. The adopted synthetic methodology permits deposition of Au nanoparticles with similar mean particle sizes up to 12.5 wt% loading that allows for the evaluation of the influence of the Au amount (without changing the particle size) on its photocatalytic performance for glycerol oxidation. The reaction conditions were optimized by carrying out a systematic study with different Au loadings on TiO2, reaction times, temperatures, catalyst amounts, O2 pressures and Au particle sizes for photocatalytic reactions as well as traditional heterogeneous catalysis. It has been shown that visible light irradiation during the reaction has a beneficial effect on the conversion of glycerol where the best catalytic results were observed for 7.5 wt% Au loading with an average particle size of around 3 nm. The main product observed, with selectivities up to 63%, was high-value dihydroxyacetone that has important industrial applications, particularly in the cosmetic industry. © 2016 The Royal Society of Chemistry.view abstract doi: 10.1039/c6cy01192f 2016 • 468 Precise synthesis of discrete and dispersible carbon-protected magnetic nanoparticles for efficient magnetic resonance imaging and photothermal therapy
Lu, A.-H. and Zhang, X.-Q. and Sun, Q. and Zhang, Y. and Song, Q. and Schüth, F. and Chen, C. and Cheng, F.
Nano Research 9 1460-1469 (2016)Carbon-protected magnetic nanoparticles exhibit long-term stability in acid or alkaline medium, good biocompatibility, and high saturation magnetization. As a result, they hold great promise for magnetic resonance imaging, photothermal therapy, etc. However, since pyrolysis, which is often required to convert the carbon precursors to carbon, typically leads to coalescence of the nanoparticles, the obtained carbon-protected magnetic nanoparticles are usually sintered as a non-dispersible aggregation. We have successfully synthesized discrete, dispersible, and uniform carbon-protected magnetic nanoparticles via a precise surface/interface nano-engineering approach. Remarkably, the nanoparticles possess excellent water-dispersibility, biocompatibility, a high T2 relaxivity coefficient (384 mM–1·s–1), and a high photothermal heating effect. Furthermore, they can be used as multifunctional core components suited for future extended investigation in early diagnosis, detection and therapy, catalysis, separation, and magnetism. [Figure not available: see fulltext.] © 2016, Tsinghua University Press and Springer-Verlag Berlin Heidelberg.view abstract doi: 10.1007/s12274-016-1042-9 2016 • 467 Probing the Dynamic Structure and Chemical State of Au Nanocatalysts during the Electrochemical Oxidation of 2-Propanol
Choi, Y. and Sinev, I. and Mistry, H. and Zegkinoglou, I. and Roldan Cuenya, B.
ACS Catalysis 6 3396-3403 (2016)A size-dependent trend was observed for the electrochemical total oxidation of 2-propanol to CO2 over Au nanoparticles (NPs), with increasing activity (increased current density and lower overpotential) for decreasing NP size. Furthermore, an enhanced stability against poisoning by the unreacted acetone intermediate was also obtained for NPs smaller than ∼2 nm. Operando X-ray absorption fine structure (XAFS) measurements provided insight into the dynamic evolution of the NP structure and chemical state under reaction conditions, shedding light on the nature of the most catalytically active species and catalyst deactivation phenomena via chemically driven sintering. © 2016 American Chemical Society.view abstract doi: 10.1021/acscatal.6b00057 2016 • 466 Resonant laser processing of nanoparticulate Au/TiO2 films on glass supports: Photothermal modification of a photocatalytic nanomaterial
Schade, L. and Franzka, S. and Thomas, M. and Hagemann, U. and Hartmann, N.
Surface Science 650 57-63 (2016)Resonant laser processing at λ = 532 nm is used to modify thin Au/TiO2 nanoparticle films on soda lime glass plates. A microfocused continuous-wave laser is employed for local patterning at distinct laser powers. In conjunction with microscopic techniques this approach allows for reproducible high-throughput screening of laser-induced material modifications. Optical microscopy and microspectroscopy reveal laser darkening, i.e. a significantly increased optical absorbance. Scanning electron microscopy and X-ray photoelectron spectroscopy show laser-induced film growth and roughening along with the integration of SiO2 from the glass supports. Raman spectroscopy displays a phase transition from anatase to rutile. Au evaporation and/or integration only takes place at high laser powers. All these modifications provide promising perspectives in view of photocatalytic applications. Data from complementary laser experiments with unblended pure TiO2 coatings at λ = 532 nm and λ = 355 nm point to a photothermal process, in which the optical energy is selectively deposited in the Au nanoparticles and transformed into heat. As a result, thermally activated modifications take place. General prospects of laser processing in targeted modification of nanomaterials for photocatalysis are emphasized. © 2016 Elsevier B.V. All rights reserved.view abstract doi: 10.1016/j.susc.2016.01.006 2016 • 465 Scalable and Environmentally Benign Process for Smart Textile Nanofinishing
Feng, J. and Hontañón, E. and Blanes, M. and Meyer, J. and Guo, X. and Santos, L. and Paltrinieri, L. and Ramlawi, N. and Smet, L.C.P.M.D. and Nirschl, H. and Kruis, F.E. and Schmidt-Ott, A. and Biskos, G.
ACS Applied Materials and Interfaces 8 14756-14765 (2016)A major challenge in nanotechnology is that of determining how to introduce green and sustainable principles when assembling individual nanoscale elements to create working devices. For instance, textile nanofinishing is restricted by the many constraints of traditional pad-dry-cure processes, such as the use of costly chemical precursors to produce nanoparticles (NPs), the high liquid and energy consumption, the production of harmful liquid wastes, and multistep batch operations. By integrating low-cost, scalable, and environmentally benign aerosol processes of the type proposed here into textile nanofinishing, these constraints can be circumvented while leading to a new class of fabrics. The proposed one-step textile nanofinishing process relies on the diffusional deposition of aerosol NPs onto textile fibers. As proof of this concept, we deposit Ag NPs onto a range of textiles and assess their antimicrobial properties for two strains of bacteria (i.e., Staphylococcus aureus and Klebsiella pneumoniae). The measurements show that the logarithmic reduction in bacterial count can get as high as ca. 5.5 (corresponding to a reduction efficiency of 99.96%) when the Ag loading is 1 order of magnitude less (10 ppm; i.e., 10 mg Ag NPs per kg of textile) than that of textiles treated by traditional wet-routes. The antimicrobial activity does not increase in proportion to the Ag content above 10 ppm as a consequence of a "saturation" effect. Such low NP loadings on antimicrobial textiles minimizes the risk to human health (during textile use) and to the ecosystem (after textile disposal), as well as it reduces potential changes in color and texture of the resulting textile products. After three washes, the release of Ag is in the order of 1 wt %, which is comparable to textiles nanofinished with wet routes using binders. Interestingly, the washed textiles exhibit almost no reduction in antimicrobial activity, much as those of as-deposited samples. Considering that a realm of functional textiles can be nanofinished by aerosol NP deposition, our results demonstrate that the proposed approach, which is universal and sustainable, can potentially lead to a wide number of applications. © 2016 American Chemical Society.view abstract doi: 10.1021/acsami.6b03632 2016 • 464 Silicon-based nanocomposites for thermoelectric application
Schierning, G. and Stoetzel, J. and Chavez, R. and Kessler, V. and Hall, J. and Schmechel, R. and Schneider, T. and Petermann, N. and Wiggers, H. and Angst, S. and Wolf, D.E. and Stoib, B. and Greppmair, A. and Stutzmann, M. and B...
Physica Status Solidi (A) Applications and Materials Science 213 497-514 (2016)Here we present the realization of efficient and sustainable silicon-based thermoelectric materials from nanoparticles. We employ a gas phase synthesis for the nanoparticles which is capable of producing doped silicon (Si) nanoparticles, doped alloy nanoparticles of silicon and germanium (Ge), SixGe1-x, and doped composites of Si nanoparticles with embedded metal silicide precipitation phases. Hence, the so-called "nanoparticle in alloy" approach, theoretically proposed in the literature, forms a guideline for the material development. For bulk samples, a current-activated pressure-assisted densification process of the nanoparticles was optimized in order to obtain the desired microstructure. For thin films, a laser annealing process was developed. Thermoelectric transport properties were characterized on nanocrystalline bulk samples and laser-sintered-thin films. Devices were produced from nanocrystalline bulk silicon in the form of p-n junction thermoelectric generators, and their electrical output data were measured up to hot side temperatures of 750°C. In order to get a deeper insight into thermoelectric properties and structure forming processes, a 3D-Onsager network model was developed. This model was extended further to study the p-n junction thermoelectric generator and understand the fundamental working principle of this novel device architecture. Gas phase synthesis of composite nanoparticles; nanocrystalline bulk with optimized composite microstructure; laser-annealed thin film. The authors fabricated thermoelectric nanomaterials from doped silicon and silicon and germanium alloy nanoparticles, as well as composites of Si nanoparticles with embedded metal silicide nanoparticles. Processing was performed applying a current-activated pressure-assisted densification process for bulk samples and a laser annealing process for thin film samples. Devices were produced in the form of pn junction thermoelectric generators. A 3D-Onsager network model was used to understand the fundamental working principle of this novel device architecture. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/pssa.201532602 2016 • 463 Silver nanoparticles with different size and shape: Equal cytotoxicity, but different antibacterial effects
Helmlinger, J. and Sengstock, C. and Groß-Heitfeld, C. and Mayer, C. and Schildhauer, T.A. and Köller, M. and Epple, M.
RSC Advances 6 18490-18501 (2016)The influence of silver nanoparticle morphology on the dissolution kinetics in ultrapure water as well as the biological effect on eukaryotic and prokaryotic cells was examined. Silver nanoparticles with different shapes but comparable size and identical surface functionalisation were prepared, i.e. spheres (diameter 40-80 and 120-180 nm; two different samples), platelets (20-60 nm), cubes (140-180 nm), and rods (diameter 80-120 nm, length > 1000 nm). All particles were purified by ultracentrifugation and colloidally stabilized with poly(N-vinyl pyrrolidone) (PVP). Their colloidal dispersion in ultrapure water and cell culture medium was demonstrated by dynamic light scattering. Size, shape, and colloidal stability were analysed by scanning electron microscopy, atomic force microscopy, dynamic light scattering, and differential centrifugal sedimentation. The dissolution in ultrapure water was proportional to the specific surface area of the silver nanoparticles. The averaged release rate for all particle morphologies was 30 ± 13 ng s-1 m-2 in ultrapure water (T = 25 ± 1°C; pH 4.8; oxygen saturation 93%), i.e. about 10-20 times larger than the release of silver from a macroscopic silver bar (1 oz), possibly due to the presence of surface defects in the nanoparticulate state. All particles were taken up by human mesenchymal stem cells and were cytotoxic in concentrations of >12.5 μg mL-1, but there was no significant influence of the particle shape on the cytotoxicity towards the cells. Contrary to that, the toxicity towards bacteria increased with a higher dissolution rate, suggesting that the toxic species against bacteria are dissolved silver ions. © The Royal Society of Chemistry 2016.view abstract doi: 10.1039/c5ra27836h 2016 • 462 Simultaneous Study of Brownian and Néel Relaxation Phenomena in Ferrofluids by Mössbauer Spectroscopy
Landers, J. and Salamon, S. and Remmer, H. and Ludwig, F. and Wende, H.
Nano Letters 16 1150-1155 (2016)We demonstrate the ability of Mössbauer spectroscopy to simultaneously investigate Brownian motion and Néel relaxation in ferrofluidic samples. For this purpose, Mössbauer spectra of coated iron oxide nanoparticles with core diameters of 6.0-26.4 nm dissolved in 70 vol % glycerol solution were recorded in the temperature range of 234-287 K and compared to low-temperature spectra without Brownian motion. By comparison to theory, we were able to determine the particle coating thickness and the dynamic viscosity of the fluid from the broadening of the absorption lines (Brownian motion), as well as the state of Néel relaxation. Results from Mössbauer spectroscopy were crosschecked by AC-susceptometry at several temperatures for Brownian motion and in the high-frequency regime (100 Hz-1 MHz) for Néel relaxation. © 2016 American Chemical Society.view abstract doi: 10.1021/acs.nanolett.5b04409 2016 • 461 Single Nanoparticle Voltammetry: Contact Modulation of the Mediated Current
Li, X. and Batchelor-Mcauley, C. and Whitby, S.A.I. and Tschulik, K. and Shao, L. and Compton, R.G.
Angewandte Chemie - International Edition 55 4296-4299 (2016)The cyclic voltammetric responses of individual palladium-coated carbon nanotubes are reported. Upon impact - from the solution phase - with the electrified interface, the nanoparticles act as individual nanoelectrodes catalyzing the hydrogen-oxidation reaction. At high overpotentials the current is shown to reach a quasi-steady-state diffusion limit, allowing determination of the tube length. The electrochemical response of the individual nanotubes also reveals the system to be modulated by the electrical contact between the electrode and carbon nanotube. This modulation presents itself as fluctuations in the recorded Faradaic current. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/anie.201509017 2016 • 460 Size matters - The phototoxicity of TiO2 nanomaterials
Wyrwoll, A.J. and Lautenschläger, P. and Bach, A. and Hellack, B. and Dybowska, A. and Kuhlbusch, T.A.J. and Hollert, H. and Schäffer, A. and Maes, H.M.
Environmental Pollution 208 859-867 (2016)Under solar radiation several titanium dioxide nanoparticles (nano-TiO2) are known to be phototoxic for daphnids. We investigated the influence of primary particle size (10, 25, and 220 nm) and ionic strength (IS) of the test medium on the acute phototoxicity of anatase TiO2 particles to Daphnia magna. The intermediate sized particles (25 nm) showed the highest phototoxicity followed by the 10 nm and 220 nm sized particles (median effective concentrations (EC50): 0.53, 1.28, 3.88 mg/L). Photoactivity was specified by differentiating free OH radicals (therephthalic acid method) and on the other hand surface adsorbed, as well as free OH, electron holes, and O2- (electron paramagnetic resonance spectroscopy, EPR). We show that the formation of free OH radicals increased with a decrease in primary particle size (terephthalic acid method), whereas the total measured ROS content was highest at an intermediate particle size of 25 nm, which consequently revealed the highest photoxicity. The photoactivities of the 10 and 220 nm particles as measured by EPR were comparable. We suggest that phototoxicity depends additionally on the particle-daphnia interaction area, which explains the higher photoxicity of the 10 nm particles compared to the 220 nm particles. Thus, phototoxicity is a function of the generation of different ROS and the particle-daphnia interaction area, both depending on particle size. Phototoxicity of the 10 nm and 25 nm sized nanoparticles decreased as IS of the test medium increased (EC50: 2.9 and 1.1 mg/L). In conformity with the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory we suggest that the precipitation of nano-TiO2 was more pronounced in high than in low IS medium, causing a lower phototoxicity. In summary, primary particle size and IS of the medium were identified as factors influencing phototoxicity of anatase nano-TiO2 to D. magna. © 2015 Elsevier Ltd. All rights reserved.view abstract doi: 10.1016/j.envpol.2015.10.035 2016 • 459 Size-dependent adhesion energy of shape-selected Pd and Pt nanoparticles
Ahmadi, M. and Behafarid, F. and Cuenya, B.R.
Nanoscale 8 11635-11641 (2016)Thermodynamically stable shape-selected Pt and Pd nanoparticles (NPs) were synthesized via inverse micelle encapsulation and a subsequent thermal treatment in vacuum above 1000 °C. The majority of the Pd NPs imaged via scanning tunneling microscopy (STM) had a truncated octahedron shape with (111) top and interfacial facets, while the Pt NPs were found to adopt a variety of shapes. For NPs of identical shape for both material systems, the NP-support adhesion energy calculated based on STM data was found to be size-dependent, with large NPs (e.g. ∼6 nm) having lower adhesion energies than smaller NPs (e.g. ∼1 nm). This phenomenon was rationalized based on support-induced strain that for larger NPs favors the formation of lattice dislocations at the interface rather than a lattice distortion that may propagate through the smaller NPs. In addition, identically prepared Pt NPs of the same shape were found to display a lower adhesion energy compared to Pd NPs. While in both cases, a transition from a lattice distortion to interface dislocations is expected to occur with increasing NP size, the higher elastic energy in Pt leads to a lower transition size, which in turn lowers the adhesion energy of Pt NPs compared to Pd. © 2016 The Royal Society of Chemistry.view abstract doi: 10.1039/c6nr02166b 2016 • 458 Spectra library: An assumption-free in situ method to access the kinetics of catechols binding to colloidal ZnO quantum dots
Lin, W. and Haderlein, M. and Walter, J. and Peukert, W. and Segets, D.
Angewandte Chemie - International Edition 55 932-935 (2016)Assumption-free and in situ resolving of the kinetics of ligand binding to colloidal nanoparticles (NPs) with high time resolution is still a challenge in NP research. A unique concept of using spectra library and stopped-flow together with a "search best-match" Matlab algorithm to access the kinetics of ligand binding in colloidal systems is reported. Instead of deconvoluting superimposed spectra using assumptions, species absorbance contributions (ligand@ZnO NPs and ligand in solution) are obtained by offline experiments. Therefrom, a library of well-defined targets with known ligand distribution between particle surface and solution is created. Finally, the evolution of bound ligand is derived by comparing in situ spectra recorded by stopped-flow and the library spectra with the algorithm. Our concept is a widely applicable strategy for kinetic studies of ligand adsorption to colloidal NPs and a big step towards deep understanding of surface functionalization kinetics. Well-established libraries of target spectra that are derived by means of careful offline analysis and identification of equilibrium data within larger kinetic datasets can be used for any particle-ligand system. Kinetics of ligand binding to nanoparticles can be derived free of assumption, in situ, and with high time resolution. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/anie.201508252 2016 • 457 Spray Deposition of Titania Films with Incorporated Crystalline Nanoparticles for All-Solid-State Dye-Sensitized Solar Cells Using P3HT
Song, L. and Wang, W. and Körstgens, V. and Moseguí González, D. and Yao, Y. and Minar, N.K. and Feckl, J.M. and Peters, K. and Bein, T. and Fattakhova-Rohlfing, D. and Santoro, G. and Roth, S.V. and Müller-Buschbaum, P.
Advanced Functional Materials 26 1498-1506 (2016)Spray coating, a simple and low-cost technique for large-scale film deposition, is employed to fabricate mesoporous titania films, which are electron-transporting layers in all-solid-state dye-sensitized solar cells (DSSCs). To optimize solar cell performance, presynthesized crystalline titania nanoparticles are introduced into the mesoporous titania films. The composite film morphology is examined with scanning electron microscopy, grazing incidence small-angle X-ray scattering, and nitrogen adsorption-desorption isotherms. The crystal phase and crystallite sizes are verified by X-ray diffraction measurements. The photovoltaic performance of all-solid-state DSSCs is investigated. The findings reveal that an optimal active layer of the all-solid-state DSSC is obtained by including 50 wt% titania nanoparticles, showing a foam-like morphology with an average pore size of 20 nm, featuring an anatase phase, and presenting a surface area of 225.2 m2 g-1. The optimized morphology obtained by adding 50 wt% presynthesized crystalline titania nanoparticles yields, correspondingly, the best solar cell efficiency of 2.7 ± 0.1%. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/adfm.201504498 2016 • 456 Strong competition between electromagnetic enhancement and surface-energy-transfer induced quenching in plasmonic dye-sensitized solar cells: A generic yet controllable effect
Yip, C.T. and Liu, X. and Hou, Y. and Xie, W. and He, J. and Schlücker, S. and Lei, D.Y. and Huang, H.
Nano Energy 26 297-304 (2016)Light harvesting strategy using plasmonic metal nanostructures as subwavelength light concentrators provides a highly attractive solution to enhancing the performance of dye-sensitized solar cells (DSSCs). Through comprehensive optical spectroscopy and electrical characterizations together with a theoretical analysis, we demonstrate a strong competition between the surface energy transfer induced non-radiative quenching and the plasmonic electromagnetic enhancement effect in metal-dielectric-semiconductor core-shell-shell nanoparticle doped DSSCs, a generic yet unavoidable phenomenon in all types of plasmonic solar cells. The competition of the two effects results in a non-monotonic relationship between the device efficiency and the thickness of the dielectric shell covering the metal nanoparticles, and leads to an optimal thickness for the highest power conversion efficiency. This observation is further corroborated by photoluminescence spectroscopic measurements. Our experimental results are in good agreement with the Persson model that predicts a strong energy quenching effect when the distance between the photogenerated charge carrier and the metal core is short enough. Both experiment and theory show that the localized surface plasmon resonance enhanced light harvesting efficiency is suppressed by the surface energy transfer to the metal cores for the dielectric shell thickness shorter than a characteristic value (~7 nm in our study). Our work sheds new insights into the fundamental understanding of the photophysics mechanisms of plasmonic DSSCs and could push forward the study of plasmonic solar cells in terms of device design and fabrication. © 2016 Elsevier Ltd.view abstract doi: 10.1016/j.nanoen.2016.05.016 2016 • 455 Structure-Activity-Stability Relationships for Space-Confined PtxNiy Nanoparticles in the Oxygen Reduction Reaction
Mezzavilla, S. and Baldizzone, C. and Swertz, A.-C. and Hodnik, N. and Pizzutilo, E. and Polymeros, G. and Keeley, G.P. and Knossalla, J. and Heggen, M. and Mayrhofer, K.J.J. and Schüth, F.
ACS Catalysis 6 8058-8068 (2016)This study focuses on the synthesis and electrochemical performance (i.e, activity and stability) of advanced electrocatalysts for the oxygen reduction reaction (ORR), made of Pt-Ni nanoparticles embedded in hollow graphitic spheres (HGS). The mechanism of the confined space alloying, that is, the controlled alloying of bimetallic precursors with different compositions (i.e., Pt3Ni, PtNi, and PtNi3) within the HGS mesoporous shell, was examined in detail. It was found that the presence of platinum during the reduction step, as well as the application of high annealing temperatures (at least 850°C for 3.5h in Ar), are necessary conditions to achieve the complete encapsulation and the full stability of the catalysts. The evolution of the activity, the electrochemical surface area, and the residual alloy composition of the Pt-Ni@HGS catalysts was thoroughly monitored (at the macro- and nanoscale level) under different degradation conditions. After the initial activation, the embedded Pt-Ni nanoparticles (3-4 nm in size) yield mass activities that are 2- to 3.5-fold higher than that of pure Pt@HGS (depending on the alloy composition). Most importantly, it is demonstrated that under the normal operation range of an ORR catalyst in PEM-FCs (potential excursions between 0.4 and 1.0 VRHE) both the nanoparticle-related degradation pathways (particle agglomeration) and dealloying phenomena are effectively suppressed, irrespectively of the alloy composition. Thus, the initial enhanced activity is completely maintained over an extended degradation protocol. In addition, owing to the peculiar configuration of the catalysts consisting of space-confined nanoparticles, it was possible to elucidate the impact of the dealloying process (as a function of alloy composition and severity of the degradation protocols) separately from other parallel phenomena, providing valuable insight into this elusive degradation mechanism. (Graph Presented). © 2016 American Chemical Society.view abstract doi: 10.1021/acscatal.6b02221 2016 • 454 Synthesis of Bi2Te3 and (Bi: XSb1- x)2Te3 nanoparticles using the novel IL [C4mim]3[Bi3I12]
Loor, M. and Bendt, G. and Hagemann, U. and Wölper, C. and Assenmacher, W. and Schulz, S.
Dalton Transactions 45 15326-15335 (2016)The novel Bi-containing reactive ionic liquid [C4mim]3[Bi3I12], which was synthesized in quantitative yield by equimolar reaction of BiI3 and [C4mim]I, was used as a novel Bi-source for the ionothermal synthesis of Bi2Te3 nanoparticles by reaction with (Et3Si)2Te in the ionic liquid [C4mim]I. The solid state structure of [C4mim]3[Bi3I12] was determined by single crystal X-ray diffraction. In addition, the ionothermal synthesis of the single source precursor (Et2Sb)2Te and [C4mim]3[Bi3I12] yielded the ternary (BixSb1-x)2Te3 (x = 0.25, 0.5, 0.75) nanoparticles. The chemical composition and phase purity of the tetradymite-type materials were determined by EDX and XRD and the surface composition of the nanoparticles was further investigated by IR and XPS. In addition, the morphology of the nanoparticles was investigated by SEM and TEM. © 2016 The Royal Society of Chemistry.view abstract doi: 10.1039/c6dt02361d 2016 • 453 Synthesis of well-defined core-shell nanoparticles based on bifunctional poly(2-oxazoline) macromonomer surfactants and a microemulsion polymerization process
Kampmann, A.-L. and Grabe, T. and Jaworski, C. and Weberskirch, R.
RSC Advances 6 99752-99763 (2016)Particles in the sub-100 nm range have attracted widespread attention in the past few years due to their application in drug delivery and diagnostics. Here we describe the synthesis of two bifunctional, amphiphilic poly(2-oxazoline) macromonomers with multiple acrylate groups in their hydrophobic block and azide or primary amino end groups. The amphiphilic macromonomers were applied in a microemulsion polymerization to form well-defined core-crosslinked nanoparticles with surface functional azide or amine groups. Therefore, an amphiphilic poly(2-oxazoline) was prepared by cationic ring-opening polymerization of 2-methyl-2-oxazoline to form the hydrophilic block and a mixture of 2-heptyl-2-oxazoline and 2-(5-pentyl-[(1,2,3-triazol)-4-yl-methacrylat)]-oxazoline to form the hydrophobic block and was terminated with an azide moiety as end group. The introduction of multiple methacrylate groups into the poly(2-oxazoline) macromonomers serve as a stabilizer in the microemulsion process to covalently link the polymer to the particle core. Variable particle sizes of 20-75 nm have been prepared by encapsulating different amounts of 1,6-hexanedioldimethacrylate (HDDMA) to swell the micellar core before subsequent crosslinking takes place. Finally, particle surface functionalization was achieved by converting the terminal azide group via Staudinger-reaction to a primary amine group. Nanoparticles with surface primary amine groups were functionalized with folic acid (FA), a GRGDS-peptide derivative and fluorescein isothiocyanate (FITC) by simple amidation reaction (FA, RGD-peptide) or thiourea formation (FITC). © 2016 Royal Society of Chemistry.view abstract doi: 10.1039/c6ra22896h 2016 • 452 The Electrochemical Characterization of Single Core-Shell Nanoparticles
Holt, L.R. and Plowman, B.J. and Young, N.P. and Tschulik, K. and Compton, R.G.
Angewandte Chemie - International Edition 55 397-400 (2016)We report the direct solution-phase characterization of individual gold-core silver-shell nanoparticles through an electrochemical means, with selectivity achieved between the core and shell components based on their different redox activities. The electrochemically determined core-shell sizes are in excellent agreement with electron microscopy-based results, successfully demonstrating the electrochemical characterization of individual core-shell nanoparticles. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/anie.201509008 2016 • 451 The Formation and Morphology of Nanoparticle Supracrystals
Haubold, D. and Reichhelm, A. and Weiz, A. and Borchardt, L. and Ziegler, C. and Bahrig, L. and Kaskel, S. and Ruck, M. and Eychmüller, A.
Advanced Functional Materials 26 4890-4895 (2016)Supracrystals are highly symmetrical ordered superstructures built up from nanoparticles (NPs) via self-assembly. While the NP assembly has been intensively investigated, the formation mechanism is still not understood. To shed some light onto the formation mechanism, one of the most common supracrystal morphologies, the trigonal structures, as a model system is being used to investigate the formation process in solution. To explain the formation of the trigonal structures and determining the size of the supracrystal seeds formed in solution, the concept of substrate-affected growth is introduced. Furthermore, the influence of the NP concentration on the seed size is shown and our investigations from Ag toward Au are extended. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/adfm.201600186 2016 • 450 Tuning Catalytic Selectivity at the Mesoscale via Interparticle Interactions
Mistry, H. and Behafarid, F. and Reske, R. and Varela, A.S. and Strasser, P. and Roldan Cuenya, B.
ACS Catalysis 6 1075-1080 (2016)The selectivity of heterogeneously catalyzed chemical reactions is well-known to be dependent on nanoscale determinants, such as surface atomic geometry and composition. However, principles to control the selectivity of nanoparticle (NP) catalysts by means of mesoscopic descriptors, such as the interparticle distance, have remained largely unexplored. We used well-defined copper catalysts to deconvolute the effect of NP size and distance on product selectivity during CO2 electroreduction. Corroborated by reaction-diffusion modeling, our results reveal that mesoscale phenomena such as interparticle reactant diffusion and readsorption of intermediates play a defining role in product selectivity. More importantly, this study uncovers general principles of tailoring NP activity and selectivity by carefully engineering size and distance. These principles provide guidance for the rational design of mesoscopic catalyst architectures in order to enhance the production of desired reaction products. © 2015 American Chemical Society.view abstract doi: 10.1021/acscatal.5b02202 2016 • 449 Tuning the magnetism of ferrite nanoparticles
Viñas, S.L. and Simeonidis, K. and Li, Z.-A. and Ma, Z. and Myrovali, E. and Makridis, A. and Sakellari, D. and Angelakeris, M. and Wiedwald, U. and Spasova, M. and Farle, M.
Journal of Magnetism and Magnetic Materials 415 20-23 (2016)The importance of magnetic interactions within an individual nanoparticle or between adjacent ones is crucial not only for the macroscopic collective magnetic behavior but for the AC magnetic heating efficiency as well. On this concept, single-(MFe2O4 where M=Fe, Co, Mn) and core-shell ferrite nanoparticles consisting of a magnetically softer (MnFe2O4) or magnetically harder (CoFe2O4) core and a magnetite (Fe3O4) shell with an overall size in the 10 nm range were synthesized and studied for their magnetic particle hyperthermia efficiency. Magnetic measurements indicate that the coating of the hard magnetic phase (CoFe2O4) by Fe3O4 provides a significant enhancement of hysteresis losses over the corresponding single-phase counterpart response, and thus results in a multiplication of the magnetic hyperthermia efficiency opening a novel pathway for high-performance, magnetic hyperthermia agents. At the same time, the existence of a biocompatible Fe3O4 outer shell, toxicologically renders these systems similar to iron-oxide ones with significantly milder side-effects. © 2016 Elsevier B.V.view abstract doi: 10.1016/j.jmmm.2016.02.098 2016 • 448 Ultrafiltration membrane-based purification of bioconjugated gold nanoparticle dispersions
Alele, N. and Streubel, R. and Gamrad, L. and Barcikowski, S. and Ulbricht, M.
Separation and Purification Technology 157 120-130 (2016)Functionalization of nanoparticles (NP) with biomolecules to form bioconjugated systems has received large attention in biomedical applications. However, purification of these nanoparticle bioconjugates from unbound free biofunctional ligands (e.g., peptides) remains a significant challenge in the production of well-defined materials. The conventional separation methods often compromise the product's properties and recovery. In this work, removal of excess of unbound peptides after the bioconjugation step to yield functionalized gold nanoparticles (AuNP) was achieved by exploiting the sieving properties of commercial regenerated cellulose (RC) ultrafiltration (UF) membranes. The RC membrane with nominal molecular weight cut-off (NMWCO) of 30 kDa precisely fractionated the mixtures and purified gold nanoparticle-peptide bioconjugates in a pressure driven semi-continuous diafiltration process. The RC 30 kDa membrane showed absolute rejection of the bioconjugated AuNP and the recovery of AuNP-peptide bioconjugate in the retentate was >87% relative to the initial amount in the mixture. In addition, the separation efficiency and throughput results were much better compared to the centrifugal membrane filtration method using an analogous membrane. All results indicate that by choice of an appropriate membrane type and barrier pore size, and with optimized solution chemistry and filtration parameters, ultrafiltration membranes, and in particular RC membranes, can be very well suited for the purification of bioconjugated nanoparticle dispersions, and the diafiltration mode is very well suited for upscaling. © 2015 Elsevier B.V.view abstract doi: 10.1016/j.seppur.2015.11.033 2016 • 447 Zeolite Beta Formation from Clear Sols: Silicate Speciation, Particle Formation and Crystallization Monitored by Complementary Analysis Methods
Castro, M. and Haouas, M. and Lim, I. and Bongard, H.J. and Schüth, F. and Taulelle, F. and Karlsson, G. and Alfredsson, V. and Breyneart, E. and Kirschhock, C.E.A. and Schmidt, W.
Chemistry - A European Journal 22 15307-15319 (2016)The formation of silicate nanoaggregates (NAs) at the very early stages of precursor sols and zeolite beta crystallization from silicate nanoparticles (NPs) are investigated in detail using a combination of different analysis methods, including liquid-state29Si,27Al,14N, and1H NMR spectroscopy, mass spectrometry (MS), small-angle X-ray scattering (SAXS), X-ray diffraction (XRD), and transmission electron microscopy at cryogenic temperatures (cryo-TEM). Prior to hydrothermal treatment, silicate NAs are observed if the Si/OH ratio in the reaction mixture is greater than 1. Condensation of oligomers within the NAs then generates NPs. Aluminum doped into the synthesis mixtures is located exclusively in the NPs, and is found exclusively in a state that is fourfold connected to silicate, favoring their condensation and aggregation. These results are in agreement with general trends observed for other systems. Silicate NAs are essential intermediates for zeolite formation and are generated by the aggregation of hydrated oligomers, aluminate, and templating cations. Subsequent further intra-nanoaggregate silicate condensation results in the formation of NPs.1H and14N liquid NMR as well as diffusion ordered spectroscopy (DOSY) experiments provide evidence for weakly restricted rotational and translational mobility of the organic template within NAs as a consequence of specific silicate–template interactions. NAs thus appear as key species in clear sols, and their presence in the precursor sol favors silicate condensation and further crystallization, promoted either by increasing the Si/OH ratio or by heating. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheimview abstract doi: 10.1002/chem.201600511 2016 • 446 ZnPd/ZnO Aerogels as Potential Catalytic Materials
Ziegler, C. and Klosz, S. and Borchardt, L. and Oschatz, M. and Kaskel, S. and Friedrich, M. and Kriegel, R. and Keilhauer, T. and Armbrüster, M. and Eychmüller, A.
Advanced Functional Materials 26 1014-1020 (2016)Many different aerogel materials are known to be accessible via the controlled destabilization of the respective nanoparticle suspensions. Especially for applications in heterogeneous catalysis such materials with high specific surface areas are highly desirable. Here, a facile method to obtain a mixed ZnPd/ZnO aerogel via a reductive treatment of a preformed Pd/ZnO aerogel is presented. Different morphologies of the Pd/ZnO aerogels could be achieved by controlling the destabilization of the ZnO sol. All aerogels show a high CO2 selectivity of up to 96% and a very good activity in methanol steam reforming that delivers hydrogen, which is one of the most important fuels for future energy concepts. The method presented is promising for different transition metal/metal oxide systems and hence opens a path to a huge variety of materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/adfm.201503000 2015 • 445 A Combined SAXS/SANS Study for the in Situ Characterization of Ligand Shells on Small Nanoparticles: The Case of ZnO
Schindler, T. and Schmiele, M. and Schmutzler, T. and Kassar, T. and Segets, D. and Peukert, W. and Radulescu, A. and Kriele, A. and Gilles, R. and Unruh, T.
Langmuir 31 10130-10136 (2015)ZnO nanoparticles (NPs) have great potential for their use in, e.g., thin film solar cells due to their electro-optical properties adjustable on the nanoscale. Therefore, the production of well-defined NPs is of major interest. For a targeted production process, the knowledge of the stabilization layer of the NPs during and after their formation is of particular importance. For the study of the stabilizer layer of ZnO NPs prepared in a wet chemical synthesis from zinc acetate, only ex situ studies have been performed so far. An acetate layer bound to the surface of the dried NPs was found; however, an in situ study which addresses the stabilizing layer surrounding the NPs in a native dispersion was missing. By the combination of small angle scattering with neutrons and X-rays (SANS and SAXS) for the same sample, we are now able to observe the acetate shell in situ for the first time. In addition, the changes of this shell could be followed during the ripening process for different temperatures. With increasing size of the ZnO core (d<inf>core</inf>) the surrounding shell (d<inf>shell</inf>) becomes larger, and the acetate concentration within the shell is reduced. For all samples, the shell thickness was found to be larger than the maximum extension of an acetate molecule with acetate concentrations within the shell below 50 vol %. Thus, there is not a monolayer of acetate molecules that covers the NPs but rather a swollen shell of acetate ions. This shell is assumed to hinder the growth of the NPs to larger macrostructures. In addition, we found that the partition coefficient μ between acetate in the shell surrounding the NPs and the total amount of acetate in the solution is about 10% which is in good agreement with ex situ data determined by thermogravimetric analysis. © 2015 American Chemical Society.view abstract doi: 10.1021/acs.langmuir.5b02198 2015 • 444 A rapid, high-yield and large-scale synthesis of uniform spherical silver nanoparticles by a microwave-assisted polyol process
Helmlinger, J. and Heise, M. and Heggen, M. and Ruck, M. and Epple, M.
RSC Advances 5 92144-92150 (2015)Silver nanoparticles are often employed in medical devices and consumer products due to their antibacterial action. For this, reliable syntheses with quantitative yield are required. Uniform spherical silver nanoparticles with a diameter of about 180 nm were synthesized by carrying out the polyol synthesis in a microwave. Silver nitrate was dissolved in ethylene glycol and poly(N-vinyl pyrrolidone) (PVP) was added as capping agent. The particles were characterized by SEM, HRTEM, XRD, and DLS. The results are compared with the classical method where silver nitrate is reduced by glucose in aqueous solution, heated with an oil-bath. The microwave-assisted synthesis leads to an almost quantitative yield of uniform silver nanoparticles after 20 min reaction time and gives exclusively spherical particles without other shapes like triangles, rods or prisms. Diethylene glycol as solvent gave a more homogeneous particle size distribution than ethylene glycol. For both kinds of particles, dissolution in ultrapure water was examined over a period of 29 days in the presence of oxygen. The dissolution was comparable in both cases (about 50% after 4 weeks), indicating the same antibacterial action for particles from the microwave and from the glucose synthesis. © The Royal Society of Chemistry 2015.view abstract doi: 10.1039/c5ra20446a 2015 • 443 Amorphous and Crystalline Sodium Tantalate Composites for Photocatalytic Water Splitting
Grewe, T. and Tüysüz, H.
ACS Applied Materials and Interfaces 7 23153-23162 (2015)A facile hydrothermal synthesis protocol for the fabrication of sodium tantalates for photocatalytic water splitting is presented. Mixtures of tantalum and sodium ethoxide precursors were dispersed in ethanol, and ammonium hydroxide solution was used as mineralizer. By adjusting the amount of mineralizer, a variety of sodium tantalates with various morphologies, textural parameters, band gaps, crystal phases, and degrees of crystallinity were fabricated. The reaction was carefully monitored with a pressure sensor inside the autoclave reactor, and the obtained samples were characterized using X-ray diffraction, transmission electron microscopy, N2-physisorption, and ultraviolet-visible light spectroscopy. Among the series, the amorphous sample and the composite sample that consists of amorphous and crystalline phases showed superior activity toward photocatalytic hydrogen production than highly crystalline samples. Particularly, an amorphous sodium tantalate with a small fraction of crystalline nanoparticles with perovskite structure was found to be the most active sample, reaching a hydrogen rate of 3.6 mmol h-1 from water/methanol without the use of any cocatalyst. Despite its amorphous nature, this photocatalyst gave an apparent photocatalyst activity of 1200 μmol g-1 L-1 h-1 W1-, which is 4.5-fold higher than highly crystalline NaTaO3. In addition, the most active sample gave promising activity for overall water splitting with a hydrogen production rate of 94 μmol h-1, which is superior to highly crystalline NaTaO3 prepared by conventional solid-solid state route. © 2015 American Chemical Society.view abstract doi: 10.1021/acsami.5b06965 2015 • 442 An approach for transparent and electrically conducting coatings: A transparent plastic varnish with nanoparticulate magnetic additives
Beck, G. and Barcikowski, S. and Chakravadhanula, V.S.K. and Comesaña-Hermo, M. and Deng, M. and Farle, M. and Hilgendorff, M. and Jakobi, J. and Janek, J. and Kienle, L. and Mogwitz, B. and Schubert, T. and Stiemke, F.
Thin Solid Films 595 96-107 (2015)For the purpose of preparing TCCs (= transparent and electrical conducting coatings), metallic and ferromagnetic nano-additives were dispersed into a transparent varnish and the obtained dispersions were coated on transparent plastic substrates. During hardening of the dispersion the magnetic nano-additives were aligned by a magnetic field. The resulting coatings have electrical pathways along lines of nano-additive chains and are highly transparent in the areas between the lines. Therefore, the electrical conductivity is anisotropic, and it depends on the alignment of the nano-additives (i.e. on the distance between the nano-additives within the chains and the length of the lines) as well as on the thickness of an oxide and/or solvent shell around the nano-additives. The transparency depends also on the alignment and here especially on the thickness and the distance between the formed lines. The quality of the alignment in turn, depends on the magnetic properties and on the size of the particles. We used commercial plastic varnishes, which form electrically isolating (≥ 10− 12 S/m) and transparent (about 90% transparency) coatings, and the following magnetic additives: Co-, Fe-, CoPt3, CoPt3@Au- and Fe@Au-nanoparticles as well as CoNi-nanowires. Coatings with Fe@Au-nanoparticles show the best results in terms of the electrical conductivity (10− 5 S/m–10− 6 S/m) at transparencies above 70%. Furthermore, in addition to the magnetic nano-additives, transparent additives (Al2O3-particles) and non-magnetic, but better conducting additives (carbon-nanotubes) were added to the varnish to increase the transparency and the electrical conductivity, respectively. © 2015 Elsevier B.V.view abstract doi: 10.1016/j.tsf.2015.10.059 2015 • 441 An efficient method for calculating the absorption enhancement in solar cells with integrated plasmonic and photonic nanoparticles
Manley, P. and Schmidt, F. and Schmid, M.
2015 9th International Congress on Advanced Electromagnetic Materials in Microwaves and Optics, METAMATERIALS 2015 193-195 (2015)We present a method for calculating the plasmonic and photonic enhancement of the absorption in solar cells. The method involves coupling between a transfer matrix method to describe light propagation in the layered stack and Mie theory for calculating the absorption and angular scattered field distribution from the nanoparticles. We also compare the method to rigorous simulations. © 2015 IEEE.view abstract doi: 10.1109/MetaMaterials.2015.7342570 2015 • 440 Are Nanoparticles Spherical or Quasi-Spherical?
Sokolov, S.V. and Batchelor-Mcauley, C. and Tschulik, K. and Fletcher, S. and Compton, R.G.
Chemistry - A European Journal 21 10741-10746 (2015)The geometry of quasi-spherical nanoparticles is investigated. The combination of SEM imaging and electrochemical nano-impact experiments is demonstrated to allow sizing and characterization of the geometry of single silver nanoparticles. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/chem.201500807 2015 • 439 Assembling Paramagnetic Ceruloplasmin at Electrode Surfaces Covered with Ferromagnetic Nanoparticles. Scanning Electrochemical Microscopy in the Presence of a Magnetic Field
Matysiak, E. and Botz, A.J.R. and Clausmeyer, J. and Wagner, B. and Schuhmann, W. and Stojek, Z. and Nowicka, A.M.
Langmuir 31 8176-8183 (2015)Adsorption of ceruloplasmin (Cp) at a gold electrode modified with ferromagnetic iron nanoparticles encapsulated in carbon (Fe@C Nps) leads to a successful immobilization of the enzyme in its electroactive form. The proper placement of Cp at the electrode surface on top of the nanocapsules containing an iron core allowed a preorientation of the enzyme, hence allowing direct electron transfer between the electrode and the enzyme. Laser ablation coupled with inductively coupled plasma mass spectrometry indicated that Cp was predominantly located at the paramagnetic nanoparticles. Scanning electrochemical microscopy measurements in the sample-generation/tip-collection mode proved that Cp was ferrooxidative inactive if it was immobilized on the bare gold surface and reached the highest activity if it was adsorbed on Fe@C Nps in the presence of a magnetic field. © 2015 American Chemical Society.view abstract doi: 10.1021/acs.langmuir.5b01155 2015 • 438 Bifunctional redox tagging of carbon nanoparticles
Poon, J. and Batchelor-McAuley, C. and Tschulik, K. and Palgrave, R.G. and Compton, R.G.
Nanoscale 7 2069-2075 (2015)Despite extensive work on the controlled surface modification of carbon with redox moieties, to date almost all available methodologies involve complex chemistry and are prone to the formation of polymerized multi-layer surface structures. Herein, the facile bifunctional redox tagging of carbon nanoparticles (diameter 27 nm) and its characterization is undertaken using the industrial dye Reactive Blue 2. The modification route is demonstrated to be via exceptionally strong physisorption. The modified carbon is found to exhibit both well-defined oxidative and reductive voltammetric redox features which are quantitatively interpreted. The method provides a generic approach to monolayer modifications of carbon and carbon nanoparticle surfaces. © The Royal Society of Chemistry 2015.view abstract doi: 10.1039/c4nr06058j 2015 • 437 Biocompatible microgel-modified electrospun fibers for zinc ion release
Wilke, P. and Coger, V. and Nachev, M. and Schachschal, S. and Million, N. and Barcikowski, S. and Sures, B. and Reimers, K. and Vogt, P.M. and Pich, A.
Polymer (United Kingdom) 61 163-173 (2015)We present a novel and facile method for the design of biocompatible microgel-modified microfibers loaded with ZnO nanoparticles capable of zinc ion release under physiological conditions. The microfibers consist of three materials hierarchically assembled in a controlled and reproducible way. We synthesized poly(N-vinylcaprolactam-co-itaconic acid) aqueous microgels with carboxylic groups located in the microgel core. The obtained microgels can be loaded with various amounts of ZnO nanoparticles by in-situ growth of ZnO in microgels. As shown by electrophoretic mobility and TEM measurements, ZnO nanoparticles are selectively loaded in the microgel core and stabilized by itaconic acid groups bearing strong negative charges. ZnO-loaded microgels were used as functional additive to produce poly(ε-caprolactone) (PCL) microfibers using the electrospinning process. The resulting microfibers consist of a PCL core coated with the microgels located at the surface of the fibers. The variation of the ZnO amount loaded into microgels allows regulating the ZnO content in microfibers and gives the possibility to tune the released amount of zinc ions in aqueous medium at pH 7.5 and 37 °C. We demonstrate that the obtained functional microfibers are biocompatible and non-toxic, thus being good candidates for biomedical applications like scaffolds for tissue engineering, biointerface coatings or wound closing dressings. © 2015 Elsevier Ltd. All rights reserved.view abstract doi: 10.1016/j.polymer.2015.01.078 2015 • 436 Bioconjugated gold nanoparticles penetrate into spermatozoa depending on plasma membrane status
Barchanski, A. and Taylor, U. and Sajti, C.L. and Gamrad, L. and Kues, W.A. and Rath, D. and Barcikowski, S.
Journal of Biomedical Nanotechnology 11 1597-1607 (2015)Spermatozoa are not only essential for animal reproduction they also represent important tools for the manipulation of animal genetics. For instance, the genetic labeling and analysis of spermatozoa could provide a prospective complementation of pre-fertilization diagnosis and could help to prevent the inheritance of defective alleles during artificial insemination or to select beneficial traits in livestock. Spermatozoa feature extremely specialized membrane organization and restricted transport mechanisms making the labeling of genetically interesting DNA-sequences, e.g., with gold nanoparticles, a particular challenge. Here, we present a systematic study on the size-related internalization of ligand-free, monovalent and bivalent polydisperse gold nanoparticles, depending on spermatozoa membrane status. While monovalent conjugates were coupled solely to either negatively-charged oligonucleotides or positively-charged cell-penetrating peptides, bivalent conjugates were functionalized with both molecules simultaneously. The results clearly indicate that the cell membrane of acrosome-intact, bovine spermatozoa was neither permeable to ligand-free or oligonucleotide-conjugated nanoparticles, nor responsive to the mechanisms of cell-penetrating peptides. Interestingly, after acrosome reaction, which comprises major changes in sperm membrane composition, fluidity and charge, high numbers of monovalent and bivalent nanoparticles were found in the postequatorial segment, depicting a close and complex correlation between particle internalization and membrane organization. Additionally, depending on the applied peptide and for nanoparticle sizes <10 nm even a successive nuclear penetration was observed, making the bivalent conjugates promising for future genetic delivery and sorting issues. Copyright © 2015 American Scientific Publishers All rights reserved.view abstract doi: 10.1166/jbn.2015.2094 2015 • 435 Calcium phosphate nanoparticles carrying BMP-7 plasmid DNA induce an osteogenic response in MC3T3-E1 pre-osteoblasts
Hadjicharalambous, C. and Kozlova, D. and Sokolova, V. and Epple, M. and Chatzinikolaidou, M.
Journal of Biomedical Materials Research - Part A 103 3834-3842 (2015)Functionalized calcium phosphate nanoparticles with osteogenic activity were prepared. Polyethyleneimine-stabilized calcium phosphate nanoparticles were coated with a shell of silica and covalently functionalized by silanization with thiol groups. Between the calcium phosphate surface and the outer silica shell, plasmid DNA which encoded either for bone morphogenetic protein 7 (BMP-7) or for enhanced green fluorescent protein was incorporated as cargo. The plasmid DNA-loaded calcium phosphate nanoparticles were used for the transfection of the pre-osteoblastic MC3T3-E1 cells. The cationic nanoparticles showed high transfection efficiency together with a low cytotoxicity. Their potential to induce an osteogenic response by transfection was demonstrated by measuring the alkaline phosphatase (ALP) activity and calcium deposition with alizarin red staining. The expression of the osteogenic markers Alp, Runx2, ColIa1 and Bsp was investigated by means of real-time quantitative polymerase chain reaction. It was shown that phBMP-7-loaded nanoparticles can provide a means of transient transfection and localized production of BMP-7 in MC3T3-E1 cells, with a subsequent increase of two osteogenic markers, specifically ALP activity and calcium accumulation in the extracellular matrix. Future strategies to stimulate bone regeneration focus into enhancing transfection efficiency and achieving higher levels of BMP-7 produced by the transfected cells. © 2015 Wiley Periodicals, Inc.view abstract doi: 10.1002/jbm.a.35527 2015 • 434 Carbon Monoxide-Induced Stability and Atomic Segregation Phenomena in Shape-Selected Octahedral PtNi Nanoparticles
Ahmadi, M. and Cui, C. and Mistry, H. and Strasser, P. and Roldan Cuenya, B.
ACS Nano 9 10686-10694 (2015)The chemical and morphological stability of size- and shape-selected octahedral PtNi nanoparticles (NP) were investigated after different annealing treatments up to a maximum temperature of 700 °C in a vacuum and under 1 bar of CO. Atomic force microscopy was used to examine the mobility of the NPs and their stability against coarsening, and X-ray photoelectron spectroscopy to study the surface composition, chemical state of Pt and Ni in the NPs, and thermally and CO-induced atomic segregation trends. Exposing the samples to 1 bar of CO at room temperature before annealing in a vacuum was found to be effective at enhancing the stability of the NPs against coarsening. In contrast, significant coarsening was observed when the sample was annealed in 1 bar of CO, most likely as a result of Ni(CO)4 formation and their enhanced mobility on the support surface. Sample exposure to CO at room temperature prior to annealing led to the segregation of Pt to the NP surface. Nevertheless, oxidic PtOx and NiOx species still remained at the NP surface, and, irrespective of the initial sample pretreatment, Ni surface segregation was observed upon annealing in a vacuum at moderate temperature (T < 300 °C). Interestingly, a distinct atomic segregation trend was detected between 300 and 500 °C for the sample pre-exposed to CO; namely, Ni surface segregation was partially hindered. This might be attributed to the higher bonding energy of CO to Pt as compared to Ni. Annealing in the presence of 1 bar CO also resulted in the initial surface segregation of Ni (T < 400 °C) as long as PtOx and NiOx species were available on the surface as a result of the higher affinity of Ni for oxygen. Above 500 °C, and regardless of the sample pretreatment, the diffusion of Pt atoms to the NP surface and the formation of a Ni-Pt alloy are observed. © 2015 American Chemical Society.view abstract doi: 10.1021/acsnano.5b01807 2015 • 433 Charge storage in β -FeSi2 nanoparticles
Theis, J. and Bywalez, R. and Küpper, S. and Lorke, A. and Wiggers, H.
Journal of Applied Physics 117 (2015)We report on the observation of a surprisingly high specific capacitance of β-FeSi2 nanoparticle layers. Lateral, interdigitated capacitor structures were fabricated on thermally grown silicon dioxide and covered with β-FeSi2 particles by drop or spin casting. The β-FeSi2-nanoparticles, with crystallite sizes in the range of 10-30nm, were fabricated by gas phase synthesis in a hot wall reactor. Compared to the bare electrodes, the nanoparticle-coated samples exhibit a 3-4 orders of magnitude increased capacitance. Time-resolved current voltage measurements show that for short times (seconds to minutes), the material is capable of storing up to 1 As/g at voltages of around 1V. The devices are robust and exhibit long-term stability under ambient conditions. The specific capacitance is highest for a saturated relative humidity, while for a relative humidity below 40% the capacitance is almost indistinguishable from a nanoparticle-free reference sample. The devices work without the need of a fluid phase, the charge storing material is abundant and cost effective, and the sample design is easy to fabricate. © 2015 AIP Publishing LLC.view abstract doi: 10.1063/1.4906500 2015 • 432 Co 3 O4 -MnO2 -CNT Hybrids Synthesized by HNO3 Vapor Oxidation of Catalytically Grown CNTs as OER Electrocatalysts
Xie, K. and Masa, J. and Madej, E. and Yang, F. and Weide, P. and Dong, W. and Muhler, M. and Schuhmann, W. and Xia, W.
ChemCatChem 7 3027-3035 (2015)An efficient two-step gas-phase method was developed for the synthesis of Co<inf>3</inf>O<inf>4</inf>-MnO<inf>2</inf>-CNT hybrids used as electrocatalysts in the oxygen evolution reaction (OER). Spinel Co-Mn oxide was used for the catalytic growth of multiwalled carbon nanotubes (CNTs) and the amount of metal species remaining in the CNTs was adjusted by varying the growth time. Gas-phase treatment in HNO<inf>3</inf> vapor at 200 °C was performed to 1)open the CNTs, 2)oxidize encapsulated Co nanoparticles to Co<inf>3</inf>O<inf>4</inf> as well as MnO nanoparticles to MnO<inf>2</inf>, and 3)to create oxygen functional groups on carbon. The hybrid demonstrated excellent OER activity and stability up to 37.5h under alkaline conditions, with longer exposure to HNO<inf>3</inf> vapor up to 72h beneficial for improved electrocatalytic properties. The excellent OER performance can be assigned to the high oxidation states of the oxide nanoparticles, the strong electrical coupling between these oxides and the CNTs as well as favorable surface properties rendering the hybrids a promising alternative to noble metal based OER catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/cctc.201500469 2015 • 431 Conductivity Mechanisms in Sb-Doped SnO 2 Nanoparticle Assemblies: DC and Terahertz Regime
Skoromets, V. and Němec, H. and Kopeček, J. and Kužel, P. and Peters, K. and Fattakhova-Rohlfing, D. and Vetushka, A. and Müller, M. and Ganzerová, K. and Fejfar, A.
Journal of Physical Chemistry C 119 19485-19495 (2015)Assemblies of undoped and antimony-doped tin oxide nanoparticles synthesized via a nonaqueous sol-gel procedure, pressed into pellets, and annealed under various conditions were investigated using time-domain terahertz spectroscopy, scanning electron microscopy, atomic force microscopy, and dc conductivity measurements. Combination of these methods made it possible to resolve the conductivity limitations imposed by intrinsic properties of the material and by the morphology of the samples. Percolation of the nanoparticles was confirmed in all samples. The undoped samples exhibit a weak hopping conductivity, whereas bandlike conduction of charges partially confined in the nanoparticles dominates in the doped samples. The conductivity of nanoparticles and their connectivity can be greatly controlled during the sample preparation, namely by the calcination temperature and by the order of technological steps. A substantial increase of the conductivity inside nanoparticles and of the charge transport between them is achieved upon calcination at 500 °C. © 2015 American Chemical Society.view abstract doi: 10.1021/acs.jpcc.5b05091 2015 • 430 Continuous electrophoretic deposition and electrophoretic mobility of ligand-free, metal nanoparticles in liquid flow
Koenen, S. and Streubel, R. and Jakobi, J. and Schwabe, K. and Krauss, J.K. and Barcikowski, S.
Journal of the Electrochemical Society 162 D174-D179 (2015)Direct current electrophoretic deposition (DC-EPD) of ligand-free metal nanoparticles in a flow-through reactor is studied by analyzing the educt colloid and the outflow of the flow through chamber while the concentration of the colloid and the strength of the electric field is varied.Metal nanoparticles synthesized by pulsed laser ablation in liquid (PLAL) are used to ensure that the colloidal nanoparticle surface is free of any ligands and that the colloid's stability and movement in an electric field is solely influenced by electrostatic forces. Electrophoretic mobility and deposition kinetics of these ligand-free nanoparticles on plain surfaces are examined for different electric field strengths. Additionally, a continuous liquid flow DC-EPD process is presented and optimized regarding deposition rate, colloid stability, and liquid flow rate. The reported parameter window for high deposition rates of nanoparticles without a negative impact on the colloid, allows to define an efficient stationary EPD process suitable for high throughput applications. © 2015 The Electrochemical Society.view abstract doi: 10.1149/2.0811504jes 2015 • 429 Controllable Synthesis of Mesoporous Peapod-like Co 3 O4 @Carbon Nanotube Arrays for High-Performance Lithium-Ion Batteries
Gu, D. and Li, W. and Wang, F. and Bongard, H. and Spliethoff, B. and Schmidt, W. and Weidenthaler, C. and Xia, Y. and Zhao, D. and Schüth, F.
Angewandte Chemie - International Edition 54 7060-7064 (2015)Abstract Transition metal oxides are regarded as promising anode materials for lithium-ion batteries because of their high theoretical capacities compared with commercial graphite. Unfortunately, the implementation of such novel anodes is hampered by their large volume changes during the Li+ insertion and extraction process and their low electric conductivities. Herein, we report a specifically designed anode architecture to overcome such problems, that is, mesoporous peapod-like Co<inf>3</inf>O<inf>4</inf>@carbon nanotube arrays, which are constructed through a controllable nanocasting process. Co<inf>3</inf>O<inf>4</inf> nanoparticles are confined exclusively in the intratubular pores of the nanotube arrays. The pores between the nanotubes are open, and thus render the Co<inf>3</inf>O<inf>4</inf> nanoparticles accessible for effective electrolyte diffusion. Moreover, the carbon nanotubes act as a conductive network. As a result, the peapod-like Co<inf>3</inf>O<inf>4</inf>@carbon nanotube electrode shows a high specific capacity, excellent rate capacity, and very good cycling performance. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/anie.201501475 2015 • 428 Core-Shell Nanoparticles: Characterizing Multifunctional Materials beyond Imaging - Distinguishing and Quantifying Perfect and Broken Shells
Tschulik, K. and Ngamchuea, K. and Ziegler, C. and Beier, M.G. and Damm, C. and Eychmueller, A. and Compton, R.G.
Advanced Functional Materials 25 5149-5158 (2015)Core-shell nanoparticles (NPs) are amongst the most promising candidates in the development of new functional materials. Their fabrication and characterization are challenging, in particular when thin and intact shells are needed. To date no technique has been available that differentiates between intact and broken or cracked shells. Here a method is presented to distinguish and quantify these types of shells in a single cyclic voltammetry experiment by using the different electrochemical reactivities of the core and the shell material. A simple comparison of the charge measured during the stripping of the core material before and after the removal of the shell makes it possible to determine the quality of the shells and to estimate their thickness. As a proof-of-concept two multifunctional examples of core-shell NPs, Fe<inf>3</inf>O<inf>4</inf>@Au and Au@SnO<inf>2</inf>, are used. This general and original method can be applied whenever core and shell materials show different redox properties. Because billions of NPs are probed simultaneously and at a low cost, this method is a convenient new screening tool for the development of new multifunctional core-shell materials and is hence a powerful complementary technique or even an alternative to the state-of-the-art characterization of core-shell NPs by TEM. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/adfm.201501556 2015 • 427 Covalently bonded compounds of heavy group 15/16 elements - Synthesis, structure and potential application in material sciences
Schulz, S.
Coordination Chemistry Reviews 297-298 49-76 (2015)Our understanding on the nature of weak intermolecular metal-metal interactions as well as of multiple bonding in group 15/16 chemistry, in particular of compounds containing the heaviest elements of both groups - Sb, Bi, Se, and Te - is still scarce. These types of interactions are particularly important for the chemical and physical properties of such main group element compounds. For instance, the formation and disruption of weak intermolecular metal-metal interactions are the origin of the so-called thermochroism. The structural characterization of compounds containing sterically less demanding organic substituents is therefore of particular interest, since the capability of small substituents to kinetically stabilize the respective metal centers - and hence to suppress intermolecular interactions - is expected to be rather less pronounced. We will herein summarize the most recent results reported for the synthesis and structural characterization of group 15/16 compounds containing a direct (polar-covalent) element-element bond including compounds containing a terminal, formally double bond. In addition, the capability of selected compounds to serve as single-source precursor for the synthesis of the corresponding nanomaterials, in particular Sb<inf>2</inf>Te<inf>3</inf> and Bi<inf>2</inf>Te<inf>3</inf>, by using wet chemical methods as well as gas phase approaches such as metal organic chemical vapor deposition (MOCVD) processes will be demonstrated. © 2014 Elsevier B.V.view abstract doi: 10.1016/j.ccr.2014.11.003 2015 • 426 Cysteine-containing oligopeptide β-sheets as redispersants for agglomerated metal nanoparticles
Mizutaru, T. and Sakuraba, T. and Nakayama, T. and Marzun, G. and Wagener, P. and Rehbock, C. and Barcikowski, S. and Murakami, K. and Fujita, J. and Ishii, N. and Yamamoto, Y.
Journal of Materials Chemistry A 3 17612-17619 (2015)Oligopeptide β-sheets comprising a fluorenyl methoxy carbonyl (Fmoc) group on its N-terminus and five amino acid residues of cysteine, lysine and valine displays redispersive properties with respect to agglomerated metal nanoparticles (MNPs, M = Au, Cu, Pt and Pd). The ligand-free MNPs prepared by a laser ablation technique in liquid maintain a high dispersion state due to the inherent surface charges delivered by anionic species present in solution, but may agglomerate after the preparation depending on concentration or salinity. We show how the agglomerated MNPs can be returned to the dispersed state by adding the Fmoc-oligopeptide β-sheets in methanol, as characterized by photoabsorption spectroscopy and transmission electron microscopy. Systematic studies in which we vary the concentration, the amino acid sequences and the secondary structures of a series of the oligopeptides clarify that the β-sheet structure is essential for the redispersion of the MNPs, where metal-binding thiol groups are integrated on one side and positively charged amino groups are located on the other side of the β-sheet. A possible mechanism for the redispersion may be that the agglomerated MNPs are subsequently enwrapped by the flexible β-sheets and gradually separated due to the reconstruction of peptide β-sheets under the assembly/disassembly equilibrium. © The Royal Society of Chemistry 2015.view abstract doi: 10.1039/c5ta02098k 2015 • 425 Diffusional impacts of nanoparticles on microdisc and microwire electrodes: The limit of detection and first passage statistics
Eloul, S. and Kätelhön, E. and Batchelor-McAuley, C. and Tschulik, K. and Compton, R.G.
Journal of Electroanalytical Chemistry 755 136-142 (2015)We derive approximate expressions for the average number of diffusive impacts/hits of nanoparticles on microdisc and microwire electrodes for the case where the impact leads to the loss of the nanoparticles from solution either via irreversible adsorption or complete electro-dissolution. The theory can also be applied to sub-micrometre size electrodes (nano-electrodes). The resulting equations can be utilised to analyse the number of impacts and its variance in the 'nano-impact' experiment. We also provide analytical expressions for the first passage time of an impact for dilute nanoparticle solutions in the continuum limit of Fickian diffusion. The expressions for the first passage times are used to estimate the lower limit of detection in ultra-dilute nanoparticle solutions for typical nano-impact experiments, and show the advantage of using microwire electrodes in ultra-dilute solutions or solutions containing larger nano-particles. © 2015 Elsevier B.V. All rights reserved.view abstract doi: 10.1016/j.jelechem.2015.07.042 2015 • 424 Effect of process parameters on the formation of laser-induced nanoparticles during material processing with continuous solid-state lasers
Scholz, T. and Dickmann, K. and Ostendorf, A. and Uphoff, H. and Michalewicz, M.
Journal of Laser Applications 27 (2015)During laser material processing with high laser beam intensities, a laser-induced vapor formation can occur. Due to the shockwave behavior of the vapor plume and the associated rapid cooling, a significant particle formation can be initiated by nucleation. The laser radiation interacts with the particles which can result in a dynamic change of the intensity distribution on the surface. Especially in the field of laser remote processing, the attenuation of laser radiation by nanoparticles can influence the process stability and reduce the processing quality. The presented work is focused on the particle formation at a height of 10 mm above the material surface during the laser welding of stainless steel with a fiber laser. The laser beam intensity on the surface was varied between 1.3 and 5.1 MW/cm2. Transmission electron microscopy images of the nanoparticles and high speed images of the vapor propagation in the ambient atmosphere were analyzed. The attenuation of a probe beam in the vapor plume was evaluated in dependence on the wavelength. The results indicate a linear connection between the laser beam power and the particle formation rate. © 2015 Laser Institute of America.view abstract doi: 10.2351/1.4916081 2015 • 423 Effect of the specific surface area on thermodynamic and kinetic properties of nanoparticle anatase TiO 2 in lithium-ion batteries
Madej, E. and Klink, S. and Schuhmann, W. and Ventosa, E. and La Mantia, F.
Journal of Power Sources 297 140-148 (2015)Anatase TiO<inf>2</inf> nanoparticles with a specific surface area of 100 m2 g-1 and 300 m2 g-1 have been investigated as negative insertion electrode material for lithium-ion batteries. Galvanostatic intermittent titration (GITT) and electrochemical impedance spectroscopy (EIS) were used to investigate the effect of the specific surface area on the performance of the material. GITT was performed at C/10 rate, followed by an EIS measurement after each relaxation step. Separation of kinetic and thermodynamic contributions to the overpotential of the phase transformation on Li+ (de-)insertion allowed revealing a dependency of both terms on the specific surface area. The material with higher surface area undergoes intrinsic transformation during the initial cycles affecting the thermodynamics of (de-)insertion while the sample with lower surface area shows large and asymmetric kinetic hindrances. For the material with 15 nm particles, Li+ de-insertion appears to have a higher resistance than lithium insertion. © 2015, Elsevier B.V. All rights reserved.view abstract doi: 10.1016/j.jpowsour.2015.07.079 2015 • 422 Electrochemical detection of single E. coli bacteria labeled with silver nanoparticles
Sepunaru, L. and Tschulik, K. and Batchelor-McAuley, C. and Gavish, R. and Compton, R.G.
Biomaterials Science 3 816-820 (2015)A proof-of-concept for the electrochemical detection of single Escherichia coli bacteria decorated with silver nanoparticles is reported. Impacts of bacteria with an electrode - held at a suitably oxidizing potential - lead to an accompanying burst of current with each collision event. The frequency of impacts scales with the concentration of bacteria and the charge indicates the extent of decoration. © The Royal Society of Chemistry.view abstract doi: 10.1039/c5bm00114e 2015 • 421 Enhanced biomedical heat-triggered carriers via nanomagnetism tuning in ferrite-based nanoparticles
Angelakeris, M. and Li, Z.-A. and Hilgendorff, M. and Simeonidis, K. and Sakellari, D. and Filippousi, M. and Tian, H. and Van Tendeloo, G. and Spasova, M. and Acet, M. and Farle, M.
Journal of Magnetism and Magnetic Materials 381 179-187 (2015)Biomedical nanomagnetic carriers are getting a higher impact in therapy and diagnosis schemes while their constraints and prerequisites are more and more successfully confronted. Such particles should possess a well-defined size with minimum agglomeration and they should be synthesized in a facile and reproducible high-yield way together with a controllable response to an applied static or dynamic field tailored for the specific application. Here, we attempt to enhance the heating efficiency in magnetic particle hyperthermia treatment through the proper adjustment of the core-shell morphology in ferrite particles, by controlling exchange and dipolar magnetic interactions at the nanoscale. Thus, core-shell nanoparticles with mutual coupling of magnetically hard (CoFe2O4) and soft (MnFe2O4) components are synthesized with facile synthetic controls resulting in uniform size and shell thickness as evidenced by high resolution transmission electron microscopy imaging, excellent crystallinity and size monodispersity. Such a magnetic coupling enables the fine tuning of magnetic anisotropy and magnetic interactions without sparing the good structural, chemical and colloidal stability. Consequently, the magnetic heating efficiency of CoFe2O4 and MnFe2O4 core-shell nanoparticles is distinctively different from that of their counterparts, even though all these nanocrystals were synthesized under similar conditions. For better understanding of the AC magnetic hyperthermia response and its correlation with magnetic-origin features we study the effect of the volume ratio of magnetic hard and soft phases in the bimagnetic core-shell nanocrystals. Eventually, such particles may be considered as novel heating carriers that under further biomedical functionalization may become adaptable multifunctional heat-triggered nanoplatforms. © 2014 Elsevier B.V. All rights reserved.view abstract doi: 10.1016/j.jmmm.2014.12.069 2015 • 420 Formation and stabilization of ZnO nanoparticles inside MCM-48 porous support via post-synthetic organometallic route
Bandyopadhyay, M. and Gies, H. and Grünert, W. and Van Den Berg, M. and Birkner, A.
Advanced Materials Letters 6 978-983 (2015)The interpenetrating 3-dimensional channel system of silica MCM-48 has been selected for the deposition of ZnO nanoparticles. The post-synthetic organometallic route was employed to load the mesoporous silica with ZnO-precursor molecule. Calcination of the composite transformed the organometallic sorbate to the corresponding metal oxide. X-ray powder diffraction, N2-Adsorption and TEM measurement have supported the efficient loading and growth of ZnO particles in the channels of mesoporous silica matrix. EXAFS analysis (ZnK-edges) also complemented the metal uptake. Presence of nano-dispersed and nanosized ZnO particles confined by the mesoporous pore system was established by TEM and EXAFS analysis. © 2015 VBRI Press.view abstract doi: 10.5185/amlett.2015.5963 2015 • 419 From in situ characterization to process control of quantum dot systems
Segets, D. and Peukert, W.
Procedia Engineering 102 575-581 (2015)Quantum confined semiconductor nanoparticles (quantum dots, QDs) are promising candidates for various applications in emerging fields like electronics, solar cells, sensors and diagnostics. However, a larger scale production of QDs at high product quality is still missing. One of the key requirements to address this issue in the near future was identified to be a fast and in situ applicable characterization method. Suitable characterization requires knowledge on the full shape of the particle size distributions (PSDs) under investigation. Thus, determination of a mean particle size together with the width of the PSD is not sufficient. In the following, a method will be presented that allows the derivation of arbitrary shaped PSDs for QDs with direct band gap based on their optical absorbance spectra. After validation of the technique by means of ZnO nanoparticles the transfer of the concept to other QD materials like PbS and PbSe will be proven. Therefore we will extend our methodology and show how our approach can be used to derive spectral properties like the size dependent band gap energy. This is realized by proper calibration of the calculation results against PSDs determined by an independent analysis technique like transmission electron microscopy (TEM). © 2015 The Authors.view abstract doi: 10.1016/j.proeng.2015.01.129 2015 • 418 Gene silencing of the pro-inflammatory cytokine TNF-α with siRNA delivered by calcium phosphate nanoparticles, quantified by different methods
Neuhaus, B. and Frede, A. and Westendorf, A.M. and Epple, M.
Journal of Materials Chemistry B 3 7186-7193 (2015)The pro-inflammatory cytokine TNF-α was silenced by treating MODE-K cells with triple-shell calcium phosphate nanoparticles. These consisted of a core of calcium phosphate, followed by a shell of siRNA, then a shell of calcium phosphate to protect the siRNA from nucleases and finally a shell of poly(ethyleneimine) for colloidal stabilization and to give the particles a positive charge. First, the gene silencing efficiency was demonstrated with HeLa-eGFP cells and determined by manually counting the green fluorescent cells, by quantitative FACS analysis of the green fluorescence per cell, and by qPCR at the RNA level. Cell counting gave the highest degrees of eGFP expression, but FACS and qPCR gave more accurate data as they are not probing the cell colour (green or not green) only as yes/no property. This was transposed to the inflammatory relevant mouse cell line MODE-K that was previously stimulated with LPS to induce the expression of TNF-α. By application of the nanoparticles, the TNF-α expression was reduced almost to the original level, as shown by qPCR. Thus, calcium phosphate nanoparticles are well suited to reduce inflammatory reactions by silencing the corresponding cytokines, e.g. TNF-α. © The Royal Society of Chemistry 2015.view abstract doi: 10.1039/c5tb01377a 2015 • 417 How electrophoretic deposition with ligand-free platinum nanoparticles affects contact angle
Heinemann, A. and Koenen, S. and Schwabe, K. and Rehbock, C. and Barcikowski, S.
Key Engineering Materials 654 218-223 (2015)Electrophoretic deposition of ligand-free platinum nanoparticles has been studied to elucidate how wettability, indicated by contact angle measurements, is linked to vital parameters of the electrophoretic deposition process. These parameters, namely the colloid concentration, electric field strength and deposition time, have been systematically varied in order to determine their influence on the contact angle. Additionally, scanning electron microscopy has been used to confirm the homogeneity of the achieved coatings. © (2015) Trans Tech Publications, Switzerland.view abstract doi: 10.4028/www.scientific.net/KEM.654.218 2015 • 416 Hybrid biocomposite with a tunable antibacterial activity and bioactivity based on RF magnetron sputter deposited coating and silver nanoparticles
Ivanova, A.A. and Surmenev, R.A. and Surmeneva, M.A. and Mukhametkaliyev, T. and Loza, K. and Prymak, O. and Epple, M.
Applied Surface Science 329 212-218 (2015)In this work, we describe fabrication techniques used to prepare a multifunctional biocomposite based on a hydroxyapatite (HA) coating and silver nanoparticles (AgNPs). AgNPs synthesized by a wet chemical reduction method were deposited on Ti substrates using a dripping/drying method followed by deposition of calcium phosphate (CaP) coating via radio-frequency (RF) magnetron sputter-deposition. The negatively charged silver nanoparticles (zeta potential -21 mV) have a spherical shape with a metallic core diameter of 50 ± 20 nm. The HA coating was deposited as a dense nanocrystalline film over a surface of AgNPs. The RF-magnetron sputter deposition of HA films on the AgNPs layer did not affect the initial content of AgNPs on the substrate surface as well as NPs size and shape. SEM cross-sectional images taken using the backscattering mode revealed a homogeneous layer of AgNPs under the CaP layer. The diffraction patterns from the coatings revealed reflexes of crystalline HA and silver. The concentration of Ag ions released from the biocomposites after 7 days of immersion in phosphate and acetate buffers was estimated. The obtained results revealed that the amount of silver in the solutions was 0.27 ± 0.02 μg mL-1 and 0.54 ± 0.02 μg mL-1 for the phosphate and acetate buffers, respectively, which corresponded well with the minimum inhibitory concentration range known for silver ions in literature. Thus, this work establishes a new route to prepare a biocompatible layer using embedded AgNPs to achieve a local antibacterial effect. © 2015 Elsevier B.V. All rights reserved.view abstract doi: 10.1016/j.apsusc.2014.12.153 2015 • 415 Impact of ambient pressure on titania nanoparticle formation during spray-flame synthesis
Hardt, S. and Wlokas, I. and Schulz, C. and Wiggers, H.
Journal of Nanoscience and Nanotechnology 15 9449-9456 (2015)Nanocrystalline titania was synthesized via liquid-fed spray-flame synthesis in a hermetically closed system at various pressures. Titanium tetraisopropoxide dissolved in isopropanol was used as precursor. The size, crystal structure, degree of agglomeration, morphology and the band gap of the as-prepared particles were investigated ex situ by nitrogen adsorption, transmission electron microscopy, X-ray diffraction, and UV-VIS absorption spectroscopy. In comparison to synthesis at atmospheric pressure it was found that decreasing pressure has a significant influence on the particle size distribution leading to smaller particles with reduced geometric standard deviation while particle morphology and crystal structure are not affected. Computational fluid dynamics simulations support the experimental findings also indicating a significant decrease in particle size at reduced pressure. Although it is well known that decreasing pressure leads to smaller particle sizes, it is (to our knowledge) the first time that this relation was investigated for spray-flame synthesis. Copyright © 2015 American Scientific Publishers All rights reserved.view abstract doi: 10.1166/jnn.2015.10607 2015 • 414 Influence of gold, silver and gold-silver alloy nanoparticles on germ cell function and embryo development
Taylor, U. and Tiedemann, D. and Rehbock, C. and Kues, W.A. and Barcikowski, S. and Rath, D.
Beilstein Journal of Nanotechnology 6 651-664 (2015)The use of engineered nanoparticles has risen exponentially over the last decade. Applications are manifold and include utilisation in industrial goods as well as medical and consumer products. Gold and silver nanoparticles play an important role in the current increase of nanoparticle usage. However, our understanding concerning possible side effects of this increased exposure to particles, which are frequently in the same size regime as medium sized biomolecules and accessorily possess highly active surfaces, is still incomplete. That particularly applies to reproductive aspects, were defects can be passed onto following generations. This review gives a brief overview of the most recent findings concerning reprotoxicological effects. The here presented data elucidate how composition, size and surface modification of nanoparticles influence viablility and functionality of reproduction relevant cells derived from various animal models. While in vitro cultured embryos displayed no toxic effects after the microinjection of gold and silver nanoparticles, sperm fertility parameters deteriorated after co-incubation with ligand free gold nanoparticles. However, the effect could be alleviated by bio-coating the nanoparticles, which even applies to silver and silver-rich alloy nanoparticles. The most sensitive test system appeared to be in vitro oocyte maturation showing a dose-dependent response towards protein (BSA) coated gold-silver alloy and silver nanoparticles leading up to complete arrest of maturation. Recent biodistribution studies confirmed that nanoparticles gain access to the ovaries and also penetrate the blood-testis and placental barrier. Thus, the design of nanoparticles with increased biosafety is highly relevant for biomedical applications. © 2015 Taylor et al.view abstract doi: 10.3762/bjnano.6.66 2015 • 413 Integration of plasmonic Ag nanoparticles as a back reflector in ultra-thin Cu(In,Ga)Se2 solar cells
Yin, G. and Steigert, A. and Andrae, P. and Goebelt, M. and Latzel, M. and Manley, P. and Lauermann, I. and Christiansen, S. and Schmid, M.
Applied Surface Science 355 800-804 (2015)Integration of plasmonic Ag nanoparticles as a back reflector in ultra-thin Cu(In,Ga)Se2 (CIGSe) solar cells is investigated. X-ray photoelectron spectroscopy results show that Ag nanoparticles underneath a Sn:In2O3 back contact could not be thermally passivated even at a low substrate temperature of 440 °C during CIGSe deposition. It is shown that a 50 nm thick Al2O3 film prepared by atomic layer deposition is able to block the diffusion of Ag, clearing the thermal obstacle in utilizing Ag nanoparticles as a back reflector in ultra-thin CIGSe solar cells. Via 3-D finite element optical simulation, it is proved that the Ag nanoparticles show the potential to contribute the effective absorption in CIGSe solar cells. © 2015 Elsevier B.V. All rights reserved.view abstract doi: 10.1016/j.apsusc.2015.07.195 2015 • 412 Iron-doped nickel oxide nanocrystals as highly efficient electrocatalysts for alkaline water splitting
Fominykh, K. and Chernev, P. and Zaharieva, I. and Sicklinger, J. and Stefanic, G. and Döblinger, M. and Müller, A. and Pokharel, A. and Böcklein, S. and Scheu, C. and Bein, T. and Fattakhova-Rohlfing, D.
ACS Nano 9 5180-5188 (2015)Efficient electrochemical water splitting to hydrogen and oxygen is considered a promising technology to overcome our dependency on fossil fuels. Searching for novel catalytic materials for electrochemical oxygen generation is essential for improving the total efficiency of water splitting processes. We report the synthesis, structural characterization, and electrochemical performance in the oxygen evolution reaction of Fe-doped NiO nanocrystals. The facile solvothermal synthesis in tert-butanol leads to the formation of ultrasmall crystalline and highly dispersible Fe<inf>x</inf>Ni<inf>1-x</inf>O nanoparticles with dopant concentrations of up to 20%. The increase in Fe content is accompanied by a decrease in particle size, resulting in nonagglomerated nanocrystals of 1.5-3.8 nm in size. The Fe content and composition of the nanoparticles are determined by X-ray photoelectron spectroscopy and energy-dispersive X-ray spectroscopy measurements, while Mössbauer and extended X-ray absorption fine structure analyses reveal a substitutional incorporation of Fe(III) into the NiO rock salt structure. The excellent dispersibility of the nanoparticles in ethanol allows for the preparation of homogeneous ca. 8 nm thin films with a smooth surface on various substrates. The turnover frequencies (TOF) of these films could be precisely calculated using a quartz crystal microbalance. Fe<inf>0.1</inf>Ni<inf>0.9</inf>O was found to have the highest electrocatalytic water oxidation activity in basic media with a TOF of 1.9 s-1 at the overpotential of 300 mV. The current density of 10 mA cm-2 is reached at an overpotential of 297 mV with a Tafel slope of 37 mV dec-1. The extremely high catalytic activity, facile preparation, and low cost of the single crystalline Fe<inf>x</inf>Ni<inf>1-x</inf>O nanoparticles make them very promising catalysts for the oxygen evolution reaction. © 2015 American Chemical Society.view abstract doi: 10.1021/acsnano.5b00520 2015 • 411 Large scale Molecular Dynamics simulation of microstructure formation during thermal spraying of pure copper
Wang, T. and Begau, C. and Sutmann, G. and Hartmaier, A.
Surface and Coatings Technology 280 72-80 (2015)Thermal spray processes are widely used for the manufacture of advanced coating systems, e.g. metallic coatings for wear and corrosion protection. The desired coating properties are closely related to the microstructure, which is highly influenced by the processing parameters, such as temperature, size and velocity of the sprayed particles. In this paper, large scale Molecular Dynamics simulations are conducted to investigate the microstructure formation mechanisms during the spraying process of hot nano-particles onto a substrate at room temperature using pure copper as a benchmark material representing for a wider class of face-centered-cubic metals. To evaluate the influence of processing parameters on the coating morphology, a number of simulations are performed in which the initial temperature, size and velocity of copper particles are systematically varied in order to investigate the thermal and microstructural evolution during impaction. Two distinct types of microstructural formation mechanisms, resulting in different coating morphologies, are observed in the present investigation, which are either governed by plastic deformation or by the process of melting and subsequent solidification. Furthermore, a thermodynamically motivated model as a function of the particle temperature and velocity is developed, which predicts the microstructural mechanisms observed in the simulations. The results provide an elementary insight into the microstructure formation mechanisms on an atomistic scale, which can serve as basic input for continuum modeling of thermal spray process. © 2015 Published by Elsevier B.V.view abstract doi: 10.1016/j.surfcoat.2015.08.034 2015 • 410 Laser-based in situ measurement and simulation of gas-phase temperature and iron atom concentration in a pilot-plant nanoparticle synthesis reactor
Feroughi, O.M. and Hardt, S. and Wlokas, I. and Hülser, T. and Wiggers, H. and Dreier, T. and Schulz, C.
Proceedings of the Combustion Institute 35 2299-2306 (2015)A scaled-up flame reactor for nanoparticle synthesis was investigated through a combination of in-situ laser-induced fluorescence (LIF) measurements and computational fluid dynamics (CFD) simulations with detailed chemistry. Multi-line NO-LIF was used for imaging gas-temperature and Fe-LIF for measurement of iron atom concentration. Despite the challenging environment of production reactors in an industrial environment, various conditions for stable flames with different gas flows with and without adding Fe(CO)5 as precursor for the synthesis of iron-oxide nanoparticles were investigated. In contrast to previous measurements in laminar lab-scale flames, a second mechanism for forming iron oxide nanoparticles was found via intermediate formation of iron clusters and elemental iron particles in hot, oxygen-free gas streams followed by subsequent oxidation. © 2014 Published by Elsevier Inc. on behalf of The Combustion Institute.view abstract doi: 10.1016/j.proci.2014.05.039 2015 • 409 Laser-induced incandescence: Particulate diagnostics for combustion, atmospheric, and industrial applications
Michelsen, H.A. and Schulz, C. and Smallwood, G.J. and Will, S.
Progress in Energy and Combustion Science 51 2-48 (2015)The understanding of soot formation in combustion processes and the optimization of practical combustion systems require in situ measurement techniques that can provide important characteristics, such as particle concentrations and sizes, under a variety of conditions. Of equal importance are techniques suitable for characterizing soot particles produced from incomplete combustion and emitted into the environment. Additionally, the production of engineered nanoparticles, such as carbon blacks, may benefit from techniques that allow for online monitoring of these processes. In this paper, we review the fundamentals and applications of laser-induced incandescence (LII) for particulate diagnostics in a variety of fields. The review takes into account two variants of LII, one that is based on pulsed-laser excitation and has been mainly used in combustion diagnostics and emissions measurements, and an alternate approach that relies on continuous-wave lasers and has become increasingly popular for measuring black carbon in environmental applications. We also review the state of the art in the determination of physical parameters central to the processes that contribute to the non-equilibrium nanoscale heat and mass balances of laser-heated particles; these parameters are important for LII-signal analysis and simulation. Awareness of the significance of particle aggregation and coatings has increased recently, and the effects of these characteristics on the LII technique are discussed. Because of the range of experimental constraints in the variety of applications for which laser-induced incandescence is suited, many implementation approaches have been developed. This review discusses considerations for selection of laser and detection characteristics to address application-specific needs. The benefits of using LII for measurements of a range of nanoparticles in the fields mentioned above are demonstrated with some typical examples, covering simple flames, internal-combustion engines, exhaust emissions, the ambient atmosphere, and nanoparticle production. We also remark on less well-known studies employing LII for particles suspended in liquids. An important aspect of the paper is to critically assess the improvement in the understanding of the fundamental physical mechanisms at the nanoscale and the determination of underlying parameters; we also identify further research needs in these contexts. Building on this enhanced capability in describing the underlying complex processes, LII has become a workhorse of particulate measurement in a variety of fields, and its utility continues to be expanding. When coupled with complementary methods, such as light scattering, probe-sampling, molecular-beam techniques, and other nanoparticle instrumentation, new directions for research and applications with LII continue to materialize. © 2015 Published by Elsevier Ltd.view abstract doi: 10.1016/j.pecs.2015.07.001 2015 • 408 Ligand-free Gold Nanoparticles as a Reference Material for Kinetic Modelling of Catalytic Reduction of 4-Nitrophenol
Gu, S. and Kaiser, J. and Marzun, G. and Ott, A. and Lu, Y. and Ballauff, M. and Zaccone, A. and Barcikowski, S. and Wagener, P.
Catalysis Letters 145 1105-1112 (2015)The reduction of 4-nitrophenol by sodium borohydride is a common model reaction to test the catalytic activity of metal nanoparticles. As all reaction steps proceed solely on the surface of the metal nanoparticles (Langmuir-Hinshelwood model), ligand-coverage of metal nanoparticles impedes the merging of theory and experiment. Therefore we analyzed the catalytic activity of bare gold nanoparticles prepared by laser ablation in liquid without any stabilizers or ligands. The catalytic reaction is characterized by a full kinetic analysis including 4-hydroxylaminophenol as an intermediate species. Excellent agreement between theory and experiment is found. Moreover, the suspension of the nanoparticles remains stable. Hence, ligand-free nanoparticles can be used as a reference material for mechanistic studies of catalytic reactions. In addition, the analysis shows that gold nanoparticles synthesized by laser ablation are among the most active catalysts for this reaction. (Graph Presented). © 2015 Springer Science+Business Media.view abstract doi: 10.1007/s10562-015-1514-7 2015 • 407 Light Coupling and Trapping in Ultrathin Cu(In,Ga)Se2 Solar Cells Using Dielectric Scattering Patterns
Van Lare, C. and Yin, G. and Polman, A. and Schmid, M.
ACS Nano 9 9603-9613 (2015)We experimentally demonstrate photocurrent enhancement in ultrathin Cu(In,Ga)Se2 (CIGSe) solar cells with absorber layers of 460 nm by nanoscale dielectric light scattering patterns printed by substrate conformal imprint lithography. We show that patterning the front side of the device with TiO2 nanoparticle arrays results in a small photocurrent enhancement in almost the entire 400-1200 nm spectral range due to enhanced light coupling into the cell. Three-dimensional finite-difference time-domain simulations are in good agreement with external quantum efficiency measurements. Patterning the Mo/CIGSe back interface using SiO2 nanoparticles leads to strongly enhanced light trapping, increasing the efficiency from 11.1% for a flat to 12.3% for a patterned cell. Simulations show that optimizing the array geometry could further improve light trapping. Including nanoparticles at the Mo/CIGSe interface leads to substantially reduced parasitic absorption in the Mo back contact. Parasitic absorption in the back contact can be further reduced by fabricating CIGSe cells on top of a SiO2-patterned In2O3:Sn (ITO) back contact. Simulations show that these semitransparent cells have similar spectrally averaged reflection and absorption in the CIGSe active layer as a Mo-based patterned cell, demonstrating that the absorption losses in the Mo can be partially turned into transmission through the semitransparent geometry. © 2015 American Chemical Society.view abstract doi: 10.1021/acsnano.5b04091 2015 • 406 Light Induced H2 Evolution from a Biophotocathode Based on Photosystem 1 - Pt Nanoparticles Complexes Integrated in Solvated Redox Polymers Films
Zhao, F. and Conzuelo, F. and Hartmann, V. and Li, H. and Nowaczyk, M.M. and Plumeré, N. and Rögner, M. and Schuhmann, W.
Journal of Physical Chemistry B 119 13726-13731 (2015)We report on a biophotocathode based on photosystem 1 (PS1)-Pt nanoparticle complexes integrated in a redox hydrogel for photoelectrocatalytic H2 evolution at low overpotential. A poly(vinyl)imidazole Os(bispyridine)2Cl polymer serves as conducting matrix to shuttle the electrons from the electrode to the PS1-Pt complexes embedded within the hydrogel. Light induced charge separation at the PS1-Pt complexes results in the generation of photocurrents (4.8 ± 0.4 μA cm-2) when the biophotocathodes are exposed to anaerobic buffer solutions. Under these conditions, the protons are the sole possible electron acceptors, suggesting that the photocurrent generation is associated with H2 evolution. Direct evidence for the latter process is provided by monitoring the H2 production with a Pt microelectrode in scanning electrochemical microscopy configuration over the redox hydrogel film containing the PS1-Pt complexes under illumination. © 2015 American Chemical Society.view abstract doi: 10.1021/acs.jpcb.5b03511 2015 • 405 Magneto-responsive alginate capsules
Degen, P. and Zwar, E. and Schulz, I. and Rehage, H.
Journal of Physics Condensed Matter 27 (2015)Upon incorporation of magnetic nanoparticles (mNPs) into gels, composite materials called ferrogels are obtained. These magneto-responsive systems have a wide range of potential applications including switches and sensors as well as drug delivery systems. In this article, we focus on the properties of calcium alginate capsules, which are widely used as carrier systems in medicine and technology. We studied the incorporation of different kinds of mNPs in matrix capsules and in the core and the shell of hollow particles. We found out that not all particle-alginate or particle-CaCl<inf>2</inf> solution combinations were suitable for a successful capsule preparation on grounds of a destabilization of the nanoparticles or the polymer. For those systems allowing the preparation of switchable beads or capsules, we systematically studied the size and microscopic structure of the capsules, their magnetic behavior and mechanical resistance. © 2015 IOP Publishing Ltd.view abstract doi: 10.1088/0953-8984/27/19/194105 2015 • 404 Mapping near-field plasmonic interactions of silver particles with scanning near-field optical microscopy measurements
Andrae, P. and Song, M. and Haggui, M. and Fumagalli, P. and Schmid, M.
Proceedings of SPIE - The International Society for Optical Engineering 9547 (2015)A scanning near-field optical microscope (SNOM) is a powerful tool to investigate optical effects that are smaller than Abbe's limit. Its greatest strength is the simultaneous measurement of high-resolution topography and optical nearfield data that can be correlated to each other. However, the resolution of an aperture SNOM is always limited by the probe. It is a technical challenge to fabricate small illumination tips with a well-defined aperture and high transmission. The aperture size and the coating homogeneity will define the optical resolution and the optical image whereas the tip size and shape influence the topographic accuracy. Although the technique has been developing for many years, the correlation between simulated near-field data and measurement is still not convincing. To overcome this challenge, the mapping of near-field plasmonic interactions of silver nanoparticles is investigated. Different nanocluster samples with diverse distributions of silver particles are characterized via SNOM in illumination and collection mode. This will lead to topographical and optical images that can be used as an input for SNOM simulations with the aim of estimating optical artifacts. Including tip, particles, and substrate, our finite-elementmethod (FEM) simulations are based on the realistic geometry. Correlating the high-precision SNOM measurement and the detailed simulation of a full image scan will enable us to draw conclusions regarding near-field enhancements caused by interacting particles. © 2015 SPIE.view abstract doi: 10.1117/12.2187358 2015 • 403 Measurements of nanoscale TiO2 and Al2O3 in industrial workplace environments – Methodology and results
Kaminski, H. and Beyer, M. and Fissan, H. and Asbach, C. and Kuhlbusch, T.A.J.
Aerosol and Air Quality Research 15 129-141 (2015)The possible release of engineered nanomaterials was investigated based on a previously developed but now refined methodology. Data from altogether eight industrial work areas in production plants of nanostructured TiO2 and Al2O3 particles were obtained and used to test the methodology and to derive a first assessment of possible exposure of workers. Particle size distributions were determined in work area environments with concurrent measurements at a comparison site. Data from the comparison site were used to estimate the particle background level in the work area and distinguish it from potentially released nanomaterial. The analysis is based on the comparison of time resolved data from the work area and the comparison site as well as data determined during periods with and without work activities in the work area. The data analysis method introduced delivers size-resolved information on the potential nanoparticle exposure of workers. A significant release of particles in the size range 100–562 nm was observed in the work area of bagging aluminum oxide and is stemming from damaging or overfilling of bags, and the necessary activities during the cleaning of the work area. The maximum particle diameter of these particles was around 340 nm. At all other investigated locations no significant releases of particles in the size range 100–562 nm were determined. Also, no significant release of particles < 100 nm was observed in all work areas. The average PM10 exposure during the work activities varied from 48 to 1,330 µg/m3 in the different work areas. The maximum concentrations of aluminum were 118 µg/m3 and 58 µg/m3 for PM10 and PM1, respectively, during the bagging of Al2O3 in small bags. In comparison, the maximum concentrations of titanium were 550 µg/m3 and 434 µg/m3 for PM10 and PM1, respectively, during the bagging of TiO2 and indicate a significant release of coarser particles. © Taiwan Association for Aerosol Research.view abstract doi: 10.4209/aaqr.2014.03.0065 2015 • 402 Mesoporous Silica Supported Au and AuCu Nanoparticles for Surface Plasmon Driven Glycerol Oxidation
Schünemann, S. and Dodekatos, G. and Tüysüz, H.
Chemistry of Materials 27 7743-7750 (2015)Herein, we report for the first time the visible-light-assisted rate enhancement for glycerol oxidation using direct plasmonic photocatalysis. Au nanoparticles were loaded on various mesoporous SiO2 supports, and the catalytic performance was investigated with and without visible-light illumination. Monodispersed mesoporous silica spheres loaded with Au nanoparticles demonstrated a superior photoassisted catalytic rate enhancement compared to Au loaded ordered mesoporous silica (SBA-15, KIT-6, and MCM-41). The enhancement is attributed to the particle size of the Au nanoparticles and better light interaction resulting from the small SiO2 domains. Au loaded monodispersed mesoporous silica spheres exhibit a constant and remarkably small particle diameter of 2 nm at Au loadings of up to 15 wt % as a result of the support's small domain size and efficient pore confinement. The performance of the Au catalyst could be further improved by preparing bimetallic AuCu nanoparticles. Synergistic effects between Au and Cu improved the glycerol conversion by a factor of 2.5 and the dihydroxyacetone selectivity from 80% to 90% compared to monometallic Au catalysts. © 2015 American Chemical Society.view abstract doi: 10.1021/acs.chemmater.5b03520 2015 • 401 Metal-halide Nanoparticle Formation: Electrolytic and Chemical Synthesis of Mercury(I) Chloride Nanoparticles
Bartlett, T.R. and Batchelor-Mcauley, C. and Tschulik, K. and Jurkschat, K. and Compton, R.G.
ChemElectroChem 2 522-528 (2015)Mercury(I) chloride (Hg<inf>2</inf>Cl<inf>2</inf>) nanoparticles (NPs) are synthesised for the first time by using two different techniques. First, particles are formed by implosion of a calomel nanolayer, induced by partial electrolysis at a mercury hemisphere microelectrode. The resulting NPs are then characterised by the nanoimpact method, demonstrating the first time metal chloride NPs have been sized by this technique and showing the ability to form and study NPs insitu. Second, Hg<inf>2</inf>Cl<inf>2</inf> NPs are synthesised by using the precipitation reaction of Hg<inf>2</inf>(NO<inf>3</inf>)<inf>2</inf> with KCl. The NPs are characterised on both mercury and carbon microelectrodes and their size is found to agree with TEM results. Sizable studies: Mercury(I) chloride (Hg<inf>2</inf>Cl<inf>2</inf>) nanoparticles (NPs) are synthesised for the first time by using two different techniques. First, particles are formed by implosion of a calomel nanolayer, induced by partial electrolysis at a mercury hemisphere microelectrode. Second, Hg<inf>2</inf>Cl<inf>2</inf> NPs are synthesised by the precipitation reaction between Hg<inf>2</inf>(NO<inf>3</inf>)<inf>2</inf> and KCl. The NPs are characterised on both mercury and carbon microelectrodes by using the nanoimpact method and their size is found to agree with TEM results. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/celc.201402401 2015 • 400 Microwave plasma synthesis of Si/Ge and Si/WSi2 nanoparticles for thermoelectric applications
Petermann, N. and Schneider, T. and Stötzel, J. and Stein, N. and Weise, C. and Wlokas, I. and Schierning, G. and Wiggers, H.
Journal of Physics D: Applied Physics 48 (2015)The utilization of microwave-based plasma systems enables a contamination-free synthesis of highly specific nanoparticles in the gas phase. A reactor setup allowing stable, long-term operation was developed with the support of computational fluid dynamics. This paper highlights the prospects of gas-phase plasma synthesis to produce specific materials for bulk thermoelectrics. Taking advantage of specific plasma reactor properties such as Coulomb repulsion in combination with gas temperatures considerably higher than 1000 K, spherical and non-aggregated nanoparticles of multiple compositions are accessible. Different strategies towards various nanostructured composites and alloys are discussed. It is shown that, based on doped silicon/germanium alloys and composites, thermoelectric materials with zT values up to almost unity can be synthesized in one step. First experimental results concerning silicon/tungsten silicide thermoelectrics applying the nanoparticle-in-alloy idea are presented indicating that this concept might work. However, it is found that tungsten silicides show a surprising sinter activity more than 1000 K below their melting temperature. © 2015 IOP Publishing Ltd.view abstract doi: 10.1088/0022-3727/48/31/314010 2015 • 399 miR-542-3p exerts tumor suppressive functions in neuroblastoma by downregulating survivin
Althoff, K. and Lindner, S. and Odersky, A. and Mestdagh, P. and Beckers, A. and Karczewski, S. and Molenaar, J.J. and Bohrer, A. and Knauer, S. and Speleman, F. and Epple, M. and Kozlova, D. and Yoon, S. and Baek, K. and Vandesom...
International Journal of Cancer 136 1308-1320 (2015)MicroRNAs (miRNAs) are deregulated in a variety of human cancers, including neuroblastoma, the most common extracranial tumor of childhood. We previously reported a signature of 42 miRNAs to be highly predictive of neuroblastoma outcome. One miRNA in this signature, miR-542, was downregulated in tumors from patients with adverse outcome. Reanalysis of quantitative PCR and next-generation sequencing transcript data revealed that miR-542-5p as well as miR-542-3p expression is inversely correlated with poor prognosis in neuroblastoma patients. We, therefore, analyzed the function of miR-542 in neuroblastoma tumor biology. Ectopic expression of miR-542-3p in neuroblastoma cell lines reduced cell viability and proliferation, induced apoptosis and downregulated Survivin. Survivin expression was also inversely correlated with miR-542-3p expression in primary neuroblastomas. Reporter assays confirmed that miR-542-3p directly targeted Survivin. Downregulating Survivin using siRNA copied the phenotype of miR-542-3p expression in neuroblastoma cell lines, while cDNA-mediated ectopic expression of Survivin partially rescued the phenotype induced by miR-542-3p expression. Treating nude mice bearing neuroblastoma xenografts with miR-542-3p-loaded nanoparticles repressed Survivin expression, decreased cell proliferation and induced apoptosis in the respective xenograft tumors. We conclude that miR-542-3p exerts its tumor suppressive function in neuroblastoma, at least in part, by targeting Survivin. Expression of miR-542-3p could be a promising therapeutic strategy for treating aggressive neuroblastoma. © 2014 UICC.view abstract doi: 10.1002/ijc.29091 2015 • 398 Multifunctional calcium phosphate nanoparticles for combining near-infrared fluorescence imaging and photodynamic therapy
Haedicke, K. and Kozlova, D. and Gräfe, S. and Teichgräber, U. and Epple, M. and Hilger, I.
Acta Biomaterialia 14 197-207 (2015)Photodynamic therapy (PDT) of tumors causes skin photosensitivity as a result of unspecific accumulation behavior of the photosensitizers. PDT of tumors was improved by calcium phosphate nanoparticles conjugated with (i) Temoporfin as a photosensitizer, (ii) the RGDfK peptide for favored tumor targeting and (iii) the fluorescent dye molecule DY682-NHS for enabling near-infrared fluorescence (NIRF) optical imaging in vivo. The nanoparticles were characterized with regard to size, spectroscopic properties and uptake into CAL-27 cells. The nanoparticles had a hydrodynamic diameter of approximately 200 nm and a zeta potential of around +22 mV. Their biodistribution at 24 h after injection was investigated via NIRF optical imaging. After treating tumor-bearing CAL-27 mice with nanoparticle-PDT, the therapeutic efficacy was assessed by a fluorescent DY-734-annexin V probe at 2 days and 2 weeks after treatment to detect apoptosis. Additionally, the contrast agent IRDye® 800CW RGD was used to assess tumor vascularization (up to 4 weeks after PDT). After nanoparticle-PDT in mice, apoptosis in the tumor was detected after 2 days. Decreases in tumor vascularization and tumor volume were detected in the next few days. Calcium phosphate nanoparticles can be used as multifunctional tools for NIRF optical imaging, PDT and tumor targeting as they exhibited a high therapeutic efficacy, being capable of inducing apoptosis and destroying tumor vascularization. © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.view abstract doi: 10.1016/j.actbio.2014.12.009 2015 • 397 Nano- And microlenses as concepts for enhanced performance of solar cells
Schmid, M. and Manley, P.
Journal of Photonics for Energy 5 (2015)Both metallic nanoparticles exhibiting plasmonic effects and dielectric nanoparticles coupling the light into resonant modes have shown successful applications to photovoltaics. On a larger scale, microconcentrator optics promise to enhance solar cell efficiency and to reduce material consumption. Here, we want to create a link between the concentrators on the nano- and on the microscale. From metallic nanospheres, we turn to dielectric ones and then look at increasing radii to approach the microscale. The lenses are investigated with respect to their interaction with light using three-dimensional simulations with the finite-element method. Resulting maps of local electric field distributions reveal the focusing behavior of the dielectric spheres. For larger lens sizes, ray tracing calculations, which give ray distributions in agreement with electric field intensities, can be applied. Calculations of back focal lengths in geometrical optics coincide with ray tracing results and allow insight into how the focal length can be tuned as a function of particle size, substrate refractive index, and the shape of the microlens. Despite the similarities we find for the nano- and the microlenses, integration into solar cells needs to be carefully adjusted, depending on the goals of material saving, concentration level, focal distance, and lens size. © 2015 Society of Photo-Optical Instrumentation Engineers (SPIE).view abstract doi: 10.1117/1.JPE.5.057003 2015 • 396 Nano-optical concept design for light management
Schmid, M. and Tsakanikas, S. and Mangalgiri, G. and Andrae, P. and Song, M. and Yin, G. and Riedel, W. and Manley, P.
Proceedings of SPIE - The International Society for Optical Engineering 9626 (2015)Efficient light management in optoelectronic devices requires nanosystems where high optical qualities coincide with suitable device integration. The requirement of chemical and electrical passivation for integrating nanostrutures in e.g.Thin film solar cells points towards the use of insulating and stable dielectric material, which however has to provide high scattering and near-fields as well. We investigate metal@dielectric core-shell nanoparticles and dielectric nanorods. Whereas core-shell nanoparticles can be simulated using Mie theory, nanorods of finite length are studied with the finite element method. We reveal that a metallic core within a thin dielectric shell can help to enhance scattering and near-field cross sections compared to a bare dielectric nanoparticle of the same radius. A dielectric nanorod has the benefit over a dielectric nanosphere in that it can generate much higher scattering cross sections and also give rise to a high near-field enhancement along its whole length. Electrical benefits of e.g. Ag@oxide nanoparticles in thin-film solar cells and ZnO nanorods in hybrid devices lie in reduction of recombination centers or close contact of the nanorod material with the surrounding organics, respectively. The optical benefit of dielectric shell material and elongated dielectric nanostructures is highlighted in this paper. © COPYRIGHT SPIE. Downloading of the abstract is permitted for personal use only.view abstract doi: 10.1117/12.2191081 2015 • 395 Nanocellulose-Templated Porous Titania Scaffolds Incorporating Presynthesized Titania Nanocrystals
Ivanova, A. and Fravventura, M.C. and Fattakhova-Rohlfing, D. and Rathouský, J. and Movsesyan, L. and Ganter, P. and Savenije, T.J. and Bein, T.
Chemistry of Materials 27 6205-6212 (2015)Nanocrystalline cellulose (NCC) is an abundant biogenic nanomaterial with unique properties that enables the efficient synthesis of mesoporous crystalline titania. We significantly enhance the photocatalytic activity of titania thin films by introducing solvothermally synthesized preformed anatase nanoparticles into a sol-gel based biotemplated titania scaffold. The resulting dual source titania thin films containing different amounts of preformed crystalline species were investigated by time-resolved microwave conductivity (TRMC) measurements and tested in the photocatalytic conversion of 4-chlorophenol. The gradual addition of preformed nanoparticles leads to a consistent increase of the mean size of titania crystalline domains, whereas the porosity of the composite is well-preserved due to the shape-persistent nature of the NCC template. Microwave conductivity studies establish increased photoconductivity of the films containing preformed anatase nanoparticles in comparison to that of films made without the nanoparticles. The synergistic features of the dual source titania, namely the improved crystalline properties brought by the preformed nanocrystals in combination with the high surface area provided by the NCC-templated sol-gel titania, result in a very high photocatalytic activity of the films in the photocatalytic decomposition of 4-chlorophenol. In quantitative terms, the dual source titania films prepared with 75% nanoparticles exhibit a first order degradation rate constant of 0.53 h-1 (1.47 × 10-4 sec-1), which strongly outperforms the activity of commercial P90 nanopowder showing a rate constant of 0.17 h-1 (0.47 × 10-4 sec-1) under the same conditions. © 2015 American Chemical Society.view abstract doi: 10.1021/acs.chemmater.5b00770 2015 • 394 Nanoparticle Capping Agent Dynamics and Electron Transfer: Polymer-Gated Oxidation of Silver Nanoparticles
Tanner, E.E.L. and Tschulik, K. and Tahany, R. and Jurkschat, K. and Batchelor-McAuley, C. and Compton, R.G.
Journal of Physical Chemistry C 119 18808-18815 (2015)Capping agent-controlled stability of nanoparticles tailors them for different applications, but the associated particle-solvent dynamics are poorly understood. Herein, previously unseen capping agent-gated nanoparticle redox activity is observed for poly(ethylene glycol)-coated silver nanoparticles. This is revealed by stochastic nanoparticle stripping, probing one individual nanoparticle at a time, from an ensemble of surface-immobilized nanoparticles. Thus, new and previously inaccessible understanding is gained on the crucial role of capping agent dynamics on nanoparticle reactivity. © 2015 American Chemical Society.view abstract doi: 10.1021/acs.jpcc.5b05789 2015 • 393 Nanostructure of wet-chemically prepared, polymer-stabilized silver-gold nanoalloys (6 nm) over the entire composition range
Ristig, S. and Prymak, O. and Loza, K. and Gocyla, M. and Meyer-Zaika, W. and Heggen, M. and Raabe, D. and Epple, M.
Journal of Materials Chemistry B 3 4654-4662 (2015)Bimetallic silver-gold nanoparticles were prepared by co-reduction using citrate and tannic acid in aqueous solution and colloidally stabilized with poly(N-vinylpyrrolidone) (PVP). The full composition range of silver:gold from 0:100 to 100:0 (n:n) was prepared with steps of 10 mol%. The nanoparticles were spherical, monodispersed, and had a diameter of ∼6 nm, except for Ag:Au 90:10 nanoparticles and pure Ag nanoparticles which were slightly larger. The size of the nanoalloys was determined by differential centrifugal sedimentation (DCS) and transmission electron microscopy (TEM). By means of X-ray powder diffraction (XRD) together with Rietveld refinement, precise lattice parameters, crystallite size and microstrain were determined. Scanning transmission electron microscopy (STEM) combined with energy-dispersive X-ray spectroscopy (EDX) and electron energy loss spectroscopy (EELS) showed that the particles consisted of a gold-rich core and a silver-rich shell. XRD and DCS indicated that the nanoparticles were not twinned, except for pure Ag and Ag:Au 90:10, although different domains were visible in the TEM. A remarkable negative deviation from Vegard's linear rule of alloy mixtures was observed (isotropic contraction of the cubic unit cell with a minimum at a 50:50 composition). This effect was also found for Ag:Au bulk alloys, but it was much more pronounced for the nanoalloys. Notably, it was much less pronounced for pure silver and gold nanoparticles. The microstrain was increased along with the contraction of the unit cell with a broad maximum at a 50:50 composition. The synthesis is based on aqueous solvents and can be easily scaled up to a yield of several mg of a well dispersed nanoalloy with application potential due to its tuneable antibacterial action (silver) and its optical properties for bioimaging. © The Royal Society of Chemistry 2015.view abstract doi: 10.1039/c5tb00644a 2015 • 392 New approaches to nanoparticle sample fabrication for atom probe tomography
Felfer, P. and Li, T. and Eder, K. and Galinski, H. and Magyar, A.P. and Bell, D.C. and Smith, G.D.W. and Kruse, N. and Ringer, S.P. and Cairney, J.M.
Ultramicroscopy 159 413-419 (2015)Due to their unique properties, nano-sized materials such as nanoparticles and nanowires are receiving considerable attention. However, little data is available about their chemical makeup at the atomic scale, especially in three dimensions (3D). Atom probe tomography is able to answer many important questions about these materials if the challenge of producing a suitable sample can be overcome. In order to achieve this, the nanomaterial needs to be positioned within the end of a tip and fixed there so the sample possesses sufficient structural integrity for analysis. Here we provide a detailed description of various techniques that have been used to position nanoparticles on substrates for atom probe analysis. In some of the approaches, this is combined with deposition techniques to incorporate the particles into a solid matrix, and focused ion beam processing is then used to fabricate atom probe samples from this composite. Using these approaches, data has been achieved from 10-20 nm core-shell nanoparticles that were extracted directly from suspension (i.e. with no chemical modification) with a resolution of better than ±1 nm. © 2015 Elsevier B.V..view abstract doi: 10.1016/j.ultramic.2015.04.014 2015 • 391 New possibilities of accurate particle characterisation by applying direct boundary models to analytical centrifugation
Walter, J. and Thajudeen, T. and Süß, S. and Segets, D. and Peukert, W.
Nanoscale 7 6574-6587 (2015)Analytical centrifugation (AC) is a powerful technique for the characterisation of nanoparticles in colloidal systems. As a direct and absolute technique it requires no calibration or measurements of standards. Moreover, it offers simple experimental design and handling, high sample throughput as well as moderate investment costs. However, the full potential of AC for nanoparticle size analysis requires the development of powerful data analysis techniques. In this study we show how the application of direct boundary models to AC data opens up new possibilities in particle characterisation. An accurate analysis method, successfully applied to sedimentation data obtained by analytical ultracentrifugation (AUC) in the past, was used for the first time in analysing AC data. Unlike traditional data evaluation routines for AC using a designated number of radial positions or scans, direct boundary models consider the complete sedimentation boundary, which results in significantly better statistics. We demonstrate that meniscus fitting, as well as the correction of radius and time invariant noise significantly improves the signal-to-noise ratio and prevents the occurrence of false positives due to optical artefacts. Moreover, hydrodynamic non-ideality can be assessed by the residuals obtained from the analysis. The sedimentation coefficient distributions obtained by AC are in excellent agreement with the results from AUC. Brownian dynamics simulations were used to generate numerical sedimentation data to study the influence of diffusion on the obtained distributions. Our approach is further validated using polystyrene and silica nanoparticles. In particular, we demonstrate the strength of AC for analysing multimodal distributions by means of gold nanoparticles. This journal is © The Royal Society of Chemistry.view abstract doi: 10.1039/c5nr00995b 2015 • 390 Non-Invasive Probing of Nanoparticle Electrostatics
Tschulik, K. and Cheng, W. and Batchelor-Mcauley, C. and Murphy, S. and Omanović, D. and Compton, R.G.
ChemElectroChem 2 112-118 (2015)Electrostatic interactions between surface-charged nanoparticles (NPs) and electrodes studied using existing techniques unavoidably and significantly alter the system being analyzed. Here we present a methodology that allows the probing of unperturbed electrostatic interactions between individual NPs and charged surfaces. The uniqueness of this approach is that stochastic NP impact events are used as the probe. During a single impact, only an attomole of the redox species reacts and is released at the interface during each sensing event. As an example, the effect of electrostatic screening on the reduction of negatively charged indigo NPs at a mercury microelectrode is explored at potentials positive and negative of the potential of zero charge. At suitable overpotentials fully driven electron transfer is seen for all but very low (<0.005M) ionic strengths. The loss of charge transfer in such dilute electrolytes is unambiguously shown to arise from a reduced driving force for the reaction rather than a reduced population of NPs near the electrode, contradicting popular perceptions. Electrostatics were found not to significantly affect the reactivity of the studied NPs. Importantly, the presented technique is general and can be applied to a wide variety of NPs, including metals, metal oxides and organic compounds. Not what you might think: A new and non-invasive technique to probe the electrostatic interaction between surface-charged nanoparticles and a charged metal/solution interface shows that electrostatic effects are insignificant in all but very dilute electrolytes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/celc.201402285 2015 • 389 NOx conversion properties of a novel material: Iron nanoparticles stabilized in carbon
Busch, M. and Kompch, A. and Suleiman, S. and Notthoff, C. and Bergmann, U. and Theissmann, R. and Atakan, B. and Winterer, M.
Applied Catalysis B: Environmental 166-167 211-216 (2015)Nitrogen oxides (NOx) belong to the most common pollutants from combustion processes and are a major threat to human health. Carbon-based catalysts exhibit strong advantages for NOx removal like low-toxic application and easy handling. However, gasification of the carbon matrix at elevated temperatures is still one of the greatest concerns. Hence, we have directed our focus on especially low temperature NOx-removal using a novel material, iron nanoparticles stabilized in a carbon matrix (nano-Fe/C). The investigations included NO2 uptake properties and catalytic conversion of NO2 in recycle flow at 425K and 328K, scanning transmission electron microscopy and 77K-N2-adsorption. Nano-Fe/C exhibits superior NOx-removal properties compared with untreated or iron-infiltrated activated carbon or magnetite reference catalysts. No severe catalyst deactivation or catalyst aging at 425K is observed. Even at 328K nano-Fe/C still exhibits NO2-conversion, although without converting the product NO. NO2 adsorption at 297K is suggested to occur in three stages with different kinetics: (1) NO2 adsorption and reduction to NO, (2) physisorption on the oxidized catalyst surface and (3) saturation of the catalyst and diffusion into the substrate matrix. At 425K, NO2 is quickly reduced to NO and the resulting NO is further converted to N2O. After complete consumption of NO, the residual NO2 is also converted to N2O. A possible reaction mechanism is suggested based on the conversion kinetics. © 2014 Published by Elsevier B.V.view abstract doi: 10.1016/j.apcatb.2014.11.013 2015 • 388 Numerical investigation of the process steps in a spray flame reactor for nanoparticle synthesis
Weise, C. and Menser, J. and Kaiser, S.A. and Kempf, A. and Wlokas, I.
Proceedings of the Combustion Institute 35 2259-2266 (2015)The synthesis of titanium dioxide nanoparticles from titanium tetraisopropoxide (TTIP) in a nanoparticle spray flame reactor was investigated. The nanoparticle properties are affected by different processes: (a) the break-up of the liquid jet from the spray nozzle, (b) the combustion of the spray and in the pilot flame and (c) the formation and growth of the nanoparticles. The spray process of the injected liquid was analyzed by volume of fluid (VOF) calculations and validated by shadowgraphy imaging which provided the size distribution and the mean velocity of the droplets. The spray angle was determined by a side illuminated long exposure image of the spray. The resulting spray properties (droplet sizes, velocity, and spray angle) served as injector boundary conditions for the downstream combustion simulations. Spray and gas phase of the flame were simulated using an Euler-Lagrange approach, turbulence was modeled by the RNG k-epsilon model, and turbulent combustion was described as a partially stirred reactor (PaSR). For the formation and growth of the nanoparticles within the synthesis reactor, the population balance equation was solved coupled to the spray combustion using a monodisperse model. The findings from experiment and simulation are discussed in terms of flow, species, temperature, and nanoparticle formation inside the reactor. The effect of the spray droplet properties as droplet size, angle, mean velocity and the dispersion behavior on the nanoparticle synthesis process are investigated and discussed, confirming the observation that this type of spray reactor is a robust design overall. © 2014 Published by Elsevier Inc. on behalf of The Combustion Institute.view abstract doi: 10.1016/j.proci.2014.05.037 2015 • 387 On the mechanism of nanoparticle formation in a flame doped by iron pentacarbonyl
Poliak, M. and Fomin, A. and Tsionsky, V. and Cheskis, S. and Wlokas, I. and Rahinov, I.
Physical Chemistry Chemical Physics 17 680-685 (2015)In this work we have investigated the mechanism of nanoparticle synthesis in a low pressure, premixed, laminar flat flame of CH4-O2, doped with iron pentacarbonyl using a combined quartz-crystal-microbalance-particle-mass-spectrometry apparatus. We have unambiguously demonstrated that the formation of nanoparticles in iron pentacarbonyl-doped flames occurs very early, in close proximity to the burner surface, prior to the flame front. This early rise of nanoparticle mass concentration is followed by a sharp drop in nanoparticle concentration at the high temperature flame front. This "prompt" nanoparticle generation is consistent with kinetic models describing iron cluster formation. The observation of this phenomenon in a quasi-one-dimensional premixed flat flame strengthens our previous findings and points out that the "prompt" nanoparticle formation is a general phenomenon, not limited to diffusion flames. It presents a challenge and a trigger for further development of the existing mechanisms for gas phase synthesis of iron oxide particles in flames. This journal is © the Owner Societies 2015.view abstract doi: 10.1039/c4cp04454a 2015 • 386 Particle-induced cell migration assay (PICMA): A new in vitro assay for inflammatory particle effects based on permanent cell lines
Westphal, G.A. and Schremmer, I. and Rostek, A. and Loza, K. and Rosenkranz, N. and Brüning, T. and Epple, M. and Bünger, J.
Toxicology in Vitro 29 997-1005 (2015)Inflammation is a decisive pathophysiologic mechanism of particle toxicity and accumulation of neutrophils in the lung is believed to be a crucial step in this process. This study describes an in vitro model for investigations of the chemotactic attraction of neutrophils in response to particles using permanent cell lines. We challenged NR8383 rat macrophages with particles that were characterized concerning chemical nature, crystallinity, and size distribution in the dry state and in the culture medium. The cell supernatants were used to investigate migration of differentiated human leukemia cells (dHL-60 cells). The dose range for the tests was determined using an impedance-based Real-Time Cell Analyzer. The challenge of NR8383 cells with 32-96μgcm-2 coarse and nanosized particles resulted in cell supernatants which induced strong and dose-dependent migration of dHL-60 cells. Quartz caused the strongest effects - exceeding the positive control "fetal calf serum" (FCS) several-fold, followed by silica, rutile, carbon black, and anatase. BaSO<inf>4</inf> served as inert control and induced no cell migration. Particles caused NR8383 cells to secrete chemotactic compounds. The assay clearly distinguished between the particles of different inflammatory potential in a highly reproducible way. Specificity of the test is suggested by negative results with BaSO<inf>4</inf>. © 2015 The Authors.view abstract doi: 10.1016/j.tiv.2015.04.005 2015 • 385 Particle-Matrix Interaction in Cross-Linked PAAm-Hydrogels Analyzed by Mössbauer Spectroscopy
Landers, J. and Roeder, L. and Salamon, S. and Schmidt, A.M. and Wende, H.
Journal of Physical Chemistry C 119 20642-20648 (2015)The constrained motion of spindle-shaped hematite nanoparticles of about 400 nm in PAAm-hydrogels with different degrees of cross-link density is measured utilizing the line broadening observable in Mössbauer spectra at 265-293 K. A slight decrease of nanoparticle mobility is observed upon increasing cross-link density. Mössbauer spectra of the same nanoparticles in 60 wt % sucrose solution, used as reference material, display line broadening of the same magnitude as the hydrogel samples, indicating a similar degree of motion at the atomic scale and the time scale of the Mössbauer experiment. AC (alternating current) susceptibility data indicate that the magnetic relaxation of the nanoparticles in sucrose solution mainly occurs by Brownian motion, while the absence of magnetic loss within the investigated frequency range observed in measurements on hydrogel samples reveals very limited particle mobility. This apparent contradiction between results on particle dynamics in hydrogels by Mössbauer spectroscopy and AC susceptibility measurements is explained in terms of constrained particle mobility at atomic scales. © 2015 American Chemical Society.view abstract doi: 10.1021/acs.jpcc.5b03697 2015 • 384 Phase transitions during formation of Ag nanoparticles on In 2 S3 precursor layers
Liu, Y. and Fu, Y. and Dittrich, T. and Sáez-Araoz, R. and Schmid, M. and Hinrichs, V. and Lux-Steiner, M.C. and Fischer, C.-H.
Thin Solid Films 590 54-59 (2015)Phase transitions have been investigated for silver deposition onto In<inf>2</inf>S<inf>3</inf> precursor layers by spray chemical vapor deposition from a trimethylphosphine (hexafluoroacetylacetonato) silver (Ag(hfacac)(PMe<inf>3</inf>)) solution. The formation of Ag nanoparticles (Ag NPs) on top of the semiconductor layer set on concomitant with the formation of AgIn<inf>5</inf>S<inf>8</inf>. The increase of the diameter of Ag NPs was accompanied by the evolution of orthorhombic AgInS<inf>2</inf>. The formation of Ag<inf>2</inf>S at the interface between Ag NPs and the semiconductor layer was observed. Surface photovoltage spectroscopy indicated charge separation and electronic transitions in the ranges of corresponding band gaps. The phase transition approach is aimed to be applied for the formation of plasmonic nanostructures on top of extremely thin semiconducting layers. © 2015 Elsevier B.V.view abstract doi: 10.1016/j.tsf.2015.07.021 2015 • 383 Plasma synthesis of titanium nitride, carbide and carbonitride nanoparticles by means of reactive anodic arc evaporation from solid titanium
Kiesler, D. and Bastuck, T. and Theissmann, R. and Kruis, F.E.
Journal of Nanoparticle Research 17 (2015)Plasma methods using the direct evaporation of a transition metal are well suited for the cost-efficient production of ceramic nanoparticles. In this paper, we report on the development of a simple setup for the production of titanium-ceramics by reactive anodic arc evaporation and the characterization of the aerosol as well as the nanopowder. It is the first report on TiCXN1 − X synthesis in a simple anodic arc plasma. By means of extensive variations of the gas composition, it is shown that the composition of the particles can be tuned from titanium nitride over a titanium carbonitride phase (TiCXN1 − X) to titanium carbide as proven by XRD data. The composition of the plasma gas especially a very low concentration of hydrocarbons around 0.2 % of the total plasma gas is crucial to tune the composition and to avoid the formation of free carbon. Examination of the particles by HR-TEM shows that the material consists mostly of cubic single crystalline particles with mean sizes between 8 and 27 nm. © 2015, Springer Science+Business Media Dordrecht.view abstract doi: 10.1007/s11051-015-2967-8 2015 • 382 Process engineering of nanoparticles below 20 nm—a fundamental discussion of characterization, particle formation, stability and post processing
Segets, D. and Peukert, W.
Colloid Process Engineering 279-305 (2015)In the following chapter fundamental aspects that have to be considered during the processing of small nanoparticles will be addressed. We investigated quantum confined manganese doped ZnS, ZnO, PbS and PbSe semiconductor nanoparticles, so-called quantum dots (QDs) and silver noble metal nanorods. All materials were chosen due to their technical relevance for future applications in the emerging fields of solar cells, sensors and diagnostics as well as due to the possibility of their in situ characterization by UV/Vis absorbance spectroscopy. After a brief introduction to the specific prospects and challenges of these materials we will focus on the important processing issues that need to be solved for producing these particles at high quality on a larger scale: (i) the modelling of particle formation including nucleation, growth and ripening based on a mechanistic understanding and on experimentally derived data on solubility and surface energies, (ii) the stabilization of nanoparticles not only against agglomeration but also against shape changes and (iii) classification. The latter is realized by size selective precipitation which allows surprisingly sharp separations (κ= 0.75) of particles with only a few nm in diameter. Although the extremely small particle sizes (feed PSD between 1.5 and 3 nm), classification results were successfully analyzed by well-known concepts from particle technology. Our results are seen to be an essential contribution to colloidal processing. They enable a future optimization of process parameters by a knowledge-based design strategy that can be applied within continuous as well as automatized batch reactor concepts. © Springer International Publishing Switzerland 2015.view abstract doi: 10.1007/978-3-319-15129-8_12 2015 • 381 Proteomic analysis of protein carbonylation: A useful tool to unravel nanoparticle toxicity mechanisms
Driessen, M.D. and Mues, S. and Vennemann, A. and Hellack, B. and Bannuscher, A. and Vimalakanthan, V. and Riebeling, C. and Ossig, R. and Wiemann, M. and Schnekenburger, J. and Kuhlbusch, T.A.J. and Renard, B. and Luch, A. and Haase, A.
Particle and Fibre Toxicology 12 (2015)Background: Oxidative stress, a commonly used paradigm to explain nanoparticle (NP)-induced toxicity, results from an imbalance between reactive oxygen species (ROS) generation and detoxification. As one consequence, protein carbonyl levels may become enhanced. Thus, the qualitative and quantitative description of protein carbonylation may be used to characterize how biological systems respond to oxidative stress induced by NPs. Methods: We investigated a representative panel of 24 NPs including functionalized amorphous silica (6), zirconium dioxide (4), silver (4), titanium dioxide (3), zinc oxide (2), multiwalled carbon nanotubes (3), barium sulfate and boehmite. Surface reactivities of all NPs were studied in a cell-free system by electron spin resonance (ESR). NRK-52E cells were treated with all NPs, analyzed for viability (WST-1 assay) and intracellular ROS production (DCFDA assay). Carbonylated proteins were assessed by 1D and/or 2D immunoblotting and identified by matrix assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF/TOF). In parallel, tissue homogenates from rat lungs intratracheally instilled with silver NPs were studied. Results: Eleven NPs induced elevated levels of carbonylated proteins. This was in good agreement with the surface reactivity of the NPs as obtained by ESR and the reduction in cell viability as assessed by WST-1 assay. By contrast, results obtained by DCFDA assay were deviating. Each NP induced an individual pattern of protein carbonyls on 2D immunoblots. Affected proteins comprised cytoskeletal components, proteins being involved in stress response, or cytoplasmic enzymes of central metabolic pathways such as glycolysis and gluconeogenesis. Furthermore, induction of carbonyls upon silver NP treatment was also verified in rat lung tissue homogenates. Conclusions: Analysis of protein carbonylation is a versatile and sensitive method to describe NP-induced oxidative stress and, therefore, can be used to identify NPs of concern. Furthermore, detailed information about compromised proteins may aid in classifying NPs according to their mode of action. © 2015 Driessen et al.view abstract doi: 10.1186/s12989-015-0108-2 2015 • 380 Pseudomorphic Generation of Supported Catalysts for Glycerol Oxidation
Deng, X. and Dodekatos, G. and Pupovac, K. and Weidenthaler, C. and Schmidt, W. and Schüth, F. and Tüysüz, H.
ChemCatChem 7 3832-3837 (2015)A catalyst consisting of copper nanoparticles (15-20 nm in size) supported on ordered mesoporous cobalt monoxide was synthesized by the one-step reduction of ethanol from nanocast copper cobalt spinel oxides. The small-angle X-ray scattering patterns showed that the ordered mesostructure was maintained after post-treatment, and the cross-section scanning electron microscopy images showed that the Cu nanoparticles were distributed homogeneously throughout the mesoporous CoO framework. The materials were tested as noble-metal-free catalysts for the oxidation of glycerol under alkaline conditions. The catalytic data showed that the presence of Cu nanoparticles greatly enhanced the catalytic performance. Nothing noble: A catalyst consisting of copper nanoparticles (NPs, 15-20 nm in size) supported on ordered mesoporous cobalt monoxide is synthesized by the one-step reduction with ethanol from nanocast copper cobalt spinel oxides. As a noble-metal-free catalyst for the oxidation of glycerol, the presence of Cu NPs greatly enhances the catalytic performance. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/cctc.201500703 2015 • 379 Quantitative replacement of citrate by phosphane on silver nanoparticle surfaces monitored by Surface-Enhanced Raman Spectroscopy (SERS)
Grass, S. and Diendorf, J. and Gebauer, J.S. and Epple, M. and Treuel, L.
Journal of Nanoscience and Nanotechnology 15 1591-1596 (2015)Chemical approaches to metal NP synthesis commonly use capping agents to achieve a desired NP size and shape. Frequently, such NPs require chemically different surface ligands after synthesis to generate desired NP properties (e.g., charge or hydrophilicity) and to increase their long term colloidal stability. Here, we prepared SERS active citrate-stabilized silver NPs (d = 38 ± 4 nm), purified them from remaining reactants by ultracentrifugation and redispersion, and immersed them into solutions containing different concentrations of Tris(sodium-m-sulfonatophenyl)phosphine (TPPTS), which is often used in such ligand replacement approaches to increase colloidal stability. After equilibration, SERS spectra were acquired, elucidating the concentration dependence of the ligand replacement reaction. SERS data were complemented by concentration dependent size measurements and relations between ligand exchange and colloidal stability are discussed. Copyright © 2015 American Scientific Publishersview abstract doi: 10.1166/jnn.2015.9143 2015 • 378 Raman-encoded microbeads for spectral multiplexing with SERS detection
Lai, Y. and Sun, S. and He, T. and Schlücker, S. and Wang, Y.
RSC Advances 5 13762-13767 (2015)Simultaneous detection of multiple molecular targets can greatly facilitate early diagnosis and drug discovery. Encoding micron-sized beads with optically active tags is one of the most popular methods to achieve multiplexing. Noble metal nanoparticle labels for optical detection by surface-enhanced Raman spectroscopy (SERS) exhibit narrow bandwidths, high photostability and intense Raman signals. In this study, we demonstrate the feasibility of spectral multiplexing by SERS using micron-sized polystyrene (PS) beads loaded with SERS-active nanoparticles. The silica-encapsulated SERS nanotags comprise gold nanocrystals with a self-assembled monolayer (SAM) of aromatic thiols as Raman reporter molecules for spectral identification. SERS microspectroscopic images of single Raman-encoded PS microbeads indicate the homogeneous spatial distribution of the SERS-active nanoparticles on the surface of the beads. By using up to five different Raman reporters, 31 spectrally distinct micron-sized beads were encoded and characterized spectroscopically at the single-bead level. This journal is © The Royal Society of Chemistry 2015.view abstract doi: 10.1039/c4ra16163g 2015 • 377 Resonant photothermal laser processing of hybrid gold/titania nanoparticle films
Schade, L. and Franzka, S. and Dzialkowski, K. and Hardt, S. and Wiggers, H. and Reichenberger, S. and Wagener, P. and Hartmann, N.
Applied Surface Science 336 48-52 (2015)Photothermal processing of thin anatase TiO2 and hybrid Au/anatase TiO2 nanoparticle films on glass supports is investigated using continuous-wave microfocused lasers at λ = 355 nm and λ = 532 nm. UV/Vis spectroscopy, Raman spectroscopy, optical microscopy, atomic force microscopy and scanning electron microscopy are used for characterization. Processing of TiO2 nanoparticle films is feasible at λ = 355 nm only. In contrast, the addition of Au nanoparticles enhances the overall absorbance of the material in the visible range and enables processing at both wavelengths, i.e. at λ = 355 nm and λ = 532 nm. Generally, laser heating induces a transition from anatase to rutile. The modification degree increases with increasing laser power and laser irradiation time. Resonant laser processing of hybrid Au/TiO2-mesoporous films provide promising perspectives in various applications, e.g. in photovoltaics, where embedded nanoparticulate Au could be exploited to enhance light trapping. © 2014 Published by Elsevier B.V.view abstract doi: 10.1016/j.apsusc.2014.09.118 2015 • 376 Reversible or Not? Distinguishing Agglomeration and Aggregation at the Nanoscale
Sokolov, S.V. and Tschulik, K. and Batchelor-McAuley, C. and Jurkschat, K. and Compton, R.G.
Analytical Chemistry 87 10033-10039 (2015)Nanoparticles are prone to clustering either via aggregation (irreversible) or agglomeration (reversible) processes. It is exceedingly difficult to distinguish the two via conventional techniques such as dynamic light scattering (DLS), nanoparticle tracking analysis (NTA), or electron microscopy imaging (scanning electron microscopy (SEM), transmission electron microscopy (TEM)) as such techniques only generally confirm the presence of large particle clusters. Herein we develop a joint approach to tackle the issue of distinguishing between nanoparticle aggregation vs agglomeration by characterizing a colloidal system of Ag NPs using DLS, NTA, SEM imaging and the electrochemical nanoimpacts technique. In contrast to the conventional techniques which all reveal the presence of large clusters of particles, electrochemical nanoimpacts provide information regarding individual nanoparticles in the solution phase and reveal the presence of small nanoparticles (<30 nm) even in high ionic strength (above 0.5 M KCl) and allow a more complete analysis. The detection of small nanoparticles in high ionic strength media evidence the clustering to be a reversible process. As a result it is concluded that agglomeration rather than irreversible aggregation takes place. This observation is of general importance for all colloids as it provides a feasible analysis technique for a wide range of systems with an ability to distinguish subtly different processes. © 2015 American Chemical Society.view abstract doi: 10.1021/acs.analchem.5b02639 2015 • 375 Ripening kinetics of laser-generated plasmonic nanoparticles in different solvents
Gökce, B. and Van't Zand, D.D. and Menéndez-Manjón, A. and Barcikowski, S.
Chemical Physics Letters 626 96-101 (2015)Abstract Pulsed laser ablation in liquid is considered to be a fast nanoparticle-synthesis method taking place on ps to μs timescale. Here, we report the comparably slow ripening kinetics of laser-generated plasmonic nanoparticles (copper, silver, and gold) immediately after ablation. The growth dynamics is studied in situ by following the surface plasmon resonance and correlated to known models. We thereby identify a two-step diffusion-controlled coalescence and growth mechanism, quantify their kinetic constants and show the effect of different solvents (water, acetone, ethanol, and ethyl acetate). © 2015 Published by Elsevier B.V.view abstract doi: 10.1016/j.cplett.2015.03.010 2015 • 374 Routes towards catalytically active TiO 2 doped porous cellulose
Wittmar, A. and Thierfeld, H. and Köcher, S. and Ulbricht, M.
RSC Advances 5 35866-35873 (2015)Cellulose-TiO<inf>2</inf> nanocomposites have been successfully prepared by non-solvent induced phase separation, either from cellulose solutions in ionic liquids or from cellulose acetate solutions in classical organic solvents followed by deacetylation ("regeneration"). Commercially available titania nanoparticles from gas phase synthesis processes have been used and processed as dispersions in the respective polymer solution. The used TiO<inf>2</inf> nanoparticles have been characterized by means of transmission electron microscopy (TEM) and X-ray diffraction (XRD), and their dispersions in ionic liquids and organic solvents have been evaluated by dynamic light scattering (DLS) and advanced rheology. The intermediate polymer solutions used in the phase separation process have been studied by advanced rheology. The resulting nanocomposites have been characterized by means of scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR). Special attention has been given to the complex relationship between the characteristics of the phase separation process and the porous structure of the formed nanocomposites. Two catalytic tests, based on the photocatalytic degradation of model organic dyes under UV irradiation, have been used for the characterization of the TiO<inf>2</inf> doped nanocomposites. The proof-of-concept experiments demonstrated the feasibility of photocatalyst immobilization in porous cellulose via phase separation of nanoparticle dispersions in polymer solutions, as indicated by UV-activated dye degradation in aqueous solution. © The Royal Society of Chemistry.2015.view abstract doi: 10.1039/c5ra03707g 2015 • 373 Sample temperature profile during the excimer laser annealing of silicon nanoparticles
Caninenberg, M. and Verheyen, E. and Kiesler, D. and Stoib, B. and Brandt, M.S. and Benson, N. and Schmechel, R.
Optics and Laser Technology 74 132-137 (2015)Based on the heat diffusion equation we describe the temperature profile of a silicon nanoparticle thin film on silicon during excimer laser annealing using COMSOL Multiphysics. For this purpose system specific material parameters are determined such as the silicon nanoparticle melting point at 1683 K, the surface reflectivity at 248 nm of 20% and the nanoparticle thermal conductivity between 0.3 and 1.2 W/m K. To validate our model, the simulation results are compared to experimental data obtained by Raman spectroscopy, SEM microscopy and electrochemical capacitance-voltage measurements (ECV). The experimental data are in good agreement with our theoretical findings and support the validity of the model. © 2015, Elsevier Ltd. All rights reserved.view abstract doi: 10.1016/j.optlastec.2015.05.020 2015 • 372 Sex-Sorted Boar Sperm - An Update on Related Production Methods
Rath, D. and Tiedemann, D. and Gamrad, L. and Johnson, L.A. and Klein, S. and Kues, W. and Mancini, R. and Rehbock, C. and Taylor, U. and Barcikowski, S.
Reproduction in domestic animals = Zuchthygiene 50 56-60 (2015)As in other mammals, sex sorting of pig sperm is based on quantitative flow cytometry. A major disadvantage of the technique is the relatively low efficiency to produce enough sorted sperm for artificial insemination. However, several approaches are on the way to make sexed pig sperm available for commercial application. In this context, for example, the growing field of nanotechnology may significantly contribute to these developments, as it provides highly efficient bio-nanoprobes, for example, based on plasmonic nanoparticles. Independent of the method, further development requires enormous investments and set-up of logistics to get the technology into the practical pig market. Only global players will be able to establish the necessary research projects, but in the end, a significant shift of sex ratios will be available for pig producers as it is already the case for the dairy industry. © 2015 Blackwell Verlag GmbH.view abstract doi: 10.1111/rda.12572 2015 • 371 Shape-Selection of Thermodynamically Stabilized Colloidal Pd and Pt Nanoparticles Controlled via Support Effects
Ahmadi, M. and Behafarid, F. and Holse, C. and Nielsen, J.H. and Roldan Cuenya, B.
Journal of Physical Chemistry C 119 29178-29185 (2015)Colloidal chemistry, in combination with nanoparticle (NP)/support epitaxial interactions is used here to synthesize shape-selected and thermodynamically stable metallic NPs over a broad range of NP sizes. The morphology of three-dimensional palladium and platinum NPs supported on TiO2(110) was investigated using scanning tunneling microscopy. Well-defined Pd and Pt NPs were synthesized via inverse micelle encapsulation. The initially spherical NPs were found to become faceted and form an epitaxial relationship with the support after high-temperature annealing (e.g., 1100 °C). Shape selection was achieved for almost all Pd NPs, namely, a truncated octahedron shape with (111) top and interfacial facets. The Pt NPs were however found to adopt a variety of shapes. The epitaxial relationship of the NPs with the support was evidenced by the alignment of the cluster's edges with TiO2(110)-[001] atomic rows and was found to be responsible for the shape control. The ability of synthesizing thermally stable shape-selected metal NPs demonstrated here is expected to be of relevance for applications in the field of catalysis, since the activity and selectivity of NP catalysts has been shown to strongly depend on the NP shape. © 2015 American Chemical Society.view abstract doi: 10.1021/acs.jpcc.5b09980 2015 • 370 Si-CNT/rGO Nanoheterostructures as High-Performance Lithium-Ion-Battery Anodes
Xiao, L. and Sehlleier, Y.H. and Dobrowolny, S. and Orthner, H. and Mahlendorf, F. and Heinzel, A. and Schulz, C. and Wiggers, H.
ChemElectroChem 2 1983-1990 (2015)A robust and electrochemically stable 3D nanoheterostructure consisting of Si nanoparticles (NPs), carbon nanotubes (CNTs) and reduced graphene oxide (rGO) is developed as an anode material (Si-CNT/rGO) for lithium-ion batteries (LIBs). It integrates the benefits from its three building blocks of Si NPs, CNTs, and rGO; Si NPs offer high capacity, CNTs act as a mechanical, electrically conductive support to connect Si NPs, and highly electrically conductive and flexible rGO provides a robust matrix with enough void space to accommodate the volume changes of Si NPs upon lithiation/delithiation and to simultaneously assure good electric contact. The composite material shows a high reversible capacity of 1665mAhg-1 with good capacity retention of 88.6% over 500 cycles when cycled at 0.5C, that is, a 0.02% capacity decay per cycle. The high-power capability is demonstrated at 10C (16.2Ag-1) where 755mAhg-1 are delivered, thus indicating promising characteristics of this material for high-performance LIBs. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/celc.201500323 2015 • 369 Size control and supporting of palladium nanoparticles made by laser ablation in saline solution as a facile route to heterogeneous catalysts
Marzun, G. and Nakamura, J. and Zhang, X. and Barcikowski, S. and Wagener, P.
Applied Surface Science 348 75-84 (2015)In the literature many investigations on colloidal stability and size control of gold nanoparticles are shown but less for ligand-free palladium nanoparticles, which can be promising materials in various applications. Palladium nanoparticles are perspective materials for a manifold of energy application like photo- and electrocatalysis or hydrogen storage. For this purpose, size-controlled nanoparticles with clean surfaces and facile immobilization on catalyst supports are wanted. Laser ablation in saline solution yields ligand-free, charged colloidal palladium nanoparticles that are supported by titania and graphene nanosheets as model systems for photo- and electrocatalysis, respectively. By adjusting the ionic strength during laser ablation in liquid, it is possible to control stability and particle size without compromising subsequent nanoparticle adsorption of supporting materials. A quantitative deposition of nearly 100% yield with up to 18 wt% nanoparticle load was achieved. The average size of the laser-generated nanoparticles remains the same after immobilization on a support material, in contrast to other preparation methods of catalysts. The characterization by X-ray photoelectron spectroscopy reveals a redox reaction between the immobilized nanoparticles and the graphene support. © 2015 Elsevier B.V. All rights reserved.view abstract doi: 10.1016/j.apsusc.2015.01.108 2015 • 368 Soft Nanocomposites-From Interface Control to Interphase Formation
Pihan, S.A. and Emmerling, S.G.J. and Butt, H.-J. and Berger, R. and Gutmann, J.S.
ACS Applied Materials and Interfaces 7 12380-12386 (2015)We report measurements of structure, mechanical properties, glass transition temperature, and contact angle of a novel nanocomposite material consisting of swellable silsesquioxane nanoparticles with grafted poly(ethyl methacrylate) (PEMA) brushes and PEMA matrices with varying molecular weight. We measured the interparticle distance at the surface of the composites using scanning probe microscopy (SPM) and in the bulk of ∼0.5 μm thick films by grazing incidence small angle X-ray scattering (GISAXS). For a given molecular weight of the brush unstable dispersions at high molecular weight of the matrix indicate an intrinsic incompatibility between polymer-grafted-nanoparticles and homopolymer matrices. This incompatibility is affirmed by a high contact angle between the polymer-grafted-nanoparticles and the high molecular weight matrix as measured by SPM. For unstable dispersions, we measured a decreased glass transition temperature along with a decreased plateau modulus by dynamic mechanical thermal analysis (DMTA) which indicates the formation of a liquid-like layer at the brush-matrix interface. This proves the ability to decouple the structural and mechanical properties from the potential to be swollen with small molecules. It opens a new area of use of these soft nanocomposites as slow release materials with tailored mechanical properties. © 2015 American Chemical Society.view abstract doi: 10.1021/am507572q 2015 • 367 Stability of Dealloyed Porous Pt/Ni Nanoparticles
Baldizzone, C. and Gan, L. and Hodnik, N. and Keeley, G.P. and Kostka, A. and Heggen, M. and Strasser, P. and Mayrhofer, K.J.J.
ACS Catalysis 5 5000-5007 (2015)We provide a comprehensive durability assessment dedicated to a promising class of electrocatalysts for the oxygen reduction reaction (i.e., porous platinum nanoparticles). The stability of these nanoengineered open structures is tested under two accelerated degradation test conditions (ADT), particularly selected to mimic the potential regimes experienced by the catalyst during the operative life of a fuel cell (i.e., load cycles (up to 1.0 V<inf>RHE</inf>) and start-up cycles (up to 1.4 V<inf>RHE</inf>)). To understand the evolution of the electrochemical performance, the catalyst properties are investigated by means of fundamental rotating disc electrode studies, identical location-transmission electron microscopy (IL-TEM) coupled with electron energy loss spectroscopy chemical mapping (IL-EELS), and post-use chemical analysis and online highly sensitive potential resolved dissolution concentration monitoring by scanning flow cell inductively coupled plasma-mass spectrometry (SFC-ICP-MS). The experimental results on the nanoporous Pt revealed distinctive degradation mechanisms that could potentially affect a wide range of other nanoengineered open structures. The study concludes that, although providing promising activity performance, under the relevant operational conditions of fuel cells, the nanoporosity is only metastable and subjected to a progressive reorganization toward the minimization of the nanoscale curvature. The rate and pathways of this specific degradation mechanism together with other well-known degradation mechanisms like carbon corrosion and platinum dissolution are strongly dependent on the selected upper limit potential, leading to distinctly different durability performance. © 2015 American Chemical Society.view abstract doi: 10.1021/acscatal.5b01151 2015 • 366 Structure-activity relationships of Co-modified Cu/ZnO/Al 2 O3 catalysts applied in the synthesis of higher alcohols from synthesis gas
Anton, J. and Nebel, J. and Song, H. and Froese, C. and Weide, P. and Ruland, H. and Muhler, M. and Kaluza, S.
Applied Catalysis A: General 505 326-333 (2015)Cu-Co-based catalysts were synthesized by co-precipitation using Cu, Co, Zn and Al nitrates and applied in higher alcohol synthesis (HAS) at 280 °C, 60 bar and a ratio of H<inf>2</inf>/CO = 1. The catalyst exhibiting a Cu/Co ratio of 2.5 was found to provide the best trade-off between product distribution and degree of CO conversion. After activation and 40 h time on stream reaching steady-state conditions the bulk and surface properties of the catalyst were thoroughly investigated without exposing it to air during the transfer and the measurements. The conditions during activation and HAS led to a significant enrichment of Zn in the surface composition of the catalysts. The XRD pattern of the catalyst after reaction compared with the reduced catalyst revealed further sintering of the metallic Cu nanoparticles and the growth of crystalline ZnO nanoparticles, but there were no indications for the presence of bulk metallic Co or for bulk alloying. With increasing time on stream the product distribution shifted favorably towards higher alcohols presumably due to an increased intimate interface contact between the large metallic Cu0 particles detected by XRD and the X-ray amorphous metallic Co surface species probed by XPS. © 2015 Elsevier B.V.view abstract doi: 10.1016/j.apcata.2015.07.002 2015 • 365 Synthesis and characterization of antimicrobial textile finishing based on Ag:ZnO nanoparticles/chitosan biocomposites
Buşilə, M. and Muşat, V. and Textor, T. and Mahltig, B.
RSC Advances 5 21562-21571 (2015)ZnO and Ag:ZnO nanoparticles were prepared by hydrolysis of zinc acetate in the presence of lithium hydroxide (LiOH). In combination with binders based on hybrid polymer sols, these metal oxide materials were applied for textile treatment. Hybrid coatings based on ZnO, Ag:ZnO/CS, chitosan (CS), 3-glycidyloxypropyltrimethoxysilane (GPTMS) and tetraethoxysilane (TEOS) prepared by sol-gel method were applied on cotton 100% and cotton/polyester (50/50%) textiles using "pad-dry-cure" technique. The obtained nanoparticles incorporated within chitosan matrix were characterised by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), UV-Vis spectroscopy and field emission scanning electron microscopy (FE-SEM). The antimicrobial activity of Ag/CS, ZnO/CS and Ag:ZnO/CS composite coatings was investigated in comparison to that of the pure chitosan using the paper disc method on Mueller-Hinton agar, against the Gram-negative E. coli and the Gram-positive S. aureus bacteria. For the same composite coatings applied on textile, the antimicrobial activity was investigated by UV-Vis absorption spectroscopy using TTC method, against the bacteria E. coli and M. luteus. The investigated nanocomposite materials showed good antimicrobial activity and are promising materials for use as medical applications. This journal is © The Royal Society of Chemistry.view abstract doi: 10.1039/c4ra13918f 2015 • 364 Synthesis of Binary Sb 2 E3 (E = S, Se) and Ternary Sb2 (S,Se)3 Nanowires Using Tailor-Made Single-Source Precursors
Heimann, S. and Assenmacher, W. and Prymak, O. and Schulz, S.
European Journal of Inorganic Chemistry 2015 2407-2415 (2015)Thermal decomposition of four single-source precursors of the type (Et<inf>2</inf>Sb)<inf>2</inf>E and Et<inf>3</inf>SbE (E = S, Se) at 170 °C in the presence of suitable capping agents yielded binary Sb<inf>2</inf>S<inf>3</inf> and Sb<inf>2</inf>Se<inf>3</inf> nanowires. In addition, simultaneous decomposition of (Et<inf>2</inf>Sb)<inf>2</inf>S and(Et<inf>2</inf>Sb)<inf>2</inf>Se gave the ternary phase Sb<inf>2</inf>(S,Se)<inf>3</inf> with almost equal S and Se concentrations. The materials were characterized by XRD, REM, EDX, ED and HRTEM. Copyright © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/ejic.201500325 2015 • 363 Synthesis, characterization and in vitro effects of 7 nm alloyed silver-gold nanoparticles
Ristig, S. and Chernousova, S. and Meyer-Zaika, W. and Epple, M.
Beilstein Journal of Nanotechnology 6 1212-1220 (2015)Alloyed silver-gold nanoparticles were prepared in nine different metal compositions with silver/gold molar ratios of ranging from 90:10 to 10:90. The one-pot synthesis in aqueous medium can easily be modified to gain control over the final particle diameter and the stabilizing agents. The purification of the particles to remove synthesis by-products (which is an important factor for subsequent in vitro experiments) was carried out by multiple ultracentrifugation steps. Characterization by transmission electron microscopy (TEM), differential centrifugal sedimentation (DCS), dynamic light scattering (DLS), UV-vis spectroscopy and atomic absorption spectroscopy (AAS) showed spherical, monodisperse, colloidally stable silver-gold nanoparticles of ≈7 nm diameter with measured molar metal compositions very close to the theoretical values. The examination of the nanoparticle cytotoxicity towards HeLa cells and human mesenchymal stem cells (hMSCs) showed that the toxicity is not proportional to the silver content. Nanoparticles with a silver/gold molar composition of 80:20 showed the highest toxicity. © 2015 Ristig et al.view abstract doi: 10.3762/bjnano.6.124 2015 • 362 The fate of nano-silver in aqueous media
Plowman, B.J. and Tschulik, K. and Walport, E. and Young, N.P. and Compton, R.G.
Nanoscale 7 12361-12364 (2015)Silver nanoparticles offer highly attractive properties for many applications, however concern has been raised over the possible toxicity of this material in environmental systems. While it is thought that the release of Ag+ can play a crucial role in this toxicity, the mechanism by which the oxidative dissolution of nano-silver occurs is not yet understood. Here we address this through the electrochemical analysis of gold-core silver-shell nanoparticles in various solutions. This novel method allows the direct quantification of silver dissolution by normalisation to the gold core signal. This is shown to be highly effective at discriminating between silver dissolution and the loss of nanoparticles from the electrode surface. We evidence through this rigorous approach that the reduction of O<inf>2</inf> drives the dissolution of nano-silver, while in the presence of Cl- this dissolution is greatly inhibited. This work is extended to the single nanoparticle level using nano-impact experiments. © The Royal Society of Chemistry.view abstract doi: 10.1039/c5nr02995c 2015 • 361 The potential of nanoparticles for the immunization against viral infections
Sokolova, V. and Westendorf, A.M. and Buer, J. and Überla, K. and Epple, M.
Journal of Materials Chemistry B 3 4767-4779 (2015)Vaccination has a great impact on the prevention and control of infectious diseases. However, there are still many infectious diseases for which an effective vaccine is missing. Thirty years after the discovery of the AIDS-pathogen (human immunodeficiency virus, HIV) and intensive research, there is still no protective immunity against the HIV infection. Over the past decade, nanoparticulate systems such as virus-like particles, liposomes, polymers and inorganic nanoparticles have received attention as potential delivery vehicles which can be loaded or functionalized with active biomolecules (antigens and adjuvants). Here we compare the properties of different nanoparticulate systems and assess their potential for the development of new vaccines against a range of viral infections. © The Royal Society of Chemistry 2015.view abstract doi: 10.1039/c5tb00618j 2015 • 360 Thermoelectrics from silicon nanoparticles: the influence of native oxide
Petermann, N. and Stötzel, J. and Stein, N. and Kessler, V. and Wiggers, H. and Theissmann, R. and Schierning, G. and Schmechel, R.
European Physical Journal B 88 (2015)Thermoelectric materials were synthesized by current-assisted sintering of doped silicon nanoparticles produced in a microwave-plasma reactor. Due to their affinity to oxygen, the nanoparticles start to oxidize when handled in air and even a thin surface layer of native silicon oxide leads to a significant increase in the oxide volume ratio. This results in a considerable incorporation of oxygen into the sintered pellets, thus affecting the thermoelectric performance. To investigate the necessity of inert handling of the raw materials, the thermoelectric transport properties of sintered nanocrystalline silicon samples were characterized with respect to their oxygen content. An innovative method allowing a quantitative silicon oxide analysis by means of electron microscopy was applied: the contrast between areas of high and low electrical conductivity was attributed to the silicon matrix and silicon oxide precipitates, respectively. Thermoelectric characterization revealed that both, electron mobility and thermal conductivity decrease with increasing silicon oxide content. A maximum figure of merit with zT = 0.45 at 950 °C was achieved for samples with a silicon oxide mass fraction of 9.5 and 21.4% while the sample with more than 25% of oxygen clearly indicates a negative impact of the oxygen on the electron mobility. © 2015, EDP Sciences, SIF, Springer-Verlag Berlin Heidelberg.view abstract doi: 10.1140/epjb/e2015-50594-7 2015 • 359 Uniform 2 nm gold nanoparticles supported on iron oxides as active catalysts for CO oxidation reaction: Structure-activity relationship
Guo, Y. and Gu, D. and Jin, Z. and Du, P.-P. and Si, R. and Tao, J. and Xu, W.-Q. and Huang, Y.-Y. and Senanayake, S. and Song, Q.-S. and Jia, C.-J. and Schüth, F.
Nanoscale 7 4920-4928 (2015)Uniform Au nanoparticles (∼2 nm) with narrow size-distribution (standard deviation: 0.5-0.6 nm) supported on both hydroxylated (Fe-OH) and dehydrated iron oxide (Fe-O) have been prepared by either deposition-precipitation (DP) or colloidal-deposition (CD) methods. Different structural and textural characterizations were applied to the dried, calcined and used gold-iron oxide samples. Transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) showed high homogeneity in the supported Au nanoparticles. The ex situ and in situ X-ray absorption fine structure (XAFS) characterization monitored the electronic and short-range local structure of active gold species. The synchrotron-based in situ X-ray diffraction (XRD), together with the corresponding temperature-programmed reduction by hydrogen (H<inf>2</inf>-TPR), indicated a structural evolution of the iron-oxide supports, correlating to their reducibility. An inverse order of catalytic activity between DP (Au/Fe-OH < Au/Fe-O) and CD (Au/Fe-OH > Au/Fe-O) was observed. Effective gold-support interaction results in a high activity for gold nanoparticles, locally generated by the sintering of dispersed Au atoms on the oxide support in the DP synthesis, while a hydroxylated surface favors the reactivity of externally introduced Au nanoparticles on Fe-OH support for the CD approach. This work reveals why differences in the synthetic protocol translate to differences in the catalytic performance of Au/FeO<inf>x</inf> catalysts with very similar structural characteristics in CO oxidation. © The Royal Society of Chemistry 2015.view abstract doi: 10.1039/c4nr06967f 2015 • 358 Unveiling the correlation between nanometer-thick molecular monolayer sensitivity and near-field enhancement and localization in coupled plasmonic oligomers
König, M. and Rahmani, M. and Zhang, L. and Lei, D.Y. and Roschuk, T.R. and Giannini, V. and Qiu, C.-W. and Hong, M. and Schlücker, S. and Maier, S.A.
ACS Nano 8 9188-9198 (2015)Metal nanoclusters, sometimes called metamolecules or plasmonic oligomers, exhibit interesting optical properties such as Fano resonances and optical chirality. These properties promise a variety of practical applications, particularly in ultrasensitive biochemical sensing. Here we investigate experimentally the sensitivities of plasmonic pentamers and quadrumers to the adsorption of self-assembled nanometer-thick alkanethiol monolayers. The monolayer sensitivity of such oligomers is found to be significantly higher than that of single plasmonic nanoparticles and depends on the nanocluster arrangement, constituent nanoparticle shape, and the plasmon resonance wavelength. Together with full-wave numerical simulation results and the electromagnetic perturbation theory, we unveil a direct correlation between the sensitivity and the near-field intensity enhancement and spatial localization in the plasmonic hot spots generated in each nanocluster. Our observation is beyond conventional considerations (such as optimizing nanoparticle geometry or narrowing resonance line width) for improving the sensing performance of metal nanoclusters-based biosensors and opens the possibilities of using plasmonic nanoclusters for single-molecule detection and identification. © 2014 American Chemical Society.view abstract doi: 10.1021/nn5028714 2015 • 357 Water-dispersible small monodisperse electrically conducting antimony doped tin oxide nanoparticles
Peters, K. and Zeller, P. and Stefanic, G. and Skoromets, V. and Němec, H. and Kužel, P. and Fattakhova-Rohlfing, D.
Chemistry of Materials 27 1090-1099 (2015)We describe the fabrication of crystalline electrically conducting antimony-doped tin oxide (ATO) nanoparticles highly dispersible in polar solvents such as water and ethanol without any stabilizing agents. Nonagglomerated monodisperse ATO nanoparticles with different doping levels are obtained by a facile solvothermal reaction in tert-butanol, leading to the formation of monodisperse nanocrystals with a size of about 3 nm directly after synthesis. Electrical conductivity of ATO nanoparticles strongly increases due to the substitutional doping with antimony, reaching 6.8 × 10-2 S cm-1 for the as-synthesized nanoparticles prepared with 3-5 mol % Sb. This increase stems from transition from hopping in the undoped samples to band-like conduction in the doped samples as revealed by terahertz (THz) spectroscopy measurements describing transport on nanometer distances. The dc conductivity of the doped nanoparticles increases by about 3 orders of magnitude up to 62 S cm-1 after annealing in air at 500 °C. The electrical conductivity, crystallinity, small size, and high dispersibility in polar solvents make the obtained ATO nanoparticles promising building blocks for the direct assembly of more complex conducting architectures using polymer templates that could be damaged in organic solvents. We illustrate the benefits of the water-dispersible ATO nanoparticles by their assembly to periodic macroporous electrodes using poly(methyl methacrylate) (PMMA) beads as the porosity templates. Aqueous dispersion of ATO nanoparticles can be directly combined with PMMA beads that are easily removed by calcination, enabling a facile deposition of 3D-macroporous ATO electrodes featuring optical transparency and a large periodically ordered conducting interface. © 2015 American Chemical Society.view abstract doi: 10.1021/cm504409k 2015 • 356 Wet-chemical synthesis of different bismuth telluride nanoparticles using metal organic precursors-single source vs. dual source approach
Bendt, G. and Weber, A. and Heimann, S. and Assenmacher, W. and Prymak, O. and Schulz, S.
Dalton Transactions 44 14272-14280 (2015)Thermolysis of the single source precursor (Et<inf>2</inf>Bi)<inf>2</inf>Te 1 in DIPB at 80 °C yielded phase-pure Bi<inf>4</inf>Te<inf>3</inf> nanoparticles, while mixtures of Bi<inf>4</inf>Te<inf>3</inf> and elemental Bi were formed at higher temperatures. In contrast, cubic Bi<inf>2</inf>Te particles were obtained by thermal decomposition of Et<inf>2</inf>BiTeEt 2 in DIPB. Moreover, a dual source approach (hot injection method) using the reaction of Te(SiEt<inf>3</inf>)<inf>2</inf> and Bi(NMe<inf>2</inf>)<inf>3</inf> was applied for the synthesis of different pure Bi-Te phases including Bi<inf>2</inf>Te, Bi<inf>4</inf>Te<inf>3</inf> and Bi<inf>2</inf>Te<inf>3</inf>, which were characterized by PXRD, REM, TEM and EDX. The influence of reaction temperature, precursor molar ratio and thermolysis conditions on the resulting material phase was verified. Moreover, reactions of alternate bismuth precursors such as Bi(NEt<inf>2</inf>)<inf>3</inf>, Bi(NMeEt)<inf>3</inf> and BiCl<inf>3</inf> with Te(SiEt<inf>3</inf>)<inf>2</inf> were investigated. © 2015 The Royal Society of Chemistry.view abstract doi: 10.1039/c5dt02072g 2014 • 355 A polyphenylene support for pd catalysts with exceptional catalytic activity
Wang, F. and Mielby, J. and Richter, F.H. and Wang, G. and Prieto, G. and Kasama, T. and Weidenthaler, C. and Bongard, H.-J. and Kegnæs, S. and Fürstner, A. and Schüth, F.
Angewandte Chemie - International Edition 53 8645-8648 (2014)We describe a solid polyphenylene support that serves as an excellent platform for metal-catalyzed reactions that are normally carried out under homogeneous conditions. The catalyst is synthesized by palladium-catalyzed Suzuki coupling which directly results in formation of palladium nanoparticles confined to a porous polyphenylene network. The composite solid is in turn highly active for further Suzuki coupling reactions, including non-activated substrates that are challenging even for molecular catalysts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/anie.201404912 2014 • 354 A radial differential mobility analyzer for the size-classification of gas-phase synthesized nanoparticles at low pressures
Nanda, K.K. and Kruis, F.E.
Measurement Science and Technology 25 (2014)Differential mobility analyzers (DMAs) are commonly used to generate monodisperse nanoparticle aerosols. Commercial DMAs operate at quasi-atmospheric pressures and are therefore not designed to be vacuum-tight. In certain particle synthesis methods, the use of a vacuum-compatible DMA is a requirement as a process step for producing high-purity metallic particles. A vacuum-tight radial DMA (RDMA) has been developed and tested at low pressures. Its performance has been evaluated by using a commercial NANO-DMA as the reference. The performance of this low-pressure RDMA (LP-RDMA) in terms of the width of its transfer function is found to be comparable with that of other NANO-DMAs at atmospheric pressure and is almost independent of the pressure down to 30 mbar. It is shown that LP-RDMA can be used for the classification of nanometer-sized particles (5-20nm) under low pressure condition (30 mbar) and has been successfully applied to nanoparticles produced by ablating FeNi at low pressures. © 2014 IOP Publishing Ltd.view abstract doi: 10.1088/0957-0233/25/7/075605 2014 • 353 Adsorption of Colloidal Platinum Nanoparticles to Supports: Charge Transfer and Effects of Electrostatic and Steric Interactions
Marzun, G. and Streich, C. and Jendrzej, S. and Barcikowski, S. and Wagener, P.
Langmuir 30 11928-11936 (2014)Adsorption of colloidal nanoparticles to surfaces and supports is a convenient approach to heterogeneous catalysts, polymer additives, or wastewater treatment. We investigated the adsorption efficiency of laser-generated and initially ligand-free platinum nanoparticles to TiO<inf>2</inf> supports as a function of pH, ionic strength, and ligand surface coverage. The nanoparticle adsorption is dominantly controlled by electrostatic interactions: if the pH of the suspension is between the isoelectric point of the nanoparticles and the support, nanoparticles are adsorbed and transfer a net charge to the support. This charge-driven adsorption is not affected by steric repulsion due to various ligands attached to the nanoparticle surface. In addition to electrostatic interactions, colloidal stability given by moderate ionic strengths and pH values above the isoelectric point of nanoparticles are prerequisites for colloidal deposition. (Chemical Equation Presented). © 2014 American Chemical Society.view abstract doi: 10.1021/la502588g 2014 • 352 Aluminum-doped ZnO nanoparticles: Gas-phase synthesis and dopant location
Schilling, C. and Zähres, M. and Mayer, C. and Winterer, M.
Journal of Nanoparticle Research 16 (2014)Aluminum-doped ZnO (AZO) nanoparticles are studied widely as transparent conducting alternatives for indium tin oxide. However, the properties of AZO vary in different investigations not only with the amount of dopant and the particle size, but also with other parameters such as synthesis method and conditions. Hence, AZO nanoparticles, synthesized in the gas phase, were investigated to study the influence of the synthesis parameters dopant level, reactor temperature and residence time in the reaction zone on the particle characteristics. The local structure of the dopant in semiconductors determines whether the doping is functional, i.e., whether mobile charge carriers are generated. Therefore, information obtained from 27Al solid-state NMR spectroscopy, X-ray diffraction, photoluminescence and UV-Vis spectroscopy was used to understand how the local structure influences particles characteristics and how the local structure itself can be influenced by the synthesis parameters. In addition to AZO particles of different Al content, pure ZnO, Al2O3, ZnAl2O4 and core-shell particles of ZnO and Al2O3 were synthesized for comparison and aid to a deeper understanding of the formation of AZO nanoparticles in the gas phase. © 2014 Springer Science+Business Media.view abstract doi: 10.1007/s11051-014-2506-z 2014 • 351 Antibacterial AgNPs/CaP biocomposites
Ivanova, A.A. and Surmenev, R.A. and Surmeneva, M.A. and Mukhametkaliyev, T. and Sharonova, A.A. and Grubova, I.Y. and Loza, K. and Chernousova, S. and Prymak, O. and Epple, M.
2014 9th International Forum on Strategic Technology, IFOST 2014 472-474 (2014)The modification of implant surface is in the focus of many scientists worldwide. In this study, multifunctional biocomposite on the basis of calcium phosphate coating and silver nanoparticles has been fabricated through the use of nanofabrication techniques. Dense nanocrystalline HA film was deposited over AgNPs. The properties as well as the in vitro behavior of the developed biocomposites have been studied. The diffraction patterns of the biocomposites revealed the peaks of crystalline HA and silver (Ag). The release of Ag from the developed biocomposites was evaluated. The concentration of the released silver ions for 7 days of dissolution was 0.27±0.02 μg/mL and 0.54±0.02 μg/mL for phosphate and acetate buffers, respectively. In order to estimate the cytotoxicity of the samples the functional activity of osteoclasts, in particular, cell morphology, multinuclearity, actin ring and resorption pit on the substrates coated with HA and AgNPs-HA have been evaluated. © 2014 IEEE.view abstract doi: 10.1109/IFOST.2014.6991166 2014 • 350 Assessment of a cylindrical and a rectangular plate differential mobility analyzer for size fractionation of nanoparticles at high-aerosol flow rates
Hontañón, E. and Rouenhoff, M. and Azabal, A. and Ramiro, E. and Kruis, F.E.
Aerosol Science and Technology 48 333-339 (2014)An existing differential mobility analyzer (DMA) of cylindrical electrodes and a novel DMA of rectangular plate electrodes are demonstrated for size fractionation of nanoparticles at high-aerosol flow rates in this work. The two DMAs are capable of delivering monodisperse size selected nanoparticles (SMPS σg < 1.1) at gas flow rates ranging from 200 slm to 500 slm. At an aerosol flow rate of 200 slm, the maximum attainable particle mean size is of about 20 nm for the cylindrical DMA and of nearly 50 nm for the rectangular plate DMA. The number concentration of the monodisperse nanoparticles delivered by the high-flow DMAs spans from 104 cm-3 to 10 6 cm-3 depending upon the particle mean size and particle size dispersion. Copyright © 2014 American Association for Aerosol Research.view abstract doi: 10.1080/02786826.2013.875116 2014 • 349 Atomic imaging of carbon-supported Pt, Pt/Co, and Ir@Pt nanocatalysts by atom-probe tomography
Li, T. and Bagot, P.A.J. and Christian, E. and Theobald, B.R.C. and Sharman, J.D.B. and Ozkaya, D. and Moody, M.P. and Tsang, S.C.E. and Smith, G.D.W.
ACS Catalysis 4 695-702 (2014)Atom probe tomography (APT) has been used to characterize commercially prepared Pt, Pt/Co alloy, and Ir@Pt core-shell nanoparticles supported on high-surface-area carbon black. Concentration profiles and 3D atom maps revealing the detailed internal structures and compositions of Pt, Pt/Co alloy, and Ir@Pt core-shell particles have been generated, and the distribution of trace impurity elements, including Na and Cl, has been examined. The observation of retained Na on the support, especially in the Pt nanoparticle system, indicates a more rigorous washing procedure is required. In the Pt/Co alloyed carbon-supported nanoparticle system, a marked variation in both compositions and particle sizes is observed. In the case of Ir@Pt, significant intermixing of the Ir core and Pt shell atoms takes place, which would be very difficult to measure by other techniques. All such observations will likely impact the catalytic performance of these materials. We envisage that the single nanoparticle analysis capability of APT, providing atomic-scale structures and chemical mapping, can also act as a means of quality control, identifying differences in the final product compared with the intended specification. Although the catalytic activity of these nanoparticles was not part of current study, the detailed information offered by such studies will permit knowledge-based improvements in nanoscale catalyst preparation methods and will also provide new ways of investigating structure and activity relationships at the nanometer scale. © 2014 American Chemical Society.view abstract doi: 10.1021/cs401117e 2014 • 348 Behavior of nanoscale titanium dioxide in laboratory wastewater treatment plants according to OECD 303 A
Gartiser, S. and Flach, F. and Nickel, C. and Stintz, M. and Damme, S. and Schaeffer, A. and Erdinger, L. and Kuhlbusch, T.A.J.
Chemosphere 104 197-204 (2014)The fate assessment of nanomaterials in municipal sewage treatment plants (STP) is a crucial step for their environmental risk assessment and may be assessed by monitoring full scale STP, dosage to medium scale pilot STP or by laboratory testing. For regulatory purposes preferably standardised test protocols such as the OECD guidelines for testing of chemicals should be used. However, these test protocols have not yet been specifically designed for nanoparticles. Therefore, the fate and behavior of a TiO2 nanomaterial (P25, average hydrodynamic diameter < 250nm) was investigated in laboratory sewage treatment plants according to the OECD Guideline for the Testing of Chemicals 303 A. It is concluded that this guideline is applicable for the testing of nanomaterials if modifications regarding the dosage, nitrifying conditions, and a characterisation of the nanoparticles in the effluent are applied. A compilation of the cumulative mass balance by comparison of the total dosage added with the amount in the outflow and in the activated sludge is recommended. In this study, the majority of the TiO2 nanomaterial (>95%) was retained in the sewage sludge and only 3-4% was found in the effluent. No effect of the TiO2 nanomaterials on the biodegradation or nitrification was observed. © 2013 Elsevier Ltd.view abstract doi: 10.1016/j.chemosphere.2013.11.015 2014 • 347 Calcium phosphate nanoparticles show an effective activation of the innate immune response in vitro and in vivo after functionalization with flagellin
Kozlova, D. and Sokolova, V. and Zhong, M. and Zhang, E. and Yang, J. and Li, W. and Yang, Y. and Buer, J. and Westendorf, A.M. and Epple, M. and Yan, H.
Virologica Sinica 29 33-39 (2014)For subunit vaccines, adjuvants play a key role in shaping the magnitude, persistence and form of targeted antigen-specific immune response. Flagellin is a potent immune activator by bridging innate inflammatory responses and adaptive immunity and an adjuvant candidate for clinical application. Calcium phosphate nanoparticles are efficient carriers for different biomolecules like DNA, RNA, peptides and proteins. Flagellin-functionalized calcium phosphate nanoparticles were prepared and their immunostimulatory effect on the innate immune system, i.e. the cytokine production, was studied. They induced the production of the proinflammatory cytokines IL-8 (Caco-2 cells) and IL-1β (bone marrow-derived macrophages; BMDM) in vitro and IL-6 in vivo after intraperitoneal injection in mice. The immunostimulation was more pronounced than with free flagellin. © 2014 Wuhan Institute of Virology, CAS and Springer-Verlag Berlin Heidelberg.view abstract doi: 10.1007/s12250-014-3379-0 2014 • 346 Carbon monoxide-assisted size confinement of bimetallic alloy nanoparticles
Cui, C. and Gan, L. and Neumann, M. and Heggen, M. and Roldan Cuenya, B. and Strasser, P.
Journal of the American Chemical Society 136 4813-4816 (2014)Colloid-based chemical synthesis methods of bimetallic alloy nanoparticles (NPs) provide good monodispersity, yet generally show a strong variation of the resulting mean particle size with alloy composition. This severely compromises accurate correlation between composition of alloy particles and their size-dependent properties. To address this issue, a general CO adsorption-assisted capping ligand-free solvothermal synthesis method is reported which provides homogeneous bimetallic NPs with almost perfectly constant particle size over an unusually wide compositional range. Using Pt-Ni alloy NPs as an example, we show that variation of the reaction temperature between 160 and 240 °C allows for precise control of the resulting alloy particle bulk composition between 15 and 70 atomic % Ni, coupled with a constant mean particle size of ∼4 nm. The size-confining and Ni content-controlling role of CO during the nucleation and growth processes are investigated and discussed. Data suggest that size-dependent CO surface chemisorption and reversible Ni-carbonyl formation are key factors for the achievement of a constant particle size and temperature-controlled Ni content. To demonstrate the usefulness of the independent control of size and composition, size-deconvoluted relations between composition and electrocatalytic properties are established. Refining earlier reports, we uncover intrinsic monotonic relations between catalytic activity and initial Ni content, as expected from theoretical considerations. © 2014 American Chemical Society.view abstract doi: 10.1021/ja4124658 2014 • 345 Charge balancing of model gold-nanoparticle-peptide conjugates controlled by the peptide's net charge and the ligand to nanoparticle ratio
Gamrad, L. and Rehbock, C. and Krawinkel, J. and Tumursukh, B. and Heisterkamp, A. and Barcikowski, S.
Journal of Physical Chemistry C 118 10302-10313 (2014)Gold nanoparticles (AuNPs) covalently bound to biomolecules, termed bioconjugates,1 are highly relevant for biological applications like drug targeting or bioimaging. Here, the net charge of the bioconjugate is one key parameter affecting biocompatibility and cell membrane interaction. However, when negatively charged AuNPs are conjugated to positively charged biomolecules, resulting charge compensation compromises the stability of the conjugates. In this work, laser-generated negatively charged AuNPs exhibiting a bare surface were used as a model and separately conjugated to cell penetrating peptides (CPPs) carrying different positive net charges. Occurring charge compensation leads to two regimes where stable bioconjugates are obtained on both sides of the bioconjugate's isoelectric point. These regimes can be controlled by the peptide's net charge. Generally, increasing the peptide's net charges yields stable positively charged bioconjugates with decreased surface coverages. To demonstrate the compatibility of the bioconjugates in bioapplications, long-term stability measurements were performed. Furthermore, the uptake by live mammalian cells was investigated with multiphoton microscopy using the luminescence of the AuNP-peptide conjugates. The results for our model system of laser-generated AuNPs and CPPs show that a precise tuning of conjugate properties is possible. They can be transferred to other oppositely charged nanoparticle-ligand systems, avoiding occurrence of charge compensation with defined ligand load. © 2014 American Chemical Society.view abstract doi: 10.1021/jp501489t 2014 • 344 Chemical interactions between silver nanoparticles and thiols: A comparison of mercaptohexanol against cysteine
Toh, H.S. and Batchelor-Mcauley, C. and Tschulik, K. and Compton, R.G.
Science China Chemistry 57 1199-1210 (2014)The interaction between citrate capped silver nanoparticles and two different thiols, mercaptohexanol (MH) and cysteine, was investigated. The thiols interacted with silver nanoparticles in a significantly contrasting manner. With MH, a sparingly soluble silver(I) thiolate complex AgSRm (Rm = -(CH2)6OH) was formed on the silver nanoparticle surface. Cyclic voltammograms and UV-vis spectra were used to infer that the AgSRm complex on the nanoparticle surface undergoes a phase transition to give a mixture of AgSRm and Ag2S-like complexes. In contrast, when silver nanoparticles were exposed to cysteine, the citrate capping agent on the silver nanoparticles was replaced by cysteine to give cysteine capped nanoparticles. As cysteine capped nanoparticles form, the electrochemical data displayed a decrease in oxidative peak charge but the UV-vis spectra showed a constant signal. Therefore, cysteine capped nanoparticles were suggested to have either inactivated the silver surface or else promoted detachment from the electrode surface. © 2014 Science China Press and Springer-Verlag Berlin Heidelberg.view abstract doi: 10.1007/s11426-014-5141-8 2014 • 343 CO 2 hydrogenation to hydrocarbons over iron nanoparticles supported on oxygen-functionalized carbon nanotubes
Chew, L.M. and Ruland, H. and Schulte, H.J. and Xia, W. and Muhler, M.
Journal of Chemical Sciences 126 481-486 (2014)Hydrogenation of CO2 to hydrocarbons over iron nanoparticles supported on oxygen-functionalized multi-walled carbon nanotubes was studied in a fixed-bed U-tube reactor at 25 bar with a H2:CO2 ratio of 3. Conversion of CO2 was approximately 35% yielding C 1-C5 products at 360°C with methane and CO as major products. The CO2 equilibrium conversion for temperatures in the range of 320° to 420°C was analysed by using CHEMCAD simulation software. Comparison between experimental and simulated degrees of CO 2 conversion shows that reverse water gas shift equilibrium had been achieved in the investigated temperature range and that less than 47% of CO 2 can be converted to CO at 420°C. © 2014 Indian Academy of Sciences.view abstract doi: 10.1007/s12039-014-0591-2 2014 • 342 Comparison of different characterization methods for nanoparticle dispersions before and after aerosolization
Fissan, H. and Ristig, S. and Kaminski, H. and Asbach, C. and Epple, M.
Analytical Methods 6 7324-7334 (2014)A well-known and accepted aerosol measurement technique, the scanning mobility particle sizer (SMPS), is applied to characterize colloidally dispersed nanoparticles. To achieve a transfer from dispersed particles to aerosolized particles, a newly developed nebulizer (N) is used that, unlike commonly used atomizers, produces significantly smaller droplets and therefore reduces the problem of the formation of residual particles. The capabilities of this new instrument combination (N + SMPS) for the analysis of dispersions were investigated, using three different dispersions, i.e. gold-PVP nanoparticles (∼20 nm), silver-PVP nanoparticles (∼70 nm) and their 1:1 (m:m) mixture. The results are compared to scanning electron microscopy (SEM) measurements and two frequently applied techniques for characterizing colloidal systems: Dynamic light scattering (DLS) and analytical disc centrifugation (ADC). The differences, advantages and disadvantages of each method are discussed, especially with respect to the size resolution of the techniques and their ability to distinguish the particle sizes of the mixed dispersion. While DLS is, as expected, unable to resolve the binary dispersion, SEM, ADC and SMPS are able to give quantitative information on the two particle sizes. However, while the high-resolving ADC is limited due to the dependency on a predefined density of the investigated system, the transfer of dispersed particles into an aerosol and subsequent analysis with SMPS are an adequate way to characterize binary systems, independent of the density of concerned particles, but matching the high resolution of the ADC. We show that it is possible to use the well-established aerosol measurement technique (N + SMPS) in colloid science with all its advantages concerning size resolution and accuracy. © the Partner Organisations 2014.view abstract doi: 10.1039/c4ay01203h 2014 • 341 Comparison of silver nanoparticles stored under air or argon with respect to the induction of intracellular free radicals and toxic effects toward keratinocytes
Ahlberg, S. and Meinke, M.C. and Werner, L. and Epple, M. and Diendorf, J. and Blume-Peytavi, U. and Lademann, J. and Vogt, A. and Rancan, F.
European Journal of Pharmaceutics and Biopharmaceutics 88 651-657 (2014)Bacterial infections decreased considerably after the discovery of antibiotics. Nevertheless, because of the rising rate of infections caused by antibiotic-resistant bacteria strains, the search for new bactericidal agents has again become a crucial topic in clinical medicine. Silver nanoparticles (AgNP) have a huge potential in dermatology and wound care management because of their ability to release silver ions (Ag+ ions) in a prolonged and sustained way. However, negative effects of silver on the patient's cells should not be underestimated. Furthermore, it has been controversially discussed whether AgNP are responsible for nanoparticle-specific outcomes or not. In this study, we investigated the effects of AgNP on human skin keratinocytes (HaCaT) in order to better understand the mechanisms of cytotoxicity and to improve the use of this highly reactive biocide in wound healing. We found that most of the cells with internalized AgNP displayed the typical morphological signs of apoptosis. The cell viability assay (XTT) showed concentration-dependent toxic effects of the AgNP toward HaCaT cells. The generation of reactive oxygen species (ROS) induced by AgNP was investigated in cell suspensions by means of electron paramagnetic resonance (EPR) spectroscopy. In order to distinguish between the effects of Ag+ ions released during AgNP storage and those of Ag+ ions released after nanoparticle application, we compared AgNP stored under air (O2) with AgNP stored under argon (Ar). Dispersions of AgNP stored under Ar have a low content of Ag+ ions because of the absence of oxygen which is needed for oxidative dissolution. The results show that Ag+ ions released during particle storage are responsible for most of the ROS produced during 1 h incubation with the cells. AgNP (Ar) also induced intracellular ROS but to a much smaller extent compared to AgNP (O2). These findings highlight the complexity of experiments to assess the toxicity of AgNP and suggest the possibility of reducing AgNP toxic effects by storing AgNP formulations and even silver-containing wound dressing under an inert gas atmosphere. © 2014 Elsevier B.V. All rights reserved.view abstract doi: 10.1016/j.ejpb.2014.07.012 2014 • 340 Confined-space alloying of nanoparticles for the synthesis of efficient PtNi fuel-cell catalysts
Baldizzone, C. and Mezzavilla, S. and Carvalho, H.W.P. and Meier, J.C. and Schuppert, A.K. and Heggen, M. and Galeano, C. and Grunwaldt, J.-D. and Schüth, F. and Mayrhofer, K.J.J.
Angewandte Chemie - International Edition 53 14250-14254 (2014)The efficiency of polymer electrolyte membrane fuel cells is strongly depending on the electrocatalyst performance, that is, its activity and stability. We have designed a catalyst material that combines both, the high activity for the decisive cathodic oxygen reduction reaction associated with nanoscale Pt alloys, and the excellent durability of an advanced nano-structured support. Owing to the high specific activity and large active surface area, the catalyst shows extraordinary mass activity values of 1.0 AmgPt -1. Moreover, the material retains its initial active surface area and intrinsic activity during an extended accelerated aging test within the typical operation range. This excellent performance is achieved by confined space alloying of the nanoparticles in a controlled manner in the pores of the support. © 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/anie.201406812 2014 • 339 Correlation of superparamagnetic relaxation with magnetic dipole interaction in capped iron-oxide nanoparticles
Landers, J. and Stromberg, F. and Darbandi, M. and Schöppner, C. and Keune, W. and Wende, H.
Journal of Physics Condensed Matter 27 (2014)Six nanometer sized iron-oxide nanoparticles capped with an organic surfactant and/or silica shell of various thicknesses have been synthesized by a microemulsion method to enable controllable contributions of interparticle magnetic dipole interaction via tunable interparticle distances. Bare particles with direct surface contact were used as a reference to distinguish between interparticle interaction and surface effects by use of Mössbauer spectroscopy. Superparamagnetic relaxation behaviour was analyzed by SQUID-magnetometry techniques, showing a decrease of the blocking temperature with decreasing interparticle interaction energies kBT 0 obtained by AC susceptibility. A many-state relaxation model enabled us to describe experimental Mössbauer spectra, leading to an effective anisotropy constant Keff ≈ 45 kJm-3 in case of weakly interacting particles, consistent with results from ferromagnetic resonance. Our unique multi-technique approach, spanning a huge regime of characteristic time windows from about 10 s to 5 ns, provides a concise picture of the correlation of superparamagnetic relaxation with interparticle magnetic dipole interaction. © 2015 IOP Publishing Ltd.view abstract doi: 10.1088/0953-8984/27/2/026002 2014 • 338 Design criteria for stable Pt/C fuel cell catalysts
Meier, J.C. and Galeano, C. and Katsounaros, I. and Witte, J. and Bongard, H.J. and Topalov, A.A. and Baldizzone, C. and Mezzavilla, S. and Schüth, F. and Mayrhofer, K.J.J.
Beilstein Journal of Nanotechnology 5 44-67 (2014)Platinum and Pt alloy nanoparticles supported on carbon are the state of the art electrocatalysts in proton exchange membrane fuel cells. To develop a better understanding on how material design can influence the degradation processes on the nanoscale, three specific Pt/C catalysts with different structural characteristics were investigated in depth: a conventional Pt/Vulcan catalyst with a particle size of 3-4 nm and two Pt@HGS catalysts with different particle size, 1-2 nm and 3-4 nm. Specifically, Pt@HGS corresponds to platinum nanoparticles incorporated and confined within the pore structure of the nanostructured carbon support, i.e., hollow graphitic spheres (HGS). All three materials are characterized by the same platinum loading, so that the differences in their performance can be correlated to the structural characteristics of each material. The comparison of the activity and stability behavior of the three catalysts, as obtained from thin film rotating disk electrode measurements and identical location electron microscopy, is also extended to commercial materials and used as a basis for a discussion of general fuel cell catalyst design principles. Namely, the effects of particle size, inter-particle distance, certain support characteristics and thermal treatment on the catalyst performance and in particular the catalyst stability are evaluated. Based on our results, a set of design criteria for more stable and active Pt/C and Pt-alloy/C materials is suggested.& copy 2014 Meier et al.view abstract doi: 10.3762/bjnano.5.5 2014 • 337 Dipole-dipole interaction in arrays of Fe/FexOy Core/shell nanocubes probed by ferromagnetic resonance
Sukhov, A. and Horley, P.P. and Berakdar, J. and Terwey, A. and Meckenstock, R. and Farle, M.
IEEE Transactions on Magnetics 50 (2014)This paper represents a detailed theoretical study of the role of the long-range magnetic dipole-dipole interaction (DDI) evidenced by the ferromagnetic resonance (FMR) spectra for the ordered arrays of cubic nanoparticles. We show that the size of the array essentially controls the stability of the system, allowing us to suppress the intermittent low-field excitations starting from the arrays formed by 6 × 6 nanoparticles. Our numerical simulations allow us to determine the threshold inter-particle distance (around 80/100 nm), after which the DDI becomes negligible so that the FMR spectrum of the nanoparticle arrays becomes the same as the spectrum featured by a single nanoparticle.We also compare our simulations with experimental FMR-spectra of 24 Fe/FexOy-nanocubes irregularly placed on a substrate. © 2014 IEEE.view abstract doi: 10.1109/TMAG.2014.2329814 2014 • 336 Dose-dependent surface endothelialization and biocompatibility of polyurethane noble metal nanocomposites
Hess, C. and Schwenke, A. and Wagener, P. and Franzka, S. and Laszlo Sajti, C. and Pflaum, M. and Wiegmann, B. and Haverich, A. and Barcikowski, S.
Journal of Biomedical Materials Research - Part A 102 1909-1920 (2014)Surface pre-endothelialization is a promising approach to improve the hemocompatibility of implants, medical devices, and artificial organs. To promote the adhesive property of thermoplastic polyurethane (TPU) for endothelial cells (ECs), up to 1 wt % of gold (Au) or platinum (Pt) nanoparticles, fabricated by pulsed laser ablation in polymer solution, were embedded into the polymer matrix. The analysis of these nanocomposites showed a homogenous dispersion of the nanoparticles, with average diameters of 7 nm for Au or 9 nm for Pt. A dose-dependent effect was found when ECs were seeded onto nanocomposites comprising different nanoparticle concentrations, resulting in a fivefold improvement of proliferation at 0.1 wt % nanoparticle load. This effect was associated with a nanoparticle concentration-dependent hydrophilicity and negative charge of the nanocomposite. In dynamic flow tests, nanocomposites containing 0.1 wt % Au or Pt nanoparticles allowed for the generation of a confluent and resistant EC layer. Real-time polymerase chain reaction quantification of specific markers for EC activation indicated that ECs cultivated on nanocomposites remain in an inactivated, nonthrombogenic and noninflammatory state; however, maintain the ability to trigger an inflammatory response upon stimulation. These findings were confirmed by a platelet and leukocyte adhesion assay. The results of this study suggest the possible applicability of TPU nanocomposites, containing 0.1 wt % Au or Pt nanoparticles, for the generation of pre-endothelialized surfaces of medical devices. © 2013 Wiley Periodicals, Inc.view abstract doi: 10.1002/jbm.a.34860 2014 • 335 Dynamic surface processes of nanostructured Pd2Ga catalysts derived from hydrotalcite-like precursors
Ota, A. and Kröhnert, J. and Weinberg, G. and Kasatkin, I. and Kunkes, E.L. and Ferri, D. and Girgsdies, F. and Hamilton, N. and Armbrüster, M. and Schlögl, R. and Behrens, M.
ACS Catalysis 4 2048-2059 (2014)The stability of the surface termination of intermetallic Pd2Ga nanoparticles and its effect on the hydrogenation of acetylene was investigated. For this purpose, a precursor synthesis approach was applied to synthesize supported intermetallic Pd2Ga nanoparticles. A series of Pd-substituted MgGa-hydrotalcite (HT)-like compounds with different Pd loading was prepared by coprecipitation and studied in terms of loading, phase formation, stability and catalytic performance in the selective hydrogenation of acetylene. Higher Pd loadings than 1 mol % revealed an incomplete incorporation of Pd into the HT lattice, as evidenced by XANES and TPR measurements. Upon thermal reduction in hydrogen, Pd2Ga nanoparticles were obtained with particle sizes varying with the Pd loading, from 2 nm to 6 nm. The formation of intermetallic Pd2Ga nanoparticles led to a change of the CO adsorption properties as was evidenced by IR spectroscopy. Dynamic changes of the surface were noticed at longer exposure times to CO and higher coverage at room temperature as a first indication of surface instability. These were ascribed to the decomposition into a Ga-depleted Pd phase and Ga 2O3, which is a process that was suppressed at liquid nitrogen temperature. The reduction of the Pd precursor at 473 K is not sufficient to form the Pd2Ga phase and yielded a poorly selective catalyst (26% selectivity to ethylene) in the semihydrogenation of acetylene. In accordance with the well-known selectivity-promoting effect of a second metal, the selectivity was increased to 80% after reduction at 773 K due to a change from the elemental to the intermetallic state of palladium in our catalysts. Interestingly, if air contact was avoided after reduction, the conversion slowly rose from initially 22% to 94% with time on stream. This effect is interpreted in the light of chemical response of Pd and Pd2Ga to the chemical potential of the reactive atmosphere. Conversely to previous interpretations, we attribute the initial low active state to the clean intermetallic surface, while the increase in conversion is related to the surface decomposition of the Pd2Ga particles. © 2014 American Chemical Society.view abstract doi: 10.1021/cs500465r 2014 • 334 Dynamical behavior of laser-induced nanoparticles during remote processing
Scholz, T. and Dickmann, K. and Ostendorf, A.
Proceedings of SPIE - The International Society for Optical Engineering 8963 (2014)Laser remote processing is used in a wide field of industrial applications. Among other things, it is characterized by flexible beam guidance in combination with high processing velocities. But in most cases process gas support in the interaction zone is omitted. Consequently, interaction mechanism between the vapor plume and the incident laser radiation can dynamically affect the process stability. Referring to remote welding with high brilliant laser sources having a wavelength around 1 μm, the interaction between the incident laser radiation and formed particles plays an important role. The presented work shows results of the investigation of the laser-induced particle formation during the laser welding of stainless steel with a 2 kW fiber laser under remote conditions. It is therefore concentrated on the dynamical behavior of the laser-induced particle formation and the dependence of the particle formation on the laser beam power. TEM images of formed particles were analyzed. In addition, the radiation of a LED was directed through the vapor plume. On the one hand, the dynamic of the attenuation was considered. On the other hand, the Rayleigh approximation was used in order to evaluate the detected signals. © 2014 SPIE.view abstract doi: 10.1117/12.2035197 2014 • 333 Effect of a side reaction involving structural changes of the surfactants on the shape control of cobalt nanoparticles
Comesaña-Hermo, M. and Estivill, R. and Ciuculescu, D. and Li, Z.-A. and Spasova, M. and Farle, M. and Amiens, C.
Langmuir 30 4474-4482 (2014)Cobalt nanoparticles with different sizes and morphologies including spheres, rods, disks, and hexagonal prisms have been synthesized through the decomposition of the olefinic precursor [Co(η3-C 8H13)(η4-C8H12)] under dihydrogen, in the presence of hexadecylamine and different rhodamine derivatives, or aromatic carboxylic acids. UV-vis spectroscopy, X-ray diffraction, low and high resolution transmission electron microscopy, and electron tomography have been used to characterize the nanomaterials. Especially, the Co nanodisks formed present characteristics that make them ideal nanocrystals for applications such as magnetic data storage. Focusing on their growth process, we have evidenced that a reaction between hexadecylamine and rhodamine B occurs during the formation of these Co nanodisks. This reaction limits the amount of free acid and amine, usually at the origin of the formation of single crystal Co rods and wires, in the growth medium of the nanocrystals. As a consequence, a growth mechanism based on the structure of the preformed seeds rather than oriented attachment or template assisted growth is postulated to explain the formation of the nanodisks. © 2014 American Chemical Society.view abstract doi: 10.1021/la5005165 2014 • 332 Effect of silver nanoparticles on human mesenchymal stem cell differentiation
Sengstock, C. and Diendorf, J. and Epple, M. and Schildhauer, T.A. and Köller, M.
Beilstein Journal of Nanotechnology 5 2058-2069 (2014)Background: Silver nanoparticles (Ag-NP) are one of the fastest growing products in nano-medicine due to their enhanced antibacterial activity at the nanoscale level. In biomedicine, hundreds of products have been coated with Ag-NP. For example, various medical devices include silver, such as surgical instruments, bone implants and wound dressings. After the degradation of these materials, or depending on the coating technique, silver in nanoparticle or ion form can be released and may come into close contact with tissues and cells. Despite incorporation of Ag-NP as an antibacterial agent in different products, the toxicological and biological effects of silver in the human body after long-term and low-concentration exposure are not well understood. In the current study, we investigated the effects of both ionic and nanoparticulate silver on the differentiation of human mesenchymal stem cells (hMSCs) into adipogenic, osteogenic and chondrogenic lineages and on the secretion of the respective differentiation markers adiponectin, osteocalcin and aggrecan. Results: As shown through laser scanning microscopy, Ag-NP with a size of 80 nm (hydrodynamic diameter) were taken up into hMSCs as nanoparticulate material. After 24 h of incubation, these Ag-NP were mainly found in the endo-lysosomal cell compartment as agglomerated material. Cytotoxicity was observed for differentiated or undifferentiated hMSCs treated with high silver concentrations (≥20 μg·mL-1 Ag-NP; ≥1.5 μg·mL-1 Ag+ ions) but not with low-concentration treatments (≤10 μg·mL-1 Ag-NP; ≤1.0 μg·mL-1 Ag+ ions). Subtoxic concentrations of Ag-NP and Ag+ ions impaired the adipogenic and osteogenic differentiation of hMSCs in a concentration-dependent manner, whereas chondrogenic differentiation was unaffected after 21 d of incubation. In contrast to aggrecan, the inhibitory effect of adipogenic and osteogenic differentiation was confirmed by a decrease in the secretion of specific biomarkers, including adiponectin (adipocytes) and osteocalcin (osteoblasts). Conclusion: Aside from the well-studied antibacterial effect of silver, little is known about the influence of nano-silver on cell differentiation processes. Our results demonstrate that ionic or nanoparticulate silver attenuates the adipogenic and osteogenic differentiation of hMSCs even at non-toxic concentrations. Therefore, more studies are needed to investigate the effects of silver species on cells at low concentrations during long-term treatment. © 2014 Sengstock et al.view abstract doi: 10.3762/bjnano.5.214 2014 • 331 Electrochemical detection and characterisation of polymer nanoparticles
Zhou, X.-F. and Cheng, W. and Batchelor-Mcauley, C. and Tschulik, K. and Compton, R.G.
Electroanalysis 26 248-253 (2014)We report the detection and characterisation of polymer nanoparticles using electrochemistry using poly(N-vinylcarbazole) nanoparticles (PVK NPs) as a model system. These were synthesised using the reprecipitation method. The number of electrons (n=2) transferred per PVK monomer was characterised by drop-casting method. Sticking and sensing experiments were then conducted, which involve PVK nanoparticle immobilisation on the electrode surface and subsequent oxidative sensing, to enable rapid detection of polymer nanoparticles in aqueous solution. It is shown for the first time, that using this "stick and sense" method, polymer nanoparticles in aqueous solution can be immobilised, preconcentrated and quantified. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.view abstract doi: 10.1002/elan.201300438 2014 • 330 Electrochemical observation of single collision events: Fullerene nanoparticles
Stuart, E.J.E. and Tschulik, K. and Batchelor-Mcauley, C. and Compton, R.G.
ACS Nano 8 7648-7654 (2014)Individual fullerene nanoparticles are detected and sized in a non-aqueous solution via cathodic particle coulometry where the direct, quantitative reduction of single nanoparticles is achieved upon collision with a potentiostated gold electrode. This is the first time that the nanoparticle impact technique has been shown to work in a non-aqueous electrolyte and utilized to coulometrically size carbonaceous nanoparticles. Contrast is drawn between single-nanoparticle electrochemistry and that seen using nanoparticle ensembles via modified electrodes. © 2014 American Chemical Society.view abstract doi: 10.1021/nn502634n 2014 • 329 Enhancing solar cell efficiency by lenses on the nano- And microscale
Schmid, M. and Manley, P.
Proceedings of SPIE - The International Society for Optical Engineering 9178 (2014)Metallic nanoparticles exhibiting plasmonic effects as well as dielectric nanoparticles coupling the light into resonant modes have both shown successful application to photovoltaics. On the larger scale, microconcentrator optics promise to enhance solar cell efficiency and reduce material consumption. Here we want to make the link between concentrators on the nano- And on the microscale. From metallic nanospheres we turn to dielectric ones and then look at increasing radii to approach concentrator optics on the mircoscale. The nano- And microlenses are investigated with respect to their interaction with light using 3D simulations with the finite element method. Resulting maps of local electric field distributions reveal the focusing behavior of the dielectric spheres. For larger lens sizes, ray tracing calculations can be applied which give ray distributions in agreement with areas of high electric field intensities. Calculations of back focal lengths using ray tracing coincide with results from geometrical optics simulations. They give us insight into how the focal length can be tuned as a function of particle size, but also depending on the substrate refractive index and the shape of the microlens. Turning from spherical to segment-shaped lenses allows us to approach the realistic case of microconcentrator optics and to draw conclusions about focus tuning and system design. Despite the similarities of focusing behavior we find for the nano- And the microlenses, the integration into solar cells needs to be carefully adjusted, depending on the ambition of material saving, concentration level, focal distance and lens size, all being closely related. © 2014 SPIE.view abstract doi: 10.1117/12.2061132 2014 • 328 Exceptional size-dependent activity enhancement in the electroreduction of CO2 over Au nanoparticles
Mistry, H. and Reske, R. and Zeng, Z. and Zhao, Z.-J. and Greeley, J. and Strasser, P. and Cuenya, B.R.
Journal of the American Chemical Society 136 16473-16476 (2014)The electrocatalytic reduction of CO2 to industrial chemicals and fuels is a promising pathway to sustainable electrical energy storage and to an artificial carbon cycle, but it is currently hindered by the low energy efficiency and low activity displayed by traditional electrode materials. We report here the size-dependent catalytic activity of micelle-synthesized Au nanoparticles (NPs) in the size range of ∼1-8 nm for the electroreduction of CO2 to CO in 0.1 M KHCO3. A drastic increase in current density was observed with decreasing NP size, along with a decrease in Faradaic selectivity toward CO. Density functional theory calculations showed that these trends are related to the increase in the number of low-coordinated sites on small NPs, which favor the evolution of H2 over CO2 reduction to CO. We show here that the H2/CO product ratio can be specifically tailored for different industrial processes by tuning the size of the catalyst particles. © 2014 American Chemical Society.view abstract doi: 10.1021/ja508879j 2014 • 327 Fetuin-A and albumin alter cytotoxic effects of calcium phosphate nanoparticles on human vascular smooth muscle cells
Dautova, Y. and Kozlova, D. and Skepper, J.N. and Epple, M. and Bootman, M.D. and Proudfoot, D.
PLoS ONE 9 (2014)Calcification is a detrimental process in vascular ageing and in diseases such as atherosclerosis and arthritis. In particular, small calcium phosphate (CaP) crystal deposits are associated with inflammation and atherosclerotic plaque de-stabilisation. We previously reported that CaP particles caused human vascular smooth muscle cell (VSMC) death and that serum reduced the toxic effects of the particles. Here, we found that the serum proteins fetuin-A and albumin (≥1 μM) reduced intracellular Ca2+ elevations and cell death in VSMCs in response to CaP particles. In addition, CaP particles functionalised with fetuin-A, but not albumin, were less toxic than naked CaP particles. Electron microscopic studies revealed that CaP particles were internalised in different ways; via macropinocytosis, membrane invagination or plasma membrane damage, which occurred within 10 minutes of exposure to particles. However, cell death did not occur until approximately 30 minutes, suggesting that plasma membrane repair and survival mechanisms were activated. In the presence of fetuin-A, CaP particle-induced damage was inhibited and CaP/plasma membrane interactions and particle uptake were delayed. Fetuin-A also reduced dissolution of CaP particles under acidic conditions, which may contribute to its cytoprotective effects after CaP particle exposure to VSMCs. These studies are particularly relevant to the calcification observed in blood vessels in patients with kidney disease, where circulating levels of fetuin-A and albumin are low, and in pathological situations where CaP crystal formation outweighs calcification-inhibitory mechanisms. © 2014 Dautova et al.view abstract doi: 10.1371/journal.pone.0097565 2014 • 326 Generation of NiTi nanoparticles by femtosecond laser ablation in liquid
Chakif, M. and Essaidi, A. and Gurevich, E. and Ostendorf, A. and Prymak, O. and Epple, M.
Journal of Materials Engineering and Performance 23 2482-2486 (2014)NiTi was investigated as a model system for a binary alloy where the properties strongly depend on the relative proportion of the two elements and on the grain size. The NiTi nanoparticles were generated by laser ablation in water. For the analysis of the particle size distribution, we used transmission electron microscopy and dynamic light scattering. Here, we found a broad particle size distribution (10-200 nm). Furthermore, the temperature-resolved x-ray powder diffraction and differential scanning calorimetry (DSC) were used to evaluate the phase transition behavior of the generated NiTi nanoparticles. Here, we found an interesting effect. During the heating by DSC, an austenite phase transition and a weak martensite phase transition in the NiTi nanoparticles appeared. Moreover, the phase transformation temperature was about 40 K lower than that of the bulk target. © 2014 ASM International.view abstract doi: 10.1007/s11665-014-1007-7 2014 • 325 Gold electrodes from recordable CDs for the sensitive, semi-quantitative detection of commercial silver nanoparticles in seawater media
Stuart, E.J.E. and Tschulik, K. and Lowinsohn, D. and Cullen, J.T. and Compton, R.G.
Sensors and Actuators, B: Chemical 195 223-229 (2014)We report the use of homemade disposable gold electrodes fabricated from commercial recordable CDs for the detection and quantification of silver nanoparticles from a consumer product in a seawater sample. The "CDtrode" is immersed in a seawater sample containing silver nanoparticles for a certain amount of time during which the silver nanoparticles adsorb onto the CDtrode surface under open circuit conditions. The CDtrode is then transferred to an aqueous electrolyte and oxidative stripping is used to determine the amount of silver nanoparticles that have become stuck to the electrode surface. Depending on immersion time and silver nanoparticle concentration, up to a full monolayer coverage of silver nanoparticles on the CDtrode surface has been achieved. © 2014 Elsevier B.V.view abstract doi: 10.1016/j.snb.2014.01.040 2