Prof. Dr.-Ing. Stephan Barcikowski

Technical Chemistry
University of Duisburg-Essen


  • 3D printing of magnetic parts by laser powder bed fusion of iron oxide nanoparticle functionalized polyamide powders
    Hupfeld, T. and Salamon, S. and Landers, J. and Sommereyns, A. and Doñate-Buendía, C. and Schmidt, J. and Wende, H. and Schmidt, M. and Barcikowski, S. and Gökce, B.
    Journal of Materials Chemistry C 8 (2020)
    The development of new feedstock materials is a central prerequisite for advances in Additive Manufacturing (AM). To increase the breadth of potential applications for 3D and 4D printing of polymers, micro- and nano-additives incorporated into the feedstock material play an important role. In this context, magnetic materials are of great interest. Our study describes a way to fabricate polymer powders for laser powder bed fusion (PBF-LB) with a homogeneous, well-dispersed coating of iron oxide nanoparticles. Without the addition of chemical precursors, spherical superparamagnetic FeOxnanoparticles with monomodal size distribution below 10 nm are generated from FeOxmicropowder by laser fragmentation in liquid. The adsorption of the nanoparticles on polyamide (PA12) powder is conducted directly in an aqueous dispersion after laser fragmentation, followed by drying, powder analysis and PBF-LB processing.ViaMössbauer spectroscopy and magnetometry, we determined that the saturation magnetization and structure of the iron oxide nanoparticles were not influenced by PBF-LB processing, and the magnetic properties were successfully transferred to the final 3D-printed magnetic part. © The Royal Society of Chemistry 2020.
    view abstract10.1039/d0tc02740e
  • 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 abstract10.3390/ma13153312
  • Composition and structure of magnetic high-temperature-phase, stable Fe-Au core-shell nanoparticles with zero-valent bcc Fe core
    Kamp, M. and Tymoczko, A. and Popescu, R. and Schürmann, U. and Nadarajah, R. and Gökce, B. and Rehbock, C. and Gerthsen, D. and Barcikowski, S. and Kienle, L.
    Nanoscale Advances 2 (2020)
    Advanced quantitative TEM/EDXS methods were used to characterize different ultrastructures of magnetic Fe-Au core-shell nanoparticles formed by laser ablation in liquids. The findings demonstrate the presence of Au-rich alloy shells with varying composition in all structures and elemental bcc Fe cores. The identified structures are metastable phases interpreted by analogy to the bulk phase diagram. Based on this, we propose a formation mechanism of these complex ultrastructures. To show the magnetic response of these magnetic core nanoparticles protected by a noble metal shell, we demonstrate the formation of nanostrands in the presence of an external magnetic field. We find that it is possible to control the lengths of these strands by the iron content within the alloy nanoparticles. This journal is © The Royal Society of Chemistry.
    view abstract10.1039/d0na00514b
  • Dynamics of laser-induced cavitation bubbles at a solid-liquid interface in high viscosity and high capillary number regimes
    Hupfeld, T. and Laurens, G. and Merabia, S. and Barcikowski, S. and Gökce, B. and Amans, D.
    Journal of Applied Physics 127 (2020)
    No unified model is available yet to explain the dynamics of laser-induced cavitation bubbles during laser ablation of solid targets in liquids, when an extremely high capillary number is achieved (>100), i.e., when the viscous forces strongly contribute to the friction. By investigating laser-induced bubbles on gold and yttrium-iron-garnet targets as a function of the liquid viscosity, using a nanosecond laser and an ultrafast shadowgraph imaging setup, we give a deeper insight into what determines the bubble dynamics. We find that the competition between the viscous forces and the surface tension (capillary number Ca), on the one hand, and the competition between the viscous forces and inertia (Reynolds number Re), on the other hand, are both key factors. Increasing the viscous forces, and hereby Ca up to 100 has an impact on the bubble shape and results in a very pronounced rim, which separates the bubble in a spherical cap driven by inertia and an interlayer. The temporal evolution of the footprint radius of the interlayer can be addressed in the framework of the inertiocapillary regime. For an intermediate viscosity, the thickness of the interlayer is consistent with a boundary layer equation. Interestingly, our data cannot be interpreted with simplified hydrodynamic (Cox-Voinov) or molecular-kinetic theory models, highlighting the originality of the dynamics reported when extremely high capillary numbers are achieved. Upon bubble collapse, spherical persistent microbubbles are created and partly dispersed in water, whereas the high-viscous polyalphaolefines lead to long-standing oblate persistent bubbles sticking to the target's surface, independent of the ablated target. Overall, liquid's viscosity determines laser ablation-induced cavitation. © 2020 Author(s).
    view abstract10.1063/1.5116111
  • 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 (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 abstract10.1016/j.procir.2020.09.009
  • 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 abstract10.1088/1361-6528/ab55bd
  • Evaluation of essential powder properties through complementary particle size analysis methods for laser powder bed fusion of polymers
    Sommereyns, A. and Hupfeld, T. and Gökce, B. and Barcikowski, S. and Schmidt, M.
    Procedia CIRP 94 (2020)
    The resolution of complex parts produced by laser powder bed fusion of polymers (PBF-LB/P) is defined significantly by the shape and size distribution of the feedstock powder. Its analysis is usually performed by optical measurement systems such as laser diffraction or image analysis. In this study, the most relevant particle size parameters will be extracted from a set of different measuring methods, as well as the Hausner ratio and finally discussed regarding safe and successful processability. Extracted data include the sphericity, fine fraction, volume- and number-weighted diameter distributions, and statistical significance analysis, including comparison of PA12 and carbon-black-additivated PA12. The presented results should give researchers a first impression about the suitability of polymer powders for PBF-LB/P, based on powder feedstock characterization. © 2020 The Authors. Published by Elsevier B.V.
    view abstract10.1016/j.procir.2020.09.023
  • How colloidal surface additivation of polyamide 12 powders with well-dispersed silver nanoparticles influences the crystallization already at low 0.01 vol%
    Hupfeld, T. and Sommereyns, A. and Schuffenhauer, T. and Zhuravlev, E. and Krebs, M. and Gann, S. and Keßler, O. and Schmidt, M. and Gökce, B. and Barcikowski, S.
    Additive Manufacturing 36 (2020)
    As Additive Manufacturing (AM) is fast-growing, properties adaption of feedstock materials for AM is becoming more and more relevant due to high quality standards in industrial applications. Compared to traditional manufacturing techniques like injection molding, laser powder bed fusion (PBF-LB) of polymers has a very limited variety of processable materials, which is a major obstacle for future growth. Nanocomposites are an established material class for addressing the limitations in PBF-LB but often show poor dispersion of the nanomaterial in/on the polymer powder. Especially in the context of plasmonic nanomaterials and composites, where the state of aggregation considerably influences the optical properties, dispersion plays an important role. Our study presents a deeper understanding of the colloidal surface additivation of polyamide 12 (PA12) powders with laser-generated plasmonic silver nanoparticles, leading to high dispersion of the nanoparticles on the micropowder surface with good reproducibility. The additivation is ruled by colloidal stability and control of electrostatic forces between particles and resulted in powders that could successfully be processed on a PBF-LB machine to generate plasmonic-functionalized parts. Finally, we introduce the surface specific nanoparticle dose (surf%) as scaling key parameter complementary to the commonly used mass specific dose (wt%) to appropriately describe nanoparticle load, proving the effect of such surface additivation on the recrystallization behavior of PA12. Via flash calorimetry, already at 0.01 vol% silver load, significant nanoparticle-induced heterogeneous nucleation effects are evident, whereas the thermal properties analyzed by conventional calorimetry remain unaffected. © 2020 Elsevier B.V.
    view abstract10.1016/j.addma.2020.101419
  • In situ speciation and spatial mapping of Zn products during pulsed laser ablation in liquids (PLAL) by combined synchrotron methods
    Reich, S. and Göttlicher, J. and Ziefuss, A. and Streubel, R. and Letzel, A. and Menzel, A. and Mathon, O. and Pascarelli, S. and Baumbach, T. and Zuber, M. and Gökce, B. and Barcikowski, S. and Plech, A.
    Nanoscale 12 (2020)
    Pulsed laser ablation in liquids is a hierarchical multi-step process to produce pure inorganic nanoparticle colloids. Controlling this process is hampered by the partial understanding of individual steps and structure formation. In situ X-ray methods are employed to resolve macroscopic dynamics of nanosecond PLAL as well to analyse the distribution and speciation of ablated species with a microsecond time resolution. High time resolution can be achieved by synchrotron-based methods that are capable of 'single-shot' acquisition. X-ray multicontrast imaging by a Shack-Hartmann setup (XHI) and small angle X-ray scattering (SAXS) resolve evolving nanoparticles inside the transient cavitation bubble, while X-ray absorption spectroscopy in dispersive mode opens access to the total material yield and the chemical state of the ejecta. It is confirmed that during ablation nanoparticles are produced directly as well as reactive material is detected, which is identified in the early stage as Zn atoms. Nanoparticles within the cavitation bubble show a metal signature, which prevails for milliseconds, before gradual oxidation sets in. Ablation is described by a phase explosion of the target coexisting with full evaporation. Oxidation occurs only as a later step to already formed nanoparticles. © 2020 The Royal Society of Chemistry.
    view abstract10.1039/d0nr01500h
  • Increasing the size-selectivity in laser-based g/h liquid flow synthesis of pt and ptpd nanoparticles for co and no oxidation in industrial automotive exhaust gas treatment benchmarking
    Dittrich, S. and Kohsakowski, S. and Wittek, B. and Hengst, C. and Gökce, B. and Barcikowski, S. and Reichenberger, S.
    Nanomaterials 10 (2020)
    PtPd catalysts are state-of-the-art for automotive diesel exhaust gas treatment. Although wet-chemical preparation of PtPd nanoparticles below 3 nm and kg-scale synthesis of supported PtPd/Al2 O3 are already established, the partial segregation of the bimetallic nanoparticles remains an issue that adversely affects catalytic performance. As a promising alternative, laser-based catalyst preparation allows the continuous synthesis of surfactant-free, solid-solution alloy nanoparticles at the g/h-scale. However, the required productivity of the catalytically relevant size fraction <10 nm has yet to be met. In this work, by optimization of ablation and fragmentation conditions, the continuous flow synthesis of nanoparticles with a productivity of the catalytically relevant size fraction <10 nm of >1 g/h is presented via an in-process size tuning strategy. After the laser-based preparation of hectoliters of colloid and more than 2 kg of PtPd/Al2 O3 wash coat, the laser-generated catalysts were benchmarked against an industry-relevant reference catalyst. The conversion of CO by laser-generated catalysts was found to be equivalent to the reference, while improved activity during NO oxidation was achieved. Finally, the present study validates that laser-generated catalysts meet the size and productivity requirements for industrial standard operating procedures. Hence, laser-based catalyst synthesis appears to be a promising alternative to chemical-based preparation of alloy nanoparticles for developing industrial catalysts, such as those needed in the treatment of exhaust gases. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.
    view abstract10.3390/nano10081582
  • 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 (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 abstract10.1021/acsabm.0c00297
  • 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 (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 abstract10.1002/cssc.201903186
  • Manipulation of the size and phase composition of yttrium iron garnet nanoparticles by pulsed laser post-processing in liquid
    Hupfeld, T. and Stein, F. and Barcikowski, S. and Gökce, B. and Wiedwald, U.
    Molecules 25 (2020)
    Modification of the size and phase composition of magnetic oxide nanomaterials dispersed in liquids by laser synthesis and processing of colloids has high implications for applications in biomedicine, catalysis and for nanoparticle-polymer composites. Controlling these properties for ternary oxides, however, is challenging with typical additives like salts and ligands and can lead to unwanted byproducts and various phases. In our study, we demonstrate how additive-free pulsed laser post-processing (LPP) of colloidal yttrium iron oxide nanoparticles using high repetition rates and power at 355 nm laser wavelength can be used for phase transformation and phase purification of the garnet structure by variation of the laser fluence as well as the applied energy dose. Furthermore, LPP allows particle size modification between 5 nm (ps laser) and 20 nm (ns laser) and significant increase of the monodispersity. Resulting colloidal nanoparticles are investigated regarding their size, structure and temperature-dependent magnetic properties. © 2020 by the authors.
    view abstract10.3390/molecules25081869
  • 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 abstract10.1088/1361-6528/ab94da
  • 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 (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 abstract10.1021/acs.jpcc.0c06257
  • Picosecond laser-induced surface structures on alloys in liquids and their influence on nanoparticle productivity during laser ablation
    Nadarajah, R. and Barcikowski, S. and Gökce, B.
    Optics Express 28 (2020)
    The productivity of nanoparticles formed by laser ablation of gold-silver and iron-gold alloy as well as copper and iron-nickel alloy targets in water is correlated with the formation of laser-induced surface structures. At a laser fluence optimized for maximum nanoparticle productivity, it is found that a binary alloy with an equimolar ratio forms laser-induced periodic surface structures (LIPSS) after ablation, if one of the constituent metals also form LIPSS. The ablation rate of nanoparticles linearly depends on the laser fluence if LIPSS is not formed, while a logarithmic trend and a decrease in productivity is evident when LIPSS is formed. To cancel LIPSS formation and recover from this decrease, a change to circularly polarized light is performed and an increase in nanoparticle productivity of more than 30% is observed. © 2020 Optical Society of America under the terms of the OSA Open Access Publishing Agreement
    view abstract10.1364/OE.28.002909
  • Plasmonic Seasoning: Giving Color to Desktop Laser 3D Printed Polymers by Highly Dispersed Nanoparticles
    Hupfeld, T. and Wegner, A. and Blanke, M. and Doñate-Buendía, C. and Sharov, V. and Nieskens, S. and Piechotta, M. and Giese, M. and Barcikowski, S. and Gökce, B.
    Advanced Optical Materials 8 (2020)
    Material development is key for continuing the exponential growth in the field of 3D printing. However, 3D printing of polymers by laser powder bed fusion (PBF-LB) still is limited to a few polymer powder materials, which restricts the range of applications. Tailoring the chemical, rheological, mechanical, or optical properties of the feedstock powder to the requirements of the laser printing process poses a significant challenge. In order to meet global trends in the commercialization of desktop 3D printers, the use of inexpensive and compact diode lasers for PBF-LB in the visible or near-infrared range is highly desired. However, at present, only black objects can be printed by desktop laser printers since only commercial carbon black-based composite powders meet their laser absorption requirements. In this study, a route for tuning the absorption properties of thermoplastic polyurethane polymers and incorporating color into printed objects by using minute amounts (i.e., 0.01 vol%) of highly dispersed plasmonic silver nanoparticles is reported, presenting a new way for colored parts to be produced through laser 3D printing. © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstract10.1002/adom.202000473
  • Recent progress in laser materials processing and synthesis
    Gökce, B. and Filipescu, M. and Barcikowski, S.
    Applied Surface Science 513 (2020)
    view abstract10.1016/j.apsusc.2020.145762
  • Research trends in laser powder bed fusion of Al alloys within the last decade
    Kusoglu, I.M. and Gökce, B. and Barcikowski, S.
    Additive Manufacturing 36 (2020)
    Research on Laser Powder Bed Fusion (L-PBF) of Al alloy powders increased exponentially over the last decade, and Al powders have become the third most studied metal alloy composition for L-PBF. This study evaluates the trends of the literature in this field to understand which material properties, process properties, and as-built part properties were decisive and of interest for L-PBF processing within the last decade. Even though the effect of the powder properties is often not discussed in detail within the studied 100 referenced Sci-Index articles, it was found that the use of particulate additives in Al powders overcame the main processing and metallurgic problems, such as anisotropic microstructure, segregations, and crack formation in the as-built parts during L-PBF. By quantifying related statistics and extracting data from the studied articles, it is found that powder size ranges of Al feedstock powders overlap in a narrower size range. AlSi10Mg is the most studied alloy; it is a eutectic Al composition that avoids the problems associated with resolidification in L-PBF. The latest research trends focused on additives for grain refinement to improve the mechanical properties and to avoid crack sensitivity in the as-built Al-Zn-Mg-(Cu) and Al-Cu-Mg parts. Additives are found to be promising to industrialize new Al alloy compositions in L-PBF. A Principle Component Analysis is carried out to determine the correlation between reported material, process, and as-built part properties. © 2020 Elsevier B.V.
    view abstract10.1016/j.addma.2020.101489
  • Room-Temperature Laser Synthesis in Liquid of Oxide, Metal-Oxide Core-Shells, and Doped Oxide Nanoparticles
    Amendola, V. and Amans, D. and Ishikawa, Y. and Koshizaki, N. and Scirè, S. and Compagnini, G. and Reichenberger, S. and Barcikowski, S.
    Chemistry - A European Journal 26 (2020)
    Although oxide nanoparticles are ubiquitous in science and technology, a multitude of compositions, phases, structures, and doping levels exist, each one requiring a variety of conditions for their synthesis and modification. Besides, experimental procedures are frequently dominated by high temperatures or pressures and by chemical contaminants or waste. In recent years, laser synthesis of colloids emerged as a versatile approach to access a library of clean oxide nanoparticles relying on only four main strategies running at room temperature and ambient pressure: laser ablation in liquid, laser fragmentation in liquid, laser melting in liquid and laser defect-engineering in liquid. Here, established laser-based methodologies are reviewed through the presentation of a panorama of oxide nanoparticles which include pure oxidic phases, as well as unconventional structures like defective or doped oxides, non-equilibrium compounds, metal-oxide core–shells and other anisotropic morphologies. So far, these materials showed several useful properties that are discussed with special emphasis on catalytic, biomedical and optical application. Yet, given the endless number of mixed compounds accessible by the laser-assisted methodologies, there is still a lot of room to expand the library of nano-crystals and to refine the control over products as well as to improve the understanding of the whole process of nanoparticle formation. To that end, this review aims to identify the perspectives and unique opportunities of laser-based synthesis and processing of colloids for future studies of oxide nanomaterial-oriented sciences. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
    view abstract10.1002/chem.202000686
  • Scaling up colloidal surface additivation of polymer powders for laser powder bed fusion
    Hupfeld, T. and Doñate-Buendía, C. and Krause, M. and Sommereyns, A. and Wegner, A. and Sinnemann, T. and Schmidt, M. and Gökce, B. and Barcikowski, S.
    Procedia CIRP 94 (2020)
    Nanoadditivation of polymer materials has high potential to meet the needs of material modification for laser powder bed fusion (PBF-LB/P), e.g. by tuning optical or mechanical properties. Colloidal additivation of polymer powders has proven to avoid aggregation of nanofillers on the polymer surface during additivation. In our study, we demonstrate kg-scale, continuous colloidal surface additivation of polymer powders to generate sufficient amounts for PBF-LB/P process development and manufacturing of test specimens. Furthermore, colloidal additivation achieves a high surface coverage even at low wt% and allows PBF-LB/P with CO2 and diode lasers to form parts preserving the superior nanoparticle dispersion within TPU and PA12. © 2020 The Authors. Published by Elsevier B.V.
    view abstract10.1016/j.procir.2020.09.022
  • Selective Aerobic Oxidation of 5-(Hydroxymethyl)furfural over Heterogeneous Silver-Gold Nanoparticle Catalysts
    Schade, O.R. and Stein, F. and Reichenberger, S. and Gaur, A. and Saraҫi, E. and Barcikowski, S. and Grunwaldt, J.-D.
    Advanced Synthesis and Catalysis 362 (2020)
    Bimetallic silver-gold alloy nanoparticles on zirconia with varying Ag/Au ratios were designed by a rational approach and tested as catalysts for the selective oxidation of the promising biomass platform molecule 5-(hydroxymethyl)furfural (HMF). For this purpose, colloidal AgxAu10-x particles with molar compositions x=1/3/5/7/9 were prepared by laser ablation in liquids, a surfactant-free method for the preparation of highly pure nanoparticles, before adsorption on zirconia. In-depth characterization of the supported catalysts evidenced alloyed nanoparticles with distinct trends of the surface and bulk composition depending on the overall Ag/Au molar ratio as determined by X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS), respectively. To uncover the synergistic effect of the Ag/Au ratio, the catalysts were further studied in terms of the catalytic activity and selectivity in HMF oxidation. Either the aldehyde moiety or both functional groups of HMF were selectively oxidized depending on the Ag/Au composition resulting in 5-hydroxymethyl-2-furan-carboxylic acid (HFCA) or 2,5-furandicarboxylic acid (FDCA), respectively. Optimization of the reaction conditions allowed the quantitative production of HFCA over most catalysts, also after re-use. Only gold rich catalysts Ag1Au9/ZrO2 and particularly Ag3Au7/ZrO2 were highly active in FDCA synthesis. While Ag3Au7/ZrO2 deactivated upon re-use due to sintering, no structural changes were observed for the other catalysts and all catalysts were stable against metal leaching. The present work thus provides fundamental insights into the synergistic effect of Ag and Au in alloyed nanoparticles as active and stable catalysts for the oxidation of HMF. (Figure presented.). © 2020 The Authors. Advanced Synthesis & Catalysis published by Wiley-VCH GmbH
    view abstract10.1002/adsc.202001003
  • 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 Saénz, J.J. and Maier, S.A. and Stefani, F.D.
    Proceedings of SPIE - The International Society for Optical Engineering 11297 (2020)
    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 by tuning the light wavelength to their size-dependent magnetic dipolar resonance. © 2020 SPIE.
    view abstract10.1117/12.2539265
  • Synthesis of Fluorescent Silver Nanoclusters: Introducing Bottom-Up and Top-Down Approaches to Nanochemistry in a Single Laboratory Class
    Zhu, L. and Gharib, M. and Becker, C. and Zeng, Y. and Ziefuß, A.R. and Chen, L. and Alkilany, A.M. and Rehbock, C. and Barcikowski, S. and Parak, W.J. and Chakraborty, I.
    Journal of Chemical Education 97 (2020)
    A laboratory class was developed and evaluated to illustrate the synthesis of metal nanoclusters (NCs) and to explain their photoluminescence properties for the case of silver. The described experiment employs a synthetic protocol that consists of two sequential phases in a single reaction pot: The reduction of silver ions into plasmonic silver nanoparticles (NPs) (bottom-up), followed by etching the formed silver NPs into ultrasmall atomically precise fluorescent silver NCs (top-down), Ag29(DHLA)12 (DHLA: Dihydrolipoic acid). UV-vis absorption and fluorescence spectroscopy were employed as a function of reaction time to confirm the development of the plasmonic character of silver NPs (reaction intermediate) and, later on, the onset of fluorescence emission of the silver NCs (final product). Collectively, this experiment was found to be simple to carry out, safe, reproducible, and cost-effective, and it achieved the intended learning outcomes. Participating students found this laboratory class suitable to be implemented into an upper-division undergraduate or graduate curriculum. Copyright © 2019 American Chemical Society and Division of Chemical Education, Inc.
    view abstract10.1021/acs.jchemed.9b00342
  • The effect of downstream laser fragmentation on the specific surface area and photoelectrochemical performance of barium tantalum oxynitride
    Haydous, F. and Waag, F. and Si, W. and Li, F. and Barcikowski, S. and Gökce, B. and Lippert, T.
    Applied Surface Science 510 (2020)
    One approach to improve the photoelectrochemical solar water splitting performance of photoanodes based on oxynitride perovskite particles is through increasing the active surface area which allows the generation of more electron-hole pairs that contribute in the water reduction and oxidation reactions. In this study, we explore the pros and cons of downstream laser fragmentation as a method to increase the specific surface area of oxynitride particles and highlight the important issues that must be considered for effective solar water splitting. The synthesis of particles with a high surface area of up to 32.4 m2 g−1 is demonstrated. Furthermore, the fragmented oxynitrides revealed lower absorbance values, a blue shift in the absorption edge and a higher background absorbance. These observations, in addition to the lower crystalline quality of the fragmented oxynitrides, were attributed to the loss of N content during fragmentation and the formation of secondary phases. The photoanodes based on the fragmented particles showed lower photocurrents than those prepared from the un-fragmented particles even though the surface area was increased. The decrease in photoactivity was ascribed to the presence of more grain boundaries in the fragmented oxynitride photoanodes which leads to more recombinations of the photogenerated carriers. Interestingly, after seven fragmentation passages, the photocurrent starts to increase again due to the formation of an amorphous layer which improves the transport of the photogenerated carriers. © 2020
    view abstract10.1016/j.apsusc.2020.145429
  • Use of (nano-)additives in Laser Powder Bed Fusion of Al powder feedstocks: Research directions within the last decade
    Kusoglu, I.M. and Gökce, B. and Barcikowski, S.
    Procedia CIRP 94 (2020)
    An exponential increase for the number of Scientific Citation Index (SCI) expanded articles in the field of Laser Powder Bed Fusion (L-PBF) of metal powder feedstocks are generated within the last decade. Al powder feedstocks have become one of the most cited metal alloys in this field. By in-depth analyzing the experimental research data provided within SCI-expanded articles, it is obvious that material properties and laser process properties have a high impact to produce as-built parts with crack free microstructure, high density, high mechanical properties and high repetition rates of as-built parts. As a future research trend of using additive powders in Al powder feedstocks are found to be promising candidates to develop L-PBF of as-built Al parts. This study quantitatively evaluates the effect of compositions and mass fractions on several Al alloy powder feedstocks by extracting research data given in the SCI-expanded articles. The latest research directions showed that several additives are useful to refine microstructure and to enhance the mechanical properties of as-built Al parts. The effect of additives on processability, as-built density, tensile properties, and flexural properties of several Al alloy parts are discussed. © 2020 The Authors. Published by Elsevier B.V.
    view abstract10.1016/j.procir.2020.09.003
  • 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 (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 abstract10.1016/j.apsusc.2018.10.030
  • 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 (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 abstract10.1016/j.apsusc.2019.02.080
  • Comparison of the productivity and ablation efficiency of different laser classes for laser ablation of gold in water and air
    Dittrich, S. and Streubel, R. and McDonnell, C. and Huber, H.P. and Barcikowski, S. and Gökce, B.
    Applied Physics A: Materials Science and Processing 125 (2019)
    In this study, we compare different laser systems used for the synthesis of nanoparticles. The productivity and ablation efficiency of laser ablation of gold in water and in air are determined for three pulsed laser systems with comparable pulse energy but different pulse duration and repetition rate. All experiments are performed in a fluence range of up to 20J/cm2. The highest productivity among the considered lasers is found for a high-power picosecond laser, which shows 12 times higher ablation rate for the ablation in air compared to ablation in liquid. Further, we find that the threshold fluence for ablation in air is up to 1.9 times higher than for ablation in water. The highest ablation efficiency, which is defined as an energy specific ablation volume by the ablation rate divided by the laser power, is found for the low power, compact nanosecond laser system. © 2019, Springer-Verlag GmbH Germany, part of Springer Nature.
    view abstract10.1007/s00339-019-2704-8
  • Correction: Determining the role of redox-active materials during laser-induced water decomposition (Physical Chemistry Chemical Physics (2019) 21 (18636-18651) DOI: 10.1039/C9CP02663K)
    Kalus, M.-R. and Lanyumba, R. and Lorenzo-Parodi, N. and Jochmann, M.A. and Kerpen, K. and Hagemann, U. and Schmidt, T.C. and Barcikowski, S. and Gökce, B.
    Physical Chemistry Chemical Physics 21 (2019)
    The authors would like to correct Fig. 6d. The values on the y-axis were incorrectly scaled by a factor of 100 which makes no sense from chemical point of view. The corrected figure is shown below. Note that the correction of this figure will not change the core message of the manuscript,1 as the statements in the text refer to the qualitative trend. (Figure Presented). The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers. © 2019 the Owner Societies.
    view abstract10.1039/c9cp90263e
  • Determining the role of redox-active materials during laser-induced water decomposition
    Kalus, M.-R. and Lanyumba, R. and Lorenzo-Parodi, N. and Jochmann, M.A. and Kerpen, K. and Hagemann, U. and Schmidt, T.C. and Barcikowski, S. and Gökce, B.
    Physical Chemistry Chemical Physics 21 (2019)
    Laser ablation in liquids (LAL) drives the decomposition of the liquid inducing the formation of a large number of different redox equivalents and gases. This not only leads to shielding effects and a decrease of the nanoparticle (NP) productivity but also can directly affect the NP properties such as the oxidation degree. In this study, we demonstrate that liquid decomposition during laser ablation in water is triggered by the redox activity of the 7 different bulk materials used; Au, Pt, Ag, Cu, Fe, Ti and Al, as well as by the reactivity of water with the plasma. Laser ablation of less-noble metals like aluminum leads to a massive gas evolution up to 390 cm3 per hour with molar hydrogen to oxygen ratios of 17.1. For more noble metals such as gold and platinum, water splitting induced by LAL is the dominant feature leading to gas volume formation rates of 10 up to 30 cm3 per hour and molar hydrogen to oxygen ratios of 1.2. We quantify the material-dependent ablation rate, shielding effects as well as the amount of hydrogen peroxide produced, directly affecting the yield and oxidation of the nanoparticles on the long-time scale. © 2019 the Owner Societies.
    view abstract10.1039/c9cp02663k
  • 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 (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 abstract10.1016/j.apsusc.2018.09.224
  • 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 (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 abstract10.1016/j.apsusc.2018.10.061
  • Early appearance of crystalline nanoparticles in pulsed laser ablation in liquids dynamics
    Reich, S. and Letzel, A. and Menzel, A. and Kretzschmar, N. and Gökce, B. and Barcikowski, S. and Plech, A.
    Nanoscale 11 (2019)
    The size and crystallinity of gold and silver nanoparticles during the process of pulsed laser ablation in water (PLAL) is investigated with microsecond and sub-microsecond time resolution. While basic observations have already been established, such as detection of particles inside the cavitation bubble, trapping of ablated matter by the bubble or the action of size quenching on a sub-millisecond time scale, the structure formation mechanism is still a matter of debate. Quantifying the nanoparticle release and crystallinity close to the irradiated metal target by wide and small angle X-ray scattering reveals the presence of nanoparticles ahead of the developing vapour bubble and inside the bubble. While the (temporal) distribution is in agreement with a homogeneously particle-filled bubble, solid particles are detected at the advancing bubble front. Wide-angle X-ray scattering confirms the crystalline nature of these large particles. This reveals that for picosecond ablation the expulsion of condensed phases of material during the ablation process adds significantly to the bimodal size distribution, relating to recent models of film lift-off and liquid metal Rayleigh instabilities. © 2019 The Royal Society of Chemistry.
    view abstract10.1039/c9nr01203f
  • 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 (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 abstract10.1021/acsaem.9b01103
  • 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 (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 abstract10.1016/j.apsusc.2018.10.145
  • How the re-irradiation of a single ablation spot affects cavitation bubble dynamics and nanoparticles properties in laser ablation in liquids
    Letzel, A. and Santoro, M. and Frohleiks, J. and Ziefuß, A.R. and Reich, S. and Plech, A. and Fazio, E. and Neri, F. and Barcikowski, S. and Gökce, B.
    Applied Surface Science 473 (2019)
    Fundamental theoretical and experimental studies on the formation of nanoparticles and cavitation during laser synthesis of colloids usually employ single-pulse conditions, whereas studies of the properties of nanoparticles naturally require prolonged ablation. We explored how a defined number of pulses changes a silver target's surface geometry and thereby the dynamics of the laser-induced cavitation bubble and the resulting properties of the nanoparticles. The shape of the cavitation bubble transforms from hemispherical to almost spherical. The indirectly calculated mass concentration in the cavitation bubble follows a decay with the number of laser pulses. Surprisingly, the ablated mass does not set the volume of the extended cavitation bubble, as one would expect, because of the linear dependency of both the volume of the bubble and the ablation mass per pulse on the laser fluence. No influence of the altered cavitation bubble on the nanoparticles was identified. Instead, clear evidence of a high share of silver nanoclusters (d < 3 nm) with improved instrumentation (ultracentrifuge) was found in all samples at our low concentration conditions. The influence of these reactive species on the final particle size was found to be much larger than the cavitation bubble variations caused by prolonged surface ablation. In addition, no correlation was observed between the size of the primary particles (∼8 nm) and the mass concentration in the cavitation bubble. © 2018
    view abstract10.1016/j.apsusc.2018.12.025
  • Impact of Preparation Method and Hydrothermal Aging on Particle Size Distribution of Pt/γ-Al 2 O 3 and Its Performance in CO and NO Oxidation
    Ogel, E. and Casapu, M. and Doronkin, D.E. and Popescu, R. and Störmer, H. and Mechler, C. and Marzun, G. and Barcikowski, S. and Türk, M. and Grunwaldt, J.-D.
    Journal of Physical Chemistry C (2019)
    The influence of the preparation method and the corresponding particle size distribution on the hydrothermal deactivation behavior at 600-800 °C and performance during CO/NO oxidation was systematically investigated for a series of Pt/Al 2 O 3 catalysts. Representative conventional (incipient wetness impregnation) and advanced preparation methods (flame spray pyrolysis, supercritical fluid reactive deposition, and laser ablation in liquid) were selected, which generated samples containing narrow and homogeneous but also heterogeneous particle size distributions. Basic characterization was conducted by inductively coupled plasma-optical emission spectrometry, N 2 physisorption, and X-ray diffraction. The particle size distribution and the corresponding oxidation state were analyzed using transmission electron microscopy and X-ray absorption spectroscopy. The systematic study shows that oxidized Pt nanoparticles smaller than 2 nm sinter very fast, already at 600 °C, but potential chlorine traces from the catalyst precursor seem to stabilize Pt nanoparticles against further sintering and consequently maintain the catalytic performance. Samples prepared by flame spray pyrolysis and laser ablation showed a superior hydrothermal resistance of the alumina support, although, due to small interparticle distance in case of laser synthesized particles, the particle size distribution increases considerably at high temperatures. Significant deceleration of the noble metal sintering process was obtained for the catalysts containing homogeneously distributed but slightly larger Pt nanoparticles (supercritical fluid reactive deposition) or for particles deposited on a thermally stable alumina support (flame spray pyrolysis). The correlations obtained between Pt particle size distribution, oxidation state, and catalytic performance indicate different trends for CO and NO oxidation reactions, in line with their structure sensitivity. © 2019 American Chemical Society.
    view abstract10.1021/acs.jpcc.8b11065
  • Impact of Preparation Method and Hydrothermal Aging on Particle Size Distribution of Pt/γ-Al2O3 and Its Performance in CO and NO Oxidation
    Ogel, E. and Casapu, M. and Doronkin, D.E. and Popescu, R. and Störmer, H. and Mechler, C. and Marzun, G. and Barcikowski, S. and Türk, M. and Grunwaldt, J.-D.
    Journal of Physical Chemistry C 123 (2019)
    The influence of the preparation method and the corresponding particle size distribution on the hydrothermal deactivation behavior at 600-800 °C and performance during CO/NO oxidation was systematically investigated for a series of Pt/Al2O3 catalysts. Representative conventional (incipient wetness impregnation) and advanced preparation methods (flame spray pyrolysis, supercritical fluid reactive deposition, and laser ablation in liquid) were selected, which generated samples containing narrow and homogeneous but also heterogeneous particle size distributions. Basic characterization was conducted by inductively coupled plasma-optical emission spectrometry, N2 physisorption, and X-ray diffraction. The particle size distribution and the corresponding oxidation state were analyzed using transmission electron microscopy and X-ray absorption spectroscopy. The systematic study shows that oxidized Pt nanoparticles smaller than 2 nm sinter very fast, already at 600 °C, but potential chlorine traces from the catalyst precursor seem to stabilize Pt nanoparticles against further sintering and consequently maintain the catalytic performance. Samples prepared by flame spray pyrolysis and laser ablation showed a superior hydrothermal resistance of the alumina support, although, due to small interparticle distance in case of laser synthesized particles, the particle size distribution increases considerably at high temperatures. Significant deceleration of the noble metal sintering process was obtained for the catalysts containing homogeneously distributed but slightly larger Pt nanoparticles (supercritical fluid reactive deposition) or for particles deposited on a thermally stable alumina support (flame spray pyrolysis). The correlations obtained between Pt particle size distribution, oxidation state, and catalytic performance indicate different trends for CO and NO oxidation reactions, in line with their structure sensitivity. © 2019 American Chemical Society.
    view abstract10.1021/acs.jpcc.8b11065
  • Incubation Effect of Pre-Irradiation on Bubble Formation and Ablation in Laser Ablation in Liquids
    Reich, S. and Letzel, A. and Gökce, B. and Menzel, A. and Barcikowski, S. and Plech, A.
    ChemPhysChem 20 (2019)
    Pulsed laser ablation in liquids (PLAL) is a multi-scale process, which is widely studied either in batch ablation with prolonged target irradiation as well as mechanistic investigations, in a defined (single-shot) process. However, fundamental studies on defined pulse series are rare. We have investigated the effect of a developing rough morphology of the target surface on the PLAL process with nanosecond pulses and, partially, picosecond pulses. At low fluence the cavitation bubble growth as well as the ablation yield depend on the irradiation history of the target. The bubble size increases with repeated irradiation on one spot for the first 2–30 pulses as well as with the applied dose. This is discussed within the framework of incubation effects. Incubation is found to be important, resulting in a bubble volume increase by a factor of six or more between pristine and corrugated targets. The target surface, changing from smooth to corrugated, induces a more efficient localization of laser energy at the solid-liquid interface. This is accompanied by a suppressed reflectivity and more efficient coupling of energy into the laser-induced plasma. Thus, the cavitation bubble size increases as well as ablation being enhanced. At high fluence, such incubation is masked by the rapid development of surface damage within the first shots, which eventually would lead to a reduction of bubble sizes. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstract10.1002/cphc.201900075
  • Kinetically-controlled laser-synthesis of colloidal high-entropy alloy nanoparticles
    Waag, F. and Li, Y. and Ziefuß, A.R. and Bertin, E. and Kamp, M. and Duppel, V. and Marzun, G. and Kienle, L. and Barcikowski, S. and Gökce, B.
    RSC Advances 9 (2019)
    The single-step incorporation of multiple immiscible elements into colloidal high-entropy alloy (HEA) nanoparticles has manifold technological potential, but it continues to be a challenge for state-of-the-art synthesis methods. Hence, the development of a synthesis approach by which the chemical composition and phase of colloidal HEA nanoparticles can be controlled could lead to a new pool of nanoalloys with unparalleled functionalities. Herein, this study reports the single-step synthesis of colloidal CoCrFeMnNi HEA nanoparticles with targeted equimolar stoichiometry and diameters less than 5 nm by liquid-phase, ultrashort-pulsed laser ablation of the consolidated and heat-treated micropowders of the five constituent metals. Further, the scalability of the process with an unprecedented productivity of 3 grams of colloidal HEA nanoparticles per hour is demonstrated. Electrochemical analysis reveals a unique redox behavior of the particles' surfaces in an alkaline environment and a potential for future application as a heterogeneous catalyst for the oxygen evolution reaction. © 2019 The Royal Society of Chemistry.
    view abstract10.1039/c9ra03254a
  • Materials synthesis in a bubble
    Barcikowski, S. and Plech, A. and Suslick, K.S. and Vogel, A.
    MRS Bulletin 44 (2019)
    Ultrasonic sonochemistry and pulsed laser ablation in liquids (LAL) are modern techniques for materials synthesis that are in different ways linked to the formation and collapse of cavitation bubbles. We provide an overview of the physics of laser-induced and acoustically driven bubble oscillations and then describe how the high pressures and temperatures associated with ablation and bubble collapse, as well as emitted shock waves, take part in material synthesis inside and around the bubble. Emphasis is placed on the mechanisms of sonochemical synthesis and modification, and on a step-by-step account of the events from laser ablation through interaction of ablation products with the surrounding liquid up to the modification or aggregation of particles within the bubble. Both sonochemistry and LALs yield nanostructured materials and colloidal nanoparticles with unique properties. The synthesis process has been demonstrated to be scalable. Copyright © Materials Research Society 2019.
    view abstract10.1557/mrs.2019.107
  • One-step synthesis of Fe-Au core-shell magnetic-plasmonic nanoparticles driven by interface energy minimization
    Tymoczko, A. and Kamp, M. and Rehbock, C. and Kienle, L. and Cattaruzza, E. and Barcikowski, S. and Amendola, V.
    Nanoscale Horizons 4 (2019)
    Directing the assembly of atoms into core-shell particles generally requires elegant but sophisticated procedures. Here we show how the thermodynamic driving force to minimization of surface and interface energy can be exploited to produce colloidal Fe-Au core-shell nanoparticles in one step and with a yield approaching 99.7% in mass. This is obtained by laser ablation with nanosecond pulses of thin bimetallic films immersed in acetone. The Fe-Au core-shell nanoparticles show magnetic and plasmonic properties, and a surface available to bioconjugation and analytical assays. This laser assisted synthetic method represents a step forward in the facile preparation of core-shell nanospheres with multiple appealing functionalities. © 2019 The Royal Society of Chemistry.
    view abstract10.1039/c9nh00332k
  • Perspective of Surfactant-Free Colloidal Nanoparticles in Heterogeneous Catalysis
    Reichenberger, S. and Marzun, G. and Muhler, M. and Barcikowski, S.
    ChemCatChem 11 (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, Weinheim
    view abstract10.1002/cctc.201900666
  • 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 (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 abstract10.1016/j.apsusc.2018.10.257
  • 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 abstract10.1088/1361-6595/ab3dbe
  • 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 (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 abstract10.1021/acsphotonics.8b01619
  • Status and demand of research to bring laser generation of nanoparticles in liquids to maturity
    Amans, D. and Cai, W. and Barcikowski, S.
    Applied Surface Science 488 (2019)
    Nanoparticles are already implemented as functional elements on surfaces and into volume, but also in hybrid nanostructures. Each application requires specific features regarding size, morphology, surface chemistry, purity, colloidal stability, defects, or doping. However, integration of the “nano-function” into products is still limited due to drawbacks of gas phase and chemical synthesis methods regarding particle aggregation and contamination by adsorbates causing deactivation of their surfaces. In addition, thermodynamically-controlled synthesis methods naturally face limited access to alloy nanoparticle systems with miscibility gaps. The development of new synthesis methods which can be reliably scaled up to industrial levels of production is mandatory to overcome these limitations and then widen the application prospectives of nanomaterials. Since the nineties, Laser Ablation in Liquids (LAL) has proven its reliability and its versatility to synthesize colloidal nanoparticles. More generally, laser/matter interaction in liquids offers several synthesis routes for nanoparticle generation. In addition to LAL, Laser Melting in Liquids (LML), Laser Fragmentation in Liquids (LFL), as well as pulsed Laser Photoreduction/oxidation in Liquids (LPL), offer different routes to obtain colloids with controled nanoparticle sizes. We will present a digest of the breakthroughs achieved in the last years not only on the synthesis control, but also on the understanding of the basics. These achievements suggest that laser generation of nanoparticles in liquids is mature enough for industrial outlets of colloid production, with series products likely to approach the real world in the near future. © 2019 Elsevier B.V.
    view abstract10.1016/j.apsusc.2019.05.117
  • 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 (&lt;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 abstract10.1021/acs.langmuir.9b00418
  • 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 (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 abstract10.1021/acs.cgd.9b00175
  • 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 (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 abstract10.1021/acs.langmuir.8b01585
  • Tribological properties of laser-generated hard ceramic particles in a gear drive contact
    Jendrzej, S. and Gondecki, L. and Debus, J. and Moldenhauer, H. and Tenberge, P. and Barcikowski, S. and Gökce, B.
    Applied Surface Science 467-468 (2019)
    The lubricant is a central element in the transmission design. It primarily separates the two contact partners through a pressure-induced solidification in the lubrication gap, thus enabling the operation of heavily loaded sliding-rolling contacts. On the one hand, the quality and properties of a lubricant depend on the base oils, which differ by their viscosity and process-technological parameters. The addition of particulate additives gives the lubricants further functional properties that are not contained in the base oil. In this study, the influence of laser-synthesized yttria-stabilized zirconia nano- or submicrometer spheres as dispersed functional elements in the lubricant is studied, and their impact on wear and fatigue on the tooth flank is investigated. The work includes systematic investigations on the influence of the particle's shape and size by running tests on a FZG gear test rig. Finally, the potential of the laser-generated particles as a lubricant additive is evaluated in a first conclusion. © 2018 Elsevier B.V.
    view abstract10.1016/j.apsusc.2018.10.060
  • 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 (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 abstract10.1016/j.procir.2018.08.103
  • Corrigendum to “Quantification of mass-specific laser energy input converted into particle properties during picosecond pulsed laser fragmentation of zinc oxide and boron carbide in liquids” [Appl. Surf. Sci. 348 (September) (2015) 22–29] (S0169433214015815) (10.1016/j.apsusc.2014.07.053))
    Lau, M. and Barcikowski, S.
    Applied Surface Science 433 (2018)
    The authors want to add the following addendum as acknowledgement to the article: The authors thank Mrs. Kyra Kujawski (M.Sc.), who supported this research. Following an established method, Mrs. Kujawski performed several experiments for determination of the fragmentation efficiency process window (Fig. 2). In details she gained and analyzed all data points required to determine the fragmentation efficiency for laser fluences higher 10 mJ/cm2, as shown in Fig. 2. She obtained the data, calculated the diagrams in Fig. 5a–c and produced the material as well as the pictures thereof (Fig. 5d, middle and bottom picture). The SEM pictures in Figs. 1 and 4 are taken of the material produced by her. Her work also included the experiments, the generation of the data and its data preparation and analysis presented in Fig. S1, as well as sample synthesis for the SEM pictures in Fig. S2. Furthermore, she performed the experiments of ultra-sonication and the related analytics, as shown in Fig. S3. Moreover, she contributed to the determination of the optical bandgap and calculated the plots and data shown in Figs. S5 and S6, and Table S1. Her experimental work helped to gain important data for this comprehensive study. This scientific work is greatly acknowledged. © 2017
    view abstract10.1016/j.apsusc.2017.09.051
  • 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 (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 abstract10.1016/j.matchemphys.2017.12.080
  • Depositing laser-generated nanoparticles on powders for additive manufacturing of oxide dispersed strengthened alloy parts via laser metal deposition
    Streubel, R. and Wilms, M.B. and Doñate-Buendía, C. and Weisheit, A. and Barcikowski, S. and Schleifenbaum, J.H. and Gökce, B.
    Japanese Journal of Applied Physics 57 (2018)
    We present a novel route for the adsorption of pulsed laser-dispersed nanoparticles onto metal powders in aqueous solution without using any binders or surfactants. By electrostatic interaction, we deposit Y2O3 nanoparticles onto iron-chromium based powders and obtain a high dispersion of nano-sized particles on the metallic powders. Within the additively manufactured component, we show that the particle spacing of the oxide inclusion can be adjusted by the initial mass fraction of the adsorbed Y2O3 particles on the micropowder. Thus, our procedure constitutes a robust route for additive manufacturing of oxide dispersion-strengthened alloys via oxide nanoparticles supported on steel micropowders. © 2018 The Japan Society of Applied Physics.
    view abstract10.7567/JJAP.57.040310
  • 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 abstract10.3390/s18061775
  • How the crystal structure and phase segregation of Au-Fe alloy nanoparticles are ruled by the molar fraction and size
    Tymoczko, A. and Kamp, M. and Prymak, O. and Rehbock, C. and Jakobi, J. and Schürmann, U. and Kienle, L. and Barcikowski, S.
    Nanoscale 10 (2018)
    The application of an Au-Fe nanoalloy is determined by its internal phase structure. Our experimental and theoretical findings explain how the prevalence of either a core-shell or a disordered solid solution structure is ruled by the target composition and the particle diameter. Furthermore, we found metastable phases not predefined by the bulk phase diagram. © The Royal Society of Chemistry 2018.
    view abstract10.1039/c8nr03962c
  • Laser additive manufacturing of oxide dispersion strengthened steels using laser-generated nanoparticle-metal composite powders
    Wilms, M.B. and Streubel, R. and Frömel, F. and Weisheit, A. and Tenkamp, J. and Walther, F. and Barcikowski, S. and Schleifenbaum, J.H. and Gökce, B.
    Procedia CIRP 74 (2018)
    A new route for the synthesis of powder composites suitable for processing with laser additive manufacturing is demonstrated. The powder composites, consisting of micrometer-sized stainless steel powder, homogenously decorated with nano-scaled Y2O3 powder particles, are manufactured by laser processing of colloids and electrostatic deposition. Consolidated by laser metal deposition and selective laser melting, the resulting specimens show superior mechanical properties at elevated temperatures, caused by the nano-sized, homogenously distributed dispersoids. © 2018 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license.
    view abstract10.1016/j.procir.2018.08.093
  • Laser Fragmentation of Colloidal Gold Nanoparticles with High-Intensity Nanosecond Pulses is Driven by a Single-Step Fragmentation Mechanism with a Defined Educt Particle-Size Threshold
    Ziefuß, A.R. and Reichenberger, S. and Rehbock, C. and Chakraborty, I. and Gharib, M. and Parak, W.J. and Barcikowski, S.
    Journal of Physical Chemistry C 122 (2018)
    Laser-inducd fragmentation is a promising tool for controlling the particle size of ligand-free colloidal nanoparticles and to synthesize ligand-free gold nanoclusters. However, because the underlying mechanisms are not fully understood, increasing the yield of this process remains challenging. In this work, we examine the pulsed laser fragmentation of gold nanoparticles in liquid under statistical single-pulse conditions with high-fluence nanosecond pulses and correlate them with the educt particle size, number of pulses, and laser fluence. We conclusively prove that the fragmentation process of gold nanoparticles is a one-pulse and one-step event, which yields monomodal particles of 10 nm down to 2.8 +/- 0.1 nm when exceeding a pulse peak power of 1.6 × 1012 W/m2 and when all educt particles are larger than 13.4 nm. This size threshold for quantitative fragmentation fits well with the size limit of 13.1 nm calculated with respect to the evaporation-heat-energy balance. Furthermore, we found strong evidence that the number of irradiation cycles, varied within the regime of one to four laser pulses/colloid volume, can be used to tune the surface chemistry and surface charge of the resulting nanoparticles in an aqueous medium. © 2018 American Chemical Society.
    view abstract10.1021/acs.jpcc.8b04374
  • Oxide dispersion-strengthened alloys generated by laser metal deposition of laser-generated nanoparticle-metal powder composites
    Doñate-Buendía, C. and Frömel, F. and Wilms, M.B. and Streubel, R. and Tenkamp, J. and Hupfeld, T. and Nachev, M. and Gökce, E. and Weisheit, A. and Barcikowski, S. and Walther, F. and Schleifenbaum, J.H. and Gökce, B.
    Materials and Design 154 (2018)
    A new method is proposed for producing nanoparticle-metal composite powders for laser additive manufacturing of oxide-dispersion strengthened (ODS) alloys. Different composite powders containing laser-generated Y2O3 and yttrium iron garnet (YIG) nanoparticles were produced and consolidated by Laser Metal Deposition (LMD). The structural properties of the manufactured ODS alloys were analyzed, and their hardness, remnant porosity, and temperature-dependent compression behavior were characterized to study the effect of the composition and size of the nanoparticles on the structural and mechanical properties. While the structural analyses did not show significant differences between the processed samples within the limits of the characterization methods that were used, the temperature-dependent compression behavior showed an increase of up to 22 ± 11% in the high-temperature strength of the specimens that contained only 0.08 wt% of laser-generated nanoparticles. This increase is attributed to the dispersed and deagglomerated nature of the nanoparticles that were used during the powder-preparation step. © 2018 Elsevier Ltd
    view abstract10.1016/j.matdes.2018.05.044
  • 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 (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 abstract10.1016/j.apsusc.2017.11.130
  • Role of Citrate and NaBr at the Surface of Colloidal Gold Nanoparticles during Functionalization
    Dinkel, R. and Jakobi, J. and Ziefuß, A.R. and Barcikowski, S. and Braunschweig, B. and Peukert, W.
    Journal of Physical Chemistry C 122 (2018)
    A molecular understanding of the ligand shell and the functionalization process is essential for the development of surface-functionalized gold nanoparticles (AuNPs). Obviously, the initial ligand shell from the synthesis plays a crucial role in this process. Here, in situ second-harmonic scattering is applied to study the adsorption of a 3-mercapto-1-propanesulfonate (MPS) at the surface of laser-ablated NaBr- and citrate-stabilized AuNPs with sizes of 5 nm. This systematic comparison is possible due to the fact that laser ablation in micromolar saline water gives access to narrowly distributed colloidal AuNPs without organic stabilizers. The Gibbs free energy of adsorption was determined to be of similar order for both AuNP batches (ca. -40 kJ/mol). The surface concentration of MPS, however, differed strongly and was more than 30% higher for NaBr-stabilized AuNP than for citrate-stabilized AuNP. Compared to planar Au substrates, the surface concentration of MPS on NaBr-AuNP suggests formation of a complete monolayer of MPS and demonstrates the fast functionalization of ligand-free AuNP up to monolayer coverage. On citrate-AuNP, however, an MPS coverage of only two-thirds of a monolayer is observed, which indicates that citrate partially resists functionalization and is mostly exchanged at low-coordinated Au surface sites. High surface coverage, however, is often closely linked to functionality, for example, when avidity effects are exploited during conjugate-receptor interactions. © 2018 American Chemical Society.
    view abstract10.1021/acs.jpcc.8b07897
  • Spontaneous shape alteration and size separation of surfactant-free silver particles synthesized by laser ablation in acetone during long-period storage
    Zhang, D. and Choi, W. and Jakobi, J. and Kalus, M.-R. and Barcikowski, S. and Cho, S.-H. and Sugioka, K.
    Nanomaterials 8 (2018)
    The technique of laser ablation in liquids (LAL) has already demonstrated its flexibility and capability for the synthesis of a large variety of surfactant-free nanomaterials with a high purity. However, high purity can cause trouble for nanomaterial synthesis, because active high-purity particles can spontaneously grow into different nanocrystals, which makes it difficult to accurately tailor the size and shape of the synthesized nanomaterials. Therefore, a series of questions arise with regards to whether particle growth occurs during colloid storage, how large the particle size increases to, and into which shape the particles evolve. To obtain answers to these questions, here, Ag particles that are synthesized by femtosecond (fs) laser ablation of Ag in acetone are used as precursors to witness the spontaneous growth behavior of the LAL-generated surfactant-free Ag dots (2–10 nm) into different polygonal particles (5–50 nm), and the spontaneous size separation phenomenon by the carbon-encapsulation induced precipitation of large particles, after six months of colloid storage. The colloids obtained by LAL at a higher power (600 mW) possess a greater ability and higher efficiency to yield colloids with sizes of &lt;40 nm than the colloids obtained at lower power (300 mW), because of the generation of a larger amount of carbon ‘captors’ by the decomposition of acetone and the stronger particle fragmentation. Both the size increase and the shape alteration lead to a redshift of the surface plasmon resonance (SPR) band of the Ag colloid from 404 nm to 414 nm, after storage. The Fourier transform infrared spectroscopy (FTIR) analysis shows that the Ag particles are conjugated with COO– and OH– groups, both of which may lead to the growth of polygonal particles. The CO and CO2 molecules are adsorbed on the particle surfaces to form Ag(CO)x and Ag(CO2)x complexes. Complementary nanosecond LAL experiments confirmed that the particle growth was inherent to LAL in acetone, and independent of pulse duration, although some differences in the final particle sizes were observed. The nanosecond-LAL yields monomodal colloids, whereas the size-separated, initially bimodal colloids from the fs-LAL provide a higher fraction of very small particles that are &lt;5 nm. The spontaneous growth of the LAL-generated metallic particles presented in this work should arouse the special attention of academia, especially regarding the detailed discussion on how long the colloids can be preserved for particle characterization and applications, without causing a mismatch between the colloid properties and their performance. The spontaneous size separation phenomenon may help researchers to realize a more reproducible synthesis for small metallic colloids, without concern for the generation of large particles. © 2018 by the authors. Licensee MDPI, Basel, Switzerland.
    view abstract10.3390/nano8070529
  • 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 (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 abstract10.1021/acs.cgd.8b00809
  • Tissue Concentrations of Zinc, Iron, Copper, and Magnesium During the Phases of Full Thickness Wound Healing in a Rodent Model
    Coger, V. and Million, N. and Rehbock, C. and Sures, B. and Nachev, M. and Barcikowski, S. and Wistuba, N. and Strauß, S. and Vogt, P.M.
    Biological Trace Element Research (2018)
    Wound healing is a complex orchestration of processes involving cell proliferation, migration, differentiation, anabolism, and catabolism in order to restore skin continuity. Within these processes, elements such as metallic ions are involved due to their implications in cell behavior and enzymatic activity regulation. This study analyzed the kinetics of zinc, iron, copper and magnesium concentrations in a full thickness open wound rat model over 14 days. We made wounds with a diameter of 6 mm on the back of Lewis rats and let them heal naturally prior to analysis by histology and inductively coupled plasma mass spectrometry analysis. Histological and immunofluorescence analysis confirmed an inflammation phase until 7 days, epithelial proliferation phase from 16 h to 10 days, and remodeling phase from 7 days onward. These defined phases were correlated with the measured metal element kinetics. Zinc concentrations showed an inverted parabolic progression between 30.4 and a maximum of 39.9 μg/g dry weight. Magnesium values had a similar pattern between 283 and 499 μg/g dry weight. Copper concentrations, on the other hand, followed an inverted sigmoid trend with a decrease from 9.8 to 1.5 μg/g dry weight. Iron had a slight decrease in concentration for 24 h followed by an increase to a maximum of 466 μg/g dry weight. In conclusion, zinc, iron, and copper, even though differing in their total mass within the wound, exhibited concentration curve transitions at day 3. Interestingly, this time point correlates with the maximum proliferating keratinocyte rate during the proliferation phase. © 2018, The Author(s).
    view abstract10.1007/s12011-018-1600-y
  • Two mechanisms of nanoparticle generation in picosecond laser ablation in liquids: The origin of the bimodal size distribution
    Shih, C.-Y. and Streubel, R. and Heberle, J. and Letzel, A. and Shugaev, M.V. and Wu, C. and Schmidt, M. and Gökce, B. and Barcikowski, S. and Zhigilei, L.V.
    Nanoscale 10 (2018)
    The synthesis of chemically clean and environmentally friendly nanoparticles through pulsed laser ablation in liquids has shown a number of advantages over conventional chemical synthesis methods and has evolved into a thriving research field attracting laboratory and industrial applications. The fundamental understanding of processes leading to the nanoparticle generation, however, still remains elusive. In particular, the origin of bimodal nanoparticle size distributions in femto- and picosecond laser ablation in liquids, where small nanoparticles (several nanometers) with narrow size distribution are commonly observed to coexist with larger (tens to hundreds of nanometers) ones, has not been explained so far. In this paper, joint computational and experimental efforts are applied to understand the mechanisms of nanoparticle formation in picosecond laser ablation in liquids and to explain the bimodal nanoparticle size distributions. The results of a large-scale atomistic simulation reveal the critical role of the dynamic interaction between the ablation plume and the liquid environment, leading to the generation of large nanoparticles through a sequence of hydrodynamic instabilities at the plume-liquid interface and a concurrent nucleation and growth of small nanoparticles in an expanding metal-liquid mixing region. The computational predictions are supported by a series of stroboscopic videography experiments showing the emergence of small satellite bubbles surrounding the main cavitation bubble generated in single pulse experiments. Carefully timed double pulse irradiation triggers expansion of secondary cavitation bubbles indicating, in accord with the simulation results, the presence of localized sites of laser energy deposition (possibly large nanoparticles) injected into the liquid at the early stage of the bubble formation. © The Royal Society of Chemistry.
    view abstract10.1039/c7nr08614h
  • 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 abstract10.1007/s00339-017-1503-3
  • A quarter-century of nanoparticle generation by lasers in liquids: Where are we now, and what's next?
    Amendola, V. and Barcikowski, S.
    Journal of Colloid and Interface Science 489 (2017)
    view abstract10.1016/j.jcis.2016.12.016
  • Adjusting the catalytic properties of cobalt ferrite nanoparticles by pulsed laser fragmentation in water with defined energy dose
    Waag, F. and Gökce, B. and Kalapu, C. and Bendt, G. and Salamon, S. and Landers, J. and Hagemann, U. and Heidelmann, M. and Schulz, S. and Wende, H. and Hartmann, N. and Behrens, M. and Barcikowski, S.
    Scientific Reports 7 (2017)
    Highly active, structurally disordered CoFe2O4/CoO electrocatalysts are synthesized by pulsed laser fragmentation in liquid (PLFL) of a commercial CoFe2O4 powder dispersed in water. A partial transformation of the CoFe2O4 educt to CoO is observed and proposed to be a thermal decomposition process induced by the picosecond pulsed laser irradiation. The overpotential in the OER in aqueous alkaline media at 10 mA cm-2 is reduced by 23% compared to the educt down to 0.32 V with a Tafel slope of 71 mV dec-1. Importantly, the catalytic activity is systematically adjustable by the number of PLFL treatment cycles. The occurrence of thermal melting and decomposition during one PLFL cycle is verified by modelling the laser beam energy distribution within the irradiated colloid volume and comparing the by single particles absorbed part to threshold energies. Thermal decomposition leads to a massive reduction in particle size and crystal transformations towards crystalline CoO and amorphous CoFe2O4. Subsequently, thermal melting forms multi-phase spherical and network-like particles. Additionally, Fe-based layered double hydroxides at higher process cycle repetitions emerge as a byproduct. The results show that PLFL is a promising method that allows modification of the structural order in oxides and thus access to catalytically interesting materials. © 2017 The Author(s).
    view abstract10.1038/s41598-017-13333-zf
  • Colloidal Stability of Metal Nanoparticles in Engine Oil under Thermal and Mechanical Load
    Jendrzej, S. and Gökce, B. and Barcikowski, S.
    Chemical Engineering and Technology 40 (2017)
    Extended colloidal stability and high dispersion degree of nanolubricants are required to avoid nanoparticle deposition in combustion engines and to reduce friction and wear. The simple and rapid one-step technique of pulsed laser ablation in liquids is employed to synthesize precursor-free and highly dispersed gold nanoparticles in lubricants while the colloidal stability is measured by optical spectroscopy and transmission electron microscopy. A remarkable colloidal stability is determined under engine-like and ambient conditions for nine months in terms of constant primary particle size. In contrast to additive-free oils, almost no agglomeration is observed, which might be attributed to the attachment of engine oil additives or pyrolyzed/oxidized molecules to the nanoparticles preventing attractive nanoparticle interactions. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstract10.1002/ceat.201600541
  • Colloids created by light: Laser-generated nanoparticles for applications in biology and medicine
    Kalus, M.-R. and Rehbock, C. and Bärsch, N. and Barcikowski, S.
    Materials Today: Proceedings 4 (2017)
    Nanomaterials play a major role in today's research and have become almost indispensable in the field of biology and medicine. However, nanomaterials used in biomedicine must meet specific criteria, among which purity has the highest priority, as it ensures maximum biocompatibility. This brief review article is intended to introduce laser ablation in liquids as a facile and rapid method for the preparation of high-purity colloidal nanoparticles. In this context, a brief introduction into the physics of the laser ablation process as well as into the unique properties of the generated nanoparticles is given, while the main focus of this article lies on the applicability of laser-fabricated nanomaterials in biology and medicine, which is illustrated with recent examples. © 2017 Elsevier Ltd.
    view abstract10.1016/j.matpr.2017.09.173
  • 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 (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 abstract10.1021/acs.iecr.7b00039
  • 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 (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, Weinheim
    view abstract10.1002/cphc.201601198
  • Germanium Sub-Microspheres Synthesized by Picosecond Pulsed Laser Melting in Liquids: Educt Size Effects
    Zhang, D. and Lau, M. and Lu, S. and Barcikowski, S. and Gökce, B.
    Scientific Reports 7 (2017)
    Pulsed laser melting in liquid (PLML) has emerged as a facile approach to synthesize submicron spheres (SMSs) for various applications. Typically lasers with long pulse durations in the nanosecond regime are used. However, recent findings show that during melting the energy absorbed by the particle will be dissipated promptly after laser-matter interaction following the temperature decrease within tens of nanoseconds and hence limiting the efficiency of longer pulse widths. Here, the feasibility to utilize a picosecond laser to synthesize Ge SMSs (200∼1000 nm in diameter) is demonstrated by irradiating polydisperse Ge powders in water and isopropanol. Through analyzing the educt size dependent SMSs formation mechanism, we find that Ge powders (200∼1000 nm) are directly transformed into SMSs during PLML via reshaping, while comparatively larger powders (1000∼2000 nm) are split into daughter SMSs via liquid droplet bisection. Furthermore, the contribution of powders larger than 2000 nm and smaller than 200 nm to form SMSs is discussed. This work shows that compared to nanosecond lasers, picosecond lasers are also suitable to produce SMSs if the pulse duration is longer than the material electron-phonon coupling period to allow thermal relaxation. © The Author(s) 2017.
    view abstract10.1038/srep40355
  • Gradual modification of ITO particle's crystal structure and optical properties by pulsed UV laser irradiation in a free liquid jet
    Lau, M. and Straube, T. and Aggarwal, A.V. and Hagemann, U. and De Oliveira Viestel, B. and Hartmann, N. and Textor, T. and Lutz, H. and Gutmann, J.S. and Barcikowski, S.
    Dalton Transactions 46 (2017)
    Indium tin oxide (ITO) particle coatings are known for high transparency in the visible, good conductive properties and near-infrared absorption. These properties depend on ITO particle's stoichiometric composition, defects and size. Here we present a method to gradually change ITO particle's optical properties by a simple and controlled laser irradiation process. The defined irradiation process and controlled energy dose input allows one to engineer the absorption and transmission of coatings made from these particles. We investigate the role of the surrounding solvent, influence of laser fluence and the specific energy dose targeting modification of the ITO particle's morphology and chemistry by stepwise laser irradiation in a free liquid jet. TEM, SEM, EDX, XPS, XRD and Raman are used to elucidate the structural, morphological and chemical changes of the laser-induced ITO particles. On the basis of these results the observed modification of the optical properties is tentatively attributed to chemical changes, e.g. laser-induced defects or partial reduction. © 2017 The Royal Society of Chemistry.
    view abstract10.1039/c7dt00010c
  • 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 (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 abstract10.1016/j.apsusc.2017.01.077
  • How persistent microbubbles shield nanoparticle productivity in laser synthesis of colloids - Quantification of their volume, dwell dynamics, and gas composition
    Kalus, M.-R. and Bärsch, N. and Streubel, R. and Gökce, E. and Barcikowski, S. and Gökce, B.
    Physical Chemistry Chemical Physics 19 (2017)
    During laser synthesis of colloids, cavitation bubbles with lifetimes in the microsecond-scale form and shield the laser pulse leading to a decrease in nanoparticle output. A second type of productivity-limiting bubble that severely affects the productivity of the process is often neglected. With lifetimes from milliseconds to seconds, these persistent bubbles are systematically studied in this work by quantifying their composition, amount, size and dwell time in liquids with different viscosities and by relating the results to the nanoparticle productivities. It is found that during synthesis in water, water splitting occurs leading to persistent bubbles consisting of hydrogen and oxygen. In glycols, hydrogen and molecular carbon species containing microbubbles are formed. These persistent microbubbles shield up to 65% of the incoming laser beam depending on the liquid as well as the laser fluence and require attention by means of reducing their dwell time in the ablation zone and enhancing the nanoparticle output by liquid flow. The highest productivities and monodisperse quality are achieved in liquids with the lowest viscosities. © the Owner Societies 2017.
    view abstract10.1039/c6cp07011f
  • How Size Determines the Value of Gold: Economic Aspects of Wet Chemical and Laser-Based Metal Colloid Synthesis
    Jendrzej, S. and Gökce, B. and Epple, M. and Barcikowski, S.
    ChemPhysChem 18 (2017)
    Gold is one of the most valuable materials, and its monetary value is enhanced by size reduction from bullions to colloidal nanoparticles by a factor of 450. Wet-chemical reduction with subsequent centrifugation and pulsed laser ablation in liquids are frequently used for pure colloidal gold synthesis. Both methods provide similar physicochemical nanoparticle properties, but are very different synthesis techniques. However, the costs inherent to these methods are surprisingly seldom discussed. Both methods have in common that the labor effort poses the majority of synthesis costs. Besides an increase in batch size and mass concentration, especially an increase of the nanoparticle productivity via higher laser power and centrifugation capacity reduces synthesis costs if pilot- or industrial-scale applications are intended. In this case, laser-based synthesis is more economical if its productivity exceeds a break-even value of 550mgh-1, where the costs arising are limited by the metal costs. In contrast to industrial scale production, wet-chemical synthesis is more feasible for laboratory-scale applications, especially if the advantageous nanoparticle properties provided by laser ablation in liquids are not needed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstract10.1002/cphc.201601139
  • Laser Micromachining of Metals with Ultra-Short Pulses: Factors Limiting the Scale-Up Process
    Jaeggi, B. and Remund, S. and Streubel, R. and Goekce, B. and Barcikowski, S. and Neuenschwander, B.
    Journal of Laser Micro Nanoengineering 12 (2017)
    Especially for metals it was shown that the material removal process with ultra-short laser pulses shows an optimum point with highest efficiency i.e. with maximum specific removal rate. A scale-up process should therefore be realized by keeping the applied fluence near this optimum value i.e. by linearly increasing the repetition rate with the average power. In this paper we show that this scale-up is affected by two factors, the heat accumulation and by shielding effects. The latter leads to a signif-icant reduction of the specific removal rate which becomes significant in the case of copper or brass when the repetition rate is increased into the multi-MHz range. In contrast shielding effects are much less pronounced for stainless steel (1.4301) but the surface quality is strongly affected by heat accu-mulation. However, we show that removal rates in the range of 40 mm3/min are achieved for all stud-ied metals with average laser powers above 300 W.
    view abstract10.2961/jlmn.2017.03.0016
  • Laser Synthesis and Processing of Colloids: Fundamentals and Applications
    Zhang, D. and Gökce, B. and Barcikowski, S.
    Chemical Reviews 117 (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 abstract10.1021/acs.chemrev.6b00468
  • 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 (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 abstract10.1016/j.jcis.2016.09.014
  • 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 (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 abstract10.1039/c6ra28118d
  • Opportunities and Challenges for Laser Synthesis of Colloids
    Gökce, B. and Amendola, V. and Barcikowski, S.
    ChemPhysChem 18 (2017)
    view abstract10.1002/cphc.201700310
  • Optimizing in Vitro Impedance and Physico-Chemical Properties of Neural Electrodes by Electrophoretic Deposition of Pt Nanoparticles
    Koenen, S. and Rehbock, C. and Heissler, H.E. and Angelov, S.D. and Schwabe, K. and Krauss, J.K. and Barcikowski, S.
    ChemPhysChem 18 (2017)
    Neural electrodes suffer from an undesired incline in impedance when in permanent contact with human tissue. Nanostructures, induced by electrophoretic deposition (EPD) of ligand-free laser-generated nanoparticles (NPs) on the electrodes are known to stabilize impedance in vivo. Hence, Pt surfaces were systematically EPD-coated with Pt NPs and evaluated for impedance as well as surface coverage, contact angle, electrochemically active surface area (ECSA) and surface oxidation. The aim was to establish a systematic correlation between EPD process parameters and physical surface properties. The findings clearly reveal a linear decrease in impedance with increasing surface coverage, which goes along with a proportional reduction of the contact angle and an increase in ECSA and surface oxidation. EPD process parameters, prone to yield surface coatings with low impedance, are long deposition times (40–60 min), while high colloid concentrations (&gt;250 μg mL−1) and electric field strengths (&gt;25 V cm−1) should be avoided due to detrimental NP assemblage effects. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstract10.1002/cphc.201601180
  • Optimizing inVitro Impedance and Physico-Chemical Properties of Neural Electrodes by Electrophoretic Deposition of Pt Nanoparticles
    Koenen, S. and Rehbock, C. and Heissler, H.E. and Angelov, S.D. and Schwabe, K. and Krauss, J.K. and Barcikowski, S.
    ChemPhysChem 18 (2017)
    Neural electrodes suffer from an undesired incline in impedance when in permanent contact with human tissue. Nanostructures, induced by electrophoretic deposition (EPD) of ligand-free laser-generated nanoparticles (NPs) on the electrodes are known to stabilize impedance invivo. Hence, Pt surfaces were systematically EPD-coated with Pt NPs and evaluated for impedance as well as surface coverage, contact angle, electrochemically active surface area (ECSA) and surface oxidation. The aim was to establish a systematic correlation between EPD process parameters and physical surface properties. The findings clearly reveal a linear decrease in impedance with increasing surface coverage, which goes along with a proportional reduction of the contact angle and an increase in ECSA and surface oxidation. EPD process parameters, prone to yield surface coatings with low impedance, are long deposition times (40-60min), while high colloid concentrations (&gt;250μgmL-1) and electric field strengths (&gt;25Vcm-1) should be avoided due to detrimental NP assemblage effects. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstract10.1002/cphc.201601180
  • 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 (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 abstract10.1021/acsami.6b16765
  • 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 (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 abstract10.1002/ceat.201600506
  • Pulsed laser ablation in liquids: Impact of the bubble dynamics on particle formation
    Reich, S. and Schönfeld, P. and Wagener, P. and Letzel, A. and Ibrahimkutty, S. and Gökce, B. and Barcikowski, S. and Menzel, A. and dos Santos Rolo, T. and Plech, A.
    Journal of Colloid and Interface Science 489 (2017)
    Pulsed laser ablation in liquids (PLAL) is a multiscale process, involving multiple mutually interacting phenomena. In order to synthesize nanoparticles with well-defined properties it is important to understand the dynamics of the underlying structure evolution. We use visible-light stroboscopic imaging and X-ray radiography to investigate the dynamics occurring during PLAL of silver and gold on a macroscopic scale, whilst X-ray small angle scattering is utilized to deepen the understanding on particle genesis. By comparing our results with earlier reports we can elucidate the role of the cavitation bubble. We find that symmetry breaking at the liquid-solid interface is a critical factor for bubble motion and that the bubble motion acts on the particle distribution as confinement and retraction force to create secondary agglomerates. © 2016 Elsevier Inc.
    view abstract10.1016/j.jcis.2016.08.030
  • Pulsed laser ablation of wire-shaped target in a thin water jet: Effects of plasma features and bubble dynamics on the PLAL process
    Dell'Aglio, M. and De Giacomo, A. and Kohsakowski, S. and Barcikowski, S. and Wagener, P. and Santagata, A.
    Journal of Physics D: Applied Physics 50 (2017)
    In this paper, emission spectroscopy and fast imaging surveys during pulsed laser ablation in liquid (PLAL) for nanoparticles (NPs) production have been used, in order to provide further details about the process involved and the potentialities offered by a wire-shaped sample ablated in a flowing water jet. This kind of set-up has been explored because the laser ablation efficiency in water increases when a thin water layer and a wire-shaped target are used. In order to understand the physical processes causing the increasing ablation efficiency, both the laser-induced plasma and bubble dynamics generated in a flowing liquid jet have been analysed. The plasma parameters and the bubble behaviour in such a system have been compared with those observed in conventional PLAL experiments, where either a bulk or a wire-shaped target is immersed in bulk water. From the data presented here it is evidenced that the plasma and shockwave induced during the breakdown process can play a direct role in the ablation efficiency variation observed. With regard to the cavitation bubbles evolving near a free surface (the interface between water and air) it should be noted that these have to be treated with caution as a consequence of the strong influence played in these circumstances by the boundary of the water jet during its expansion dynamics. The effects due to the size of the liquid layer, the presence of the water/air interface, the liquid characteristics, the target shape, the plasma evolution and the bubble dynamics together with their outcomes on the NPs' production, are presented and discussed. © 2017 IOP Publishing Ltd.
    view abstract10.1088/1361-6463/aa652a
  • Role of Dissolved and Molecular Oxygen on Cu and PtCu Alloy Particle Structure during Laser Ablation Synthesis in Liquids
    Marzun, G. and Bönnemann, H. and Lehmann, C. and Spliethoff, B. and Weidenthaler, C. and Barcikowski, S.
    ChemPhysChem 18 (2017)
    The role of molecular oxygen dissolved in the solvent is often discussed as being an influential factor on particle oxidation during pulsed laser ablation in liquids. However, the formation of the particles during laser synthesis takes place under extreme conditions that enable the decomposition of the liquid medium. Reactive species of the solvent may then affect particle formation due to a chemical reaction in the reactive plasma. Experimental results show a difference between the role of dissolved molecular oxygen and the contribution from the oxygen in water molecules. Using a metallic Cu target in air-saturated water, laser ablation led to 20.5 wt % Cu, 11.5 wt % Cu2O, and 68 wt % CuO nanoparticles, according to X-ray diffraction results. In contrast to particles obtained in air-saturated water, no CuO was observed in the colloid synthesized in a Schlenk ablation chamber in completely oxygen-free water. Under these conditions, less-oxidized nanoparticles (25 wt % Cu and 75 wt % Cu2O) were synthesized. The results show that nanoparticle oxidation during laser synthesis is mainly caused by reactive oxygen species from the decomposition of water molecules. However, the addition of molecular oxygen promotes particle oxidation. Storage of the Cu colloid in the presence of dissolved oxygen leads, due to aging, to nanostructures with a higher oxidation state than the freshly prepared colloid. The XRD pattern of the sample prepared in air-saturated acetone showed no crystalline phases, which is possibly due to small crystallites or low particle concentration. Concentration of the particles by centrifugation showed that in the large fraction (&gt;20 nm), even less oxidized nanoparticles (46 wt % Cu and 54 wt % Cu2O) were present, although the solubility of molecular oxygen is higher in acetone than in water. The nanoparticles in acetone were stable due to a Cu-catalyzed graphite layer formed on their surfaces. The influence of the solvent on alloy synthesis is also crucial. Laser ablation of PtCu3 in air-saturated water led to separated large CuO and Pt-rich spherical nanoparticles, whereas homogeneous PtCu3 alloy nanoparticles were formed in acetone. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstract10.1002/cphc.201601315
  • 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 (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 abstract10.1021/acs.jpcc.6b12554
  • Tailored protein encapsulation into a DNA host using geometrically organized supramolecular interactions
    Sprengel, A. and Lill, P. and Stegemann, P. and Bravo-Rodriguez, K. and Schöneweiß, E.-C. and Merdanovic, M. and Gudnason, D. and Aznauryan, M. and Gamrad, L. and Barcikowski, S. and Sanchez-Garcia, E. and Birkedal, V. and Gatsogiannis, C. and Ehrmann, M. and Saccà, B.
    Nature Communications 8 (2017)
    The self-organizational properties of DNA have been used to realize synthetic hosts for protein encapsulation. However, current strategies of DNA-protein conjugation still limit true emulation of natural host-guest systems, whose formation relies on non-covalent bonds between geometrically matching interfaces. Here we report one of the largest DNA-protein complexes of semisynthetic origin held in place exclusively by spatially defined supramolecular interactions. Our approach is based on the decoration of the inner surface of a DNA origami hollow structure with multiple ligands converging to their corresponding binding sites on the protein surface with programmable symmetry and range-of-action. Our results demonstrate specific host-guest recognition in a 1:1 stoichiometry and selectivity for the guest whose size guarantees sufficient molecular diffusion preserving short intermolecular distances. DNA nanocontainers can be thus rationally designed to trap single guest molecules in their native form, mimicking natural strategies of molecular recognition and anticipating a new method of protein caging. © 2017 The Author(s).
    view abstract10.1038/ncomms14472
  • Triplex-hybridizing bioconjugated gold nanoparticles for specific Y-chromosome sequence targeting of bull spermatozoa
    Gamrad, L. and Mancini, R. and Werner, D. and Tiedemann, D. and Taylor, U. and Ziefuß, A. and Rehbock, C. and Klein, S. and Kues, W. and Barcikowski, S. and Rath, D.
    Analyst 142 (2017)
    Gold nanoparticles (AuNPs) are widely used in biomedical applications for drug targeting and bioimaging. This often neccesitates their functionalization with biomolecules carrying a defined biological function, yielding gold nanoparticle bioconjugates. The utilization of triplex-forming oligonucleotides (TFOs) as ligands gives access to nanoconjugates as tools for specific DNA-related nanotargeting via triplex hybridization. Since triplex hybridization with nanobioconjugates has to date not been shown on biologically relevant samples, sex-specific sperm marking may be an appropriate model system to demonstrate the opportunities of this targeting method in vitro. In this study, we focused on specific labeling of repetitive target sites enriched on the bovine Y-chromosome using triplex forming oligonucleotides. First, the functionality of a specific locked nucleic acid (LNA) sequence was confirmed on bovine free DNA and on demembranated sperm heads. Thereafter, the influence of AuNPs on triplex hybridization was spectrophotometrically analyzed employing synthetic dsDNA, genomic DNA and demembranated sperm heads. Results from the SPR-peak shift indicate that TFO-AuNP hybridize to bovine gDNA in a qualitative and significant manner. These results confirm successful triplex hybridization on biologically relevant target sites as well as the establishment of a method to use gold nanoparticles as a suitable tool for sex-selective hybridization. © The Royal Society of Chemistry 2017.
    view abstract10.1039/c6an02461k
  • 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 (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, Weinheim
    view abstract10.1002/cphc.201601266
  • Water-based, surfactant-free cytocompatible nanoparticle-microgel-composite biomaterials-rational design by laser synthesis, processing into fiber pads and impact on cell proliferation
    Million, N. and Coger, V. and Wilke, P. and Rehbock, C. and Vogt, P.M. and Pich, A. and Barcikowski, S.
    BioNanoMaterials 18 (2017)
    This work highlights the laser-based aqueous synthesis and processing of nanocomposites, composed of zinc or iron nanoparticles embedded in a N-Vinylcaprolactam microgel matrix, with potential applicability as ion releasing fiber pads for wound healing. An in situ laser process for microgel synthesis is developed and optimized for high embedded nanoparticle yields, evaluating influences of laser repetition rate and monomer concentration. The impact of the nanoparticles on polymerization was increased by embedded zinc oxide nanoparticles, and reduced in the presence of iron oxide. Furthermore, TEM images verified that the nanoparticles were homogeneously embedded into the polymer matrix. The nanoparticle-loaded microgels were thermally stable up to 429 °C, which ensures that the composites maintain their integrity after heat sterilization and during rapid prototyping by thermal polymer processing. The general suitability of the hydrogels as active biomaterial for wound healing was assessed in toxicity, cell proliferation and migration assays using human dermal fibroblasts and keratinocytes, where cytocompatibility was verified, while the proliferation was affected by the gel alone as well as the embedded nanoparticles. The hydrogels were processed to suit their use as a biomaterial for wound coverages via electrospinning resulting in a centimeter scale fully cytocompatible fiber pad with the nanoparticle-filled microgel capsules supported on the fiber's surface. © 2017 Walter de Gruyter GmbH, Berlin/Boston.
    view abstract10.1515/bnm-2017-0004
  • 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 (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 abstract10.1016/j.jcis.2015.10.032
  • 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 (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 abstract10.1021/acsnano.6b02627
  • 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 (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 abstract10.1364/OL.41.001486
  • Debris-free rear-side picosecond laser ablation of thin germanium wafers in water with ethanol
    Zhang, D. and Gökce, B. and Sommer, S. and Streubel, R. and Barcikowski, S.
    Applied Surface Science 367 (2016)
    In this paper, we perform liquid-assisted picosecond laser cutting of 150 μm thin germanium wafers from the rear side. By investigating the cutting efficiency (the ability to allow an one-line cut-through) and quality (characterized by groove morphologies on both sides), the pros and cons of this technique under different conditions are clarified. Specifically, with laser fluence fixed, repetition rate and scanning speed are varied to show quality and efficiency control by means of laser parameter modulation. It is found that low repetition rate ablation in liquid gives rise to a better cut quality on the front side than high repetition rate ablation since it avoids dispersed nanoparticles redeposition resulting from a bubble collapse, unlike the case of 100 kHz which leads to large nanorings near the grooves resulting from a strong interaction of bubbles and the case of 50 kHz which leads to random cutting due to the interaction of the former pulse induced cavitation bubble and the subsequent laser pulse. Furthermore, ethanol is mixed with pure distilled water to assess the liquid's impact on the cutting efficiency and cutting quality. The results show that increasing the ethanol fraction decreases the ablation efficiency but simultaneously, greatly improves the cutting quality. The improvement of cut quality as ethanol ratio increases may be attributed to less laser beam interference by a lower density of bubbles which adhere near the cut kerf during ablation. A higher density of bubbles generated from ethanol vaporization during laser ablation in liquid will cause stronger bubble shielding effect toward the laser beam propagation and therefore result in less laser energy available for the cut, which is the main reason for the decrease of cut efficiency in water-ethanol mixtures. Our findings give an insight into under which condition the rear-side laser cutting of thin solar cells should be performed: high repetition, pure distilled water and high laser power are favorable for high-speed rough cutting but the cut kerf suffers from strong side effects of ripples, nanoredeposition occurrence, while low laser power at low repetition rate (10 kHz), mixed solution (1 wt% ethanol in water) and moderate scanning speed (100 μm/s) are preferable for ultrafine high-quality debris-free cutting. The feasibility of high-quality cut is a good indication of using rear laser ablation in liquid to cut thinner wafers. More importantly, this technique spares any post cleaning steps to reduce the risk to the contamination or crack of the thin wafers. © 2016 Elsevier B.V. All rights reserved.
    view abstract10.1016/j.apsusc.2016.01.071
  • 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 (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 abstract10.1016/j.apsusc.2016.08.014
  • Effect of various dispersing agents on the stability of silver microparticle dispersion and the formulation of uniform silver film by laser melting
    Letzel, A. and Maurer, E. and Meixner, M. and Poprawe, R. and Stollenwerk, J. and Hessner, S. and Lehmann, K. and Gökce, B. and Barcikowski, S.
    Journal of Laser Applications 28 (2016)
    We report on the substitution of silver nanoparticles' inks by silver microparticle dispersions as a material for the production of printable silver tracks by laser melting. This approach is promising, because it helps to reduce the production costs of such silver tracks. Though silver dispersions used as materials for laser melting mostly contain polyvinylpyrrolidone as a stabilizer, which results in the appearance of an undesired balling effect of silver during laser melting, the authors test stabilizers differing in molecular weight and functionality. The resulting differences in colloidal and physicochemical properties are investigated and related to the final silver layer quality. © 2016 Laser Institute of America.
    view abstract10.2351/1.4955011
  • Efficient nucleic acid delivery to murine regulatory T cells by gold nanoparticle conjugates
    Gamrad, L. and Rehbock, C. and Westendorf, A.M. and Buer, J. and Barcikowski, S. and Hansen, W.
    Scientific Reports 6 (2016)
    Immune responses have to be tightly controlled to guarantee maintenance of immunological tolerance and efficient clearance of pathogens and tumorigenic cells without induction of unspecific side effects. CD4+ CD25+ regulatory T cells (Tregs) play an important role in these processes due to their immunosuppressive function. Genetic modification of Tregs would be helpful to understand which molecules and pathways are involved in their function, but currently available methods are limited by time, costs or efficacy. Here, we made use of biofunctionalized gold nanoparticles as non-viral carriers to transport genetic information into murine Tregs. Confocal microscopy and transmission electron microscopy revealed an efficient uptake of the bioconjugates by Tregs. Most importantly, coupling eGFP-siRNA to those particles resulted in a dose and time dependent reduction of up to 50% of eGFP expression in Tregs isolated from Foxp3eGFP reporter mice. Thus, gold particles represent a suitable carrier for efficient import of nucleic acids into murine CD4+ CD25+ Tregs, superior to electroporation.
    view abstract10.1038/srep28709
  • 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 abstract10.1186/s12951-015-0154-9
  • Gold-manganese oxide core-shell nanoparticles produced by pulsed laser ablation in water
    Simao, T. and Chevrier, D.M. and Jakobi, J. and Korinek, A. and Goupil, G. and Lau, M. and Garbarino, S. and Zhang, P. and Barcikowski, S. and Fortin, M.-A. and Guay, D.
    Journal of Physical Chemistry C 120 (2016)
    A single-step procedure for the preparation of Au-MnOx NPs was achieved through pulsed laser ablation of a gold-manganese metal target made of a pressed metal powder mixture. First, a 248 nm nanosecond laser at 66.7 J cm-2 was used to synthesize Au-MnOx NPs from a gold-manganese metal target immersed in an aqueous solution at pH 11 (NaOH). It is demonstrated that the Au-MnOx NPs are made of a small Au core (around 5 nm in diameter) surrounded by a very thin manganese oxide layer (0.3-1.3 nm) as characterized by TEM, HAADF HR-STEM, and EELS. The superficial MnOx layer has a local structure that bears a close resemblance to that of Mn2O3 and MnO2 as revealed by EXAFS and XANES measurements. Comparative studies were also performed with a 1064 nm nanosecond laser at 1.4 J cm-2. In that case, the resulting colloids are mainly made of a mixture of Au NPs and MnOx NPs, with few Au-MnOx NPs, thereby suggesting the impact of the laser wavelength and fluence on the synthesis process. The mechanisms responsible for the production of Au-MnOx core-shell NPs are discussed. © 2016 American Chemical Society.
    view abstract10.1021/acs.jpcc.6b05838
  • 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 (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 abstract10.1021/acs.langmuir.6b00685
  • 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 (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 (&le; 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 abstract10.1007/s12274-016-1218-3
  • 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 (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 abstract10.1039/c6tb01162d
  • 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 abstract10.1186/s12951-015-0155-8
  • 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 abstract10.1088/0957-4484/27/15/154001
  • Solvent-surface interactions control the phase structure in laser-generated iron-gold core-shell nanoparticles
    Wagener, P. and Jakobi, J. and Rehbock, C. and Chakravadhanula, V.S.K. and Thede, C. and Wiedwald, U. and Bartsch, M. and Kienle, L. and Barcikowski, S.
    Scientific Reports 6 (2016)
    This work highlights a strategy for the one-step synthesis of FeAu nanoparticles by the pulsed laser ablation of alloy targets in the presence of different solvents. This method allows particle generation without the use of additional chemicals; hence, solvent-metal interactions could be studied without cross effects from organic surface ligands. A detailed analysis of generated particles via transmission electron microscopy in combination with EDX elemental mapping could conclusively verify that the nature of the used solvent governs the internal phase structure of the formed nanoparticles. In the presence of acetone or methyl methacrylate, a gold shell covering a non-oxidized iron core was formed, whereas in aqueous media, an Au core with an Fe 3 O 4 shell was generated. This core-shell morphology was the predominant species found in >90% of the examined nanoparticles. These findings indicate that fundamental chemical interactions between the nanoparticle surface and the solvent significantly contribute to phase segregation and elemental distribution in FeAu nanoparticles. A consecutive analysis of resulting Fe@Au core-shell nanoparticles revealed outstanding oxidation resistance and fair magnetic and optical properties. In particular, the combination of these features with high stability magnetism and plasmonics may create new opportunities for this hybrid material in imaging applications.
    view abstract10.1038/srep23352
  • Target geometry and rigidity determines laser-induced cavitation bubble transport and nanoparticle productivity-a high-speed videography study
    Kohsakowski, S. and Gökce, B. and Tanabe, R. and Wagener, P. and Plech, A. and Ito, Y. and Barcikowski, S.
    Physical Chemistry Chemical Physics 18 (2016)
    Laser-induced cavitation has mostly been studied in bulk liquid or at a two-dimensional wall, although target shapes for the particle synthesis may strongly affect bubble dynamics and interfere with particle productivity. We investigated the dynamics of the cavitation bubble induced by pulsed-laser ablation in liquid for different target geometries with high-speed laser microsecond videography and focus on the collapse behaviour. This method enables us observations in a high time resolution (intervals of 1 μs) and single-pulse experiments. Further, we analyzed the nanoparticle productivity, the sizes of the synthesized nanoparticles and the evolution of the bubble volume for each different target shape and geometry. For the ablation of metal (Ag, Cu, Ni) wire tips a springboard-like behaviour after the first collapse is observed which can be correlated with vertical projectile motion. Its turbulent friction in the liquid causes a very efficient transport and movement of the bubble and ablated material into the bulk liquid and prevents particle redeposition. This effect is influenced by the degree of freedom of the wire as well as the material properties and dimensions, especially the Young's modulus. The most efficient and largest bubble movement away from the wire was observed for a thin (500 μm) silver wire with velocities up to 19.8 m s-1 and for materials with a small Young's modulus and flexural rigidity. We suggest that these observations may contribute to upscaling strategies and increase of particle yield towards large synthesis of colloids based on targets that may continuously be fed. © 2016 the Owner Societies.
    view abstract10.1039/c6cp01232a
  • 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 (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 abstract10.1016/j.seppur.2015.11.033
  • A hierarchical view on material formation during pulsed-laser synthesis of nanoparticles in liquid
    Ibrahimkutty, S. and Wagener, P. and Rolo, T.D.S. and Karpov, D. and Menzel, A. and Baumbach, T. and Barcikowski, S. and Plech, A.
    Scientific Reports 5 (2015)
    Pulsed-laser assisted nanoparticle synthesis in liquids (PLAL) is a versatile tool for nanoparticle synthesis. However, fundamental aspects of structure formation during PLAL are presently poorly understood. We analyse the spatio-temporal kinetics during PLAL by means of fast X-ray radiography (XR) and scanning small-angle X-ray scattering (SAXS), which permits us to probe the process on length scales from nanometers to millimeters with microsecond temporal resolution. We find that the global structural evolution, such as the dynamics of the vapor bubble can be correlated to the locus and evolution of silver nanoparticles. The bubble plays an important role in particle formation, as it confines the primary particles and redeposits them to the substrate. Agglomeration takes place for the confined particles in the second bubble. Additionally, upon the collapse of the second bubble a jet of confined material is ejected perpendicularly to the surface. We hypothesize that these kinetics influence the final particle size distribution and determine the quality of the resulting colloids, such as polydispersity and modality through the interplay between particle cloud compression and particle release into the liquid.
    view abstract10.1038/srep16313
  • 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 (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 abstract10.1016/j.tsf.2015.10.059
  • 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 (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 abstract10.1016/j.polymer.2015.01.078
  • 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 (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 abstract10.1166/jbn.2015.2094
  • 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 (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 abstract10.1149/2.0811504jes
  • 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 (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 abstract10.1039/c5ta02098k
  • 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 (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 abstract10.4028/
  • Inclusion of supported gold nanoparticles into their semiconductor support
    Lau, M. and Ziefuss, A. and Komossa, T. and Barcikowski, S.
    Physical Chemistry Chemical Physics 17 (2015)
    Supported particles are easily accessible as standard materials used in heterogeneous catalysis and photocatalysis. This article addresses our exemplary studies on the integration of supported nanoparticles into their solid support, namely gold nanoparticles into zinc oxide sub-micrometer spheres, by energy controlled pulsed laser melting in a free liquid jet. This one-step, continuous flow-through processing route reverses the educt's structure, converting the ligand-free surface adsorbate into a spherical subsurface solid inclusion within its former support. The results show how a nanoparticulate surface adsorbate can be included in the form of crystalline nanoparticles into the resolidified support matrix, demonstrated by using plasmonic nanoparticles and semiconductor microparticles as reference materials. © the Owner Societies 2015.
    view abstract10.1039/c5cp04296h
  • 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 (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 abstract10.3762/bjnano.6.66
  • Influence of ligands in metal nanoparticle electrophoresis for the fabrication of biofunctional coatings
    Streich, C. and Koenen, S. and Lelle, M. and Peneva, K. and Barcikowski, S.
    Applied Surface Science 348 (2015)
    Electrophoretic deposition of colloidal nanoparticles shows great promise for the fabrication of nano-structured surfaces, especially relevant for the surface modification of three dimensional medical implants. Here, the role of small and bulky, chemisorbent and physisorbent ligands on metal (gold, platinum) nanoparticle deposition dynamics are systematically investigated. To be able to compare ligand-coated to ligand-free nanoparticles, pulsed laser ablation in liquid is employed as nanoparticle fabrication method. Nanoparticles' electrophoretic properties are assessed via zeta potential measurements and nanoparticle tracking analysis, while online-UV-vis spectroscopy provides information about the deposition dynamics. Electron micrographs and contact angle measurements are employed to characterize the deposit. We show that ligand-free nanoparticles feature a high electrophoretic mobility and linear deposition kinetics, representing an excellent model material for controlled electrophoretic deposition. In contrast, the electrophoretic mobility of surface-modified nanoparticles is altered due to the surrounding ligand layer, resulting in less efficient deposition. Notably, electrophoretic mobility is not solely governed by the ligand's charge and does not correlate to the zeta potential values directly. Finally, bioactive nanotopographies with tunable wettability were created when depositing nanoparticles functionalized with cell-penetrating peptides. These peptide-nanoparticle bioconjugates have great potential to be used for mediating delivery via an implant surface such as a neural electrode. (C) 2015 Published by Elsevier B.V.
    view abstract10.1016/j.apsusc.2014.02.159
  • Layered Seed-Growth of AgGe Football-like Microspheres via Precursor-Free Picosecond Laser Synthesis in Water
    Zhang, D. and Gökce, B. and Notthoff, C. and Barcikowski, S.
    Scientific Reports 5 (2015)
    Hybrid particles are of great significance in terms of their adjustable optical, electronic, magnetic, thermal and mechanical properties. As a novel technique, laser ablation in liquids (LAL) is famous for its precursor-free, "clean" synthesis of hybrid particles with various materials. Till now, almost all the LAL-generated particles originate from the nucleation-growth mechanism. Seed-growth of particles similar to chemical methods seems difficult to be achieved by LAL. Here, we not only present novel patch-joint football-like AgGe microspheres with a diameter in the range of 1 ~ 7 ìm achievable by laser ablation in distilled water but also find direct evidences of their layered seed growth mechanism. Many critical factors contribute to the formation of AgGe microspheres: fast laser-generated plasma process provide an excellent condition for generating large amount of Ge and Ag ions/atoms, their initial nucleation and galvanic replacement reaction, while cavitation bubble confinement plays an important role for the increase of AgGe nuclei and subsequent layered growth in water after bubble collapse. Driven by work function difference, Ge acts as nucleation agent for silver during alloy formation. This new seed-growth mechanism for LAL technique opens new opportunities to develop a large variety of novel hybrid materials with controllable properties.
    view abstract10.1038/srep13661
  • 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 (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 abstract10.1007/s10562-015-1514-7
  • Quantification of mass-specific laser energy input converted into particle properties during picosecond pulsed laser fragmentation of zinc oxide and boron carbide in liquids
    Lau, M. and Barcikowski, S.
    Applied Surface Science 348 (2015)
    Pulsed laser fragmentation in liquids is an effective method to fabricate organic, metal or semiconductor nanoparticles by ablation of suspended particles. However, modelling and up-scaling of this process lacks quantification of the laser energy required for a specific product property like particle diameter of the colloid or bandgap energy of the fabricated nanoparticles. A novel set-up for defined laser energy dose in a free liquid jet enables mass-specific energy balancing and exact threshold determination for pulsed laser fragmentation. By this technique laser energy and material responses can be precisely correlated. Linear decrease of the particle diameter and linear increase of the bandgap energy with mass-specific laser energy input has been observed for the examples of ZnO and B4C particles. Trends are analysed by density gradient centrifugation, electron microscopy, UV-vis and X-ray diffraction analysis of the crystal structure. The study contributes to quantitative model parameters for up-scaling and provides insight into the mechanisms occurring when suspended particles are irradiated with pulsed laser sources. © 2014 Elsevier B.V. All rights reserved.
    view abstract10.1016/j.apsusc.2014.07.053
  • 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 (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 abstract10.1016/j.cplett.2015.03.010
  • 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 (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 abstract10.1111/rda.12572
  • 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 (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 abstract10.1016/j.apsusc.2015.01.108
  • Solid solution magnetic FeNi nanostrand-polymer composites by connecting-coarsening assembly
    Barcikowski, S. and Baranowski, T. and Durmus, Y. and Wiedwald, U. and Gökce, B.
    Journal of Materials Chemistry C 3 (2015)
    An approach to assemble high aspect ratio nanostrands consisting of magnetic nanowires and their incorporation in a polymer with the aim of tailoring transparent FeNi nanostrand-PMMA-composites is presented. These nanostrands are controllable in length (<600 μm) and width (<12 μm) via process parameters and have an ultra-high aspect ratio (∼160). This rapid and universal method provides flexible and transparent magnetic materials with tunable transparency and magnetic attraction force by adjusting the density of nanoparticles in the composite. These composites can be used as a window coating for shielding radio frequency electromagnetic waves while being transparent in the optical range. © 2015 The Royal Society of Chemistry.
    view abstract10.1039/c5tc02160j
  • Strategies to harvest the unique properties of laser-generated nanomaterials in biomedical and energy applications
    Asahi, T. and Mafuné, F. and Rehbock, C. and Barcikowski, S.
    Applied Surface Science 348 (2015)
    view abstract10.1016/j.apsusc.2015.04.104
  • The effect of the Au loading on the liquid-phase aerobic oxidation of ethanol over Au/TiO2 catalysts prepared by pulsed laser ablation
    Dong, W. and Reichenberger, S. and Chu, S. and Weide, P. and Ruland, H. and Barcikowski, S. and Wagener, P. and Muhler, M.
    Journal of Catalysis 330 (2015)
    Gold nanoparticles (NPs) synthesized by pulsed laser ablation of a gold target in water were efficiently deposited on TiO<inf>2</inf> (P25) without any post-treatment yielding catalysts with Au loadings up to 10 wt%. Regardless of the loading, the Au NPs had a mean diameter of 8 nm before and after deposition. The ligand-free Au NPs strongly bind to TiO<inf>2</inf> surface oxygen vacancies and maintain a homogeneous distribution with loadings up to 4 wt%, while a further increase in Au content up to 10 wt% results in additional weakly adsorbed Au NPs. The catalytic tests of the Au/TiO<inf>2</inf> samples in the selective oxidation of ethanol in the liquid phase identified an optimal loading of 4 wt% resulting in the highest yield of acetic acid, which is ascribed to the homogeneous Au distribution and the adequate occupation of surface oxygen vacancies by strongly bound Au NPs without significant Au sintering during reaction. © 2015 Elsevier Inc. All rights reserved.
    view abstract10.1016/j.jcat.2015.07.033
  • 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 (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 abstract10.1021/la502588g
  • Alloying colloidal silver nanoparticles with gold disproportionally controls antibacterial and toxic effects
    Grade, S. and Eberhard, J. and Jakobi, J. and Winkel, A. and Stiesch, M. and Barcikowski, S.
    Gold Bulletin 47 (2014)
    Elemental silver nanoparticles are an effective antibacterial substance and are found as additive in various medical applications. Gold nanoparticles are used due to their optical properties in microscopy and cancer therapy. These advantages might be combined within alloyed nanoparticles of both elements and thereby open new fields of interest in research and medical treatment. In this context, laser ablation of solid alloys in liquid gives access to colloidal silver-gold alloy nanoparticles with a homogeneous ultrastructure. Elemental and alloy silver-gold nanoparticles with increasing molar fractions of silver (50, 80, and 100 %) were produced and stabilized with citrate or albumin (BSA). Particles were embedded in agar at concentrations of 3-100 μg cm-3 and tested on clinical relevant Staphylococcus aureus regarding their antibacterial properties. Cytotoxic effects were measured within the same particle concentration range using human gingival fibroblasts (HGFib). As expected, a reduced fraction of silver in the nanoalloys decreased the antibacterial effect on S. aureus according to the evaluated minimal inhibitory concentrations. However, this decrease turned out stronger than expected by its relative mass per particle, due to the electrochemical, disproportionally high effect of gold on the bioresponse to silver within silver-gold nanoalloy particles. BSA was able to stabilize all colloids and maintain antibacterial activity, whereas sodium citrate reduced antibacterial effects and cytotoxicity even at high nanoparticle concentrations. The alloying of silver with gold by laser ablation in liquid produced nanoparticles with both reduced antibacterial and cytotoxic properties in comparison to silver nanoparticles but still retains the application spectrum of both elements combined in one colloid. In particular, alloying with gold may render silver nanoparticles more biocompatible, and allows bioconjugation via established thiol chemistry. © 2013 The Author(s).
    view abstract10.1007/s13404-013-0125-6
  • Biocompatible gold submicrometer spheres with variable surface texture fabricated by pulsed laser melting in liquid
    Rehbock, C. and Zwartscholten, J. and Barcikowski, S.
    Chemistry Letters 43 (2014)
    This paper highlights a strategy on how totally ligand-free biocompatible gold submicrometer spheres (Au-SMSs) can be synthesized by aggregating laser-fabricated nanoparticles (NPs) with NaCl followed by subsequent post-irradiation using pulsed lasers at a moderate fluence. Interestingly, we observed significant changes in the surface structure of the SMSs, caused by the adsorption of smaller particles following a disaggregation-melting-redeposition-sintering-mechanism. Here, utilization of low fluences yielded perfectly smooth textures while higher fluences lead to wrinkled textures. Furthermore, we elucidate that prior to aggregation, the particle size distribution of the source AuNPs may significantly interfere with the surface texture of the resulting Au-SMSs, indicated by predominant formation of rough surface structures in the presence of smaller source NPs. These findings may highlight novel synthesis strategies for Au-SMSs with rough surface textures, particularly beneficial for SERS applications. © 2014 The Chemical Society of Japan.
    view abstract10.1246/cl.140455
  • 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 (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 abstract10.1021/jp501489t
  • Current state of laser synthesis of metal and alloy nanoparticles as ligand-free reference materials for nano-toxicological assays
    Rehbock, C. and Jakobi, J. and Gamrad, L. and van der Meer, S. and Tiedemann, D. and Taylor, U. and Kues, W. and Rath, D. and Barcikowski, S.
    Beilstein Journal of Nanotechnology 5 (2014)
    Due to the abundance of nanomaterials in medical devices and everyday products, toxicological effects related to nanoparticles released from these materials, e.g., by mechanical wear, are a growing matter of concern. Unfortunately, appropriate nanoparticles required for systematic toxicological evaluation of these materials are still lacking. Here, the ubiquitous presence of surface ligands, remaining from chemical synthesis are a major drawback as these organic residues may cause cross-contaminations in toxicological studies. Nanoparticles synthesized by pulsed laser ablation in liquid are a promising alternative as this synthesis route provides totally ligand-free nanoparticles. The first part of this article reviews recent methods that allow the size control of laser-fabricated nanoparticles, focusing on laser post irradiation, delayed bioconjugation and in situ size quenching by low salinity electrolytes. Subsequent or parallel applications of these methods enable precise tuning of the particle diameters in a regime from 4-400 nm without utilization of any artificial surface ligands. The second paragraph of this article highlights the recent progress concerning the synthesis of composition controlled alloy nanoparticles by laser ablation in liquids. Here, binary and ternary alloy nanoparticles with totally homogeneous elemental distribution could be fabricated and the composition of these particles closely resembled bulk implant material. Finally, the model AuAg was used to systematically evaluate composition related toxicological effects of alloy nanoparticles. Here Ag+ ion release is identified as the most probable mechanism of toxicity when recent toxicological studies with gametes, mammalian cells and bacteria are considered. © 2014 Rehbock et al.
    view abstract10.3762/bjnano.5.165
  • 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 (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 abstract10.1002/jbm.a.34860
  • Effects of silver nitrate and silver nanoparticles on a planktonic community: General trends after short-term exposure
    Boenigk, J. and Beisser, D. and Zimmermann, S. and Bock, C. and Jakobi, J. and Grabner, D. and Großmann, L. and Rahmann, S. and Barcikowski, S. and Sures, B.
    PLoS ONE 9 (2014)
    Among metal pollutants silver ions are one of the most toxic forms, and have thus been assigned to the highest toxicity class. Its toxicity to a wide range of microorganisms combined with its low toxicity to humans lead to the development of a wealth of silver-based products in many bactericidal applications accounting to more than 1000 nano-technology-based consumer products. Accordingly, silver is a widely distributed metal in the environment originating from its different forms of application as metal, salt and nanoparticle. A realistic assessment of silver nanoparticle toxicity in natural waters is, however, problematic and needs to be linked to experimental approaches. Here we apply metatranscriptome sequencing allowing for elucidating reactions of whole communities present in a water sample to stressors. We compared the toxicity of ionic silver and ligand-free silver nanoparticles by short term exposure on a natural community of aquatic microorganisms. We analyzed the effects of the treatments on metabolic pathways and species composition on the eukaryote metatranscriptome level in order to describe immediate molecular responses of organisms using a community approach. We found significant differences between the samples treated with 5 μg/L AgNO 3 compared to the controls, but no significant differences in the samples treated with AgNP compared to the control samples. Statistical analysis yielded 126 genes (KO-IDs) with significant differential expression with a false discovery rate (FDR) < 0.05 between the control (KO) and AgNO3 (NO3) groups. A KEGG pathway enrichment analysis showed significant results with a FDR below 0.05 for pathways related to photosynthesis. Our study therefore supports the view that ionic silver rather than silver nanoparticles are responsible for silver toxicity. Nevertheless, our results highlight the strength of metatranscriptome approaches for assessing metal toxicity on aquatic communities. © 2014 Boenigk et al.
    view abstract10.1371/journal.pone.0095340
  • Evaluation of pulsed laser ablation in liquids generated gold nanoparticles as novel transfection tools: Efficiency and cytotoxicity
    Willenbrock, S. and Durán, M.C. and Barchanski, A. and Barcikowski, S. and Feige, K. and Nolte, I. and Murua Escobar, H.
    Proceedings of SPIE - The International Society for Optical Engineering 8972 (2014)
    Varying transfection efficiencies and cytotoxicity are crucial aspects in cell manipulation. The utilization of gold nanoparticles (AuNP) has lately attracted special interest to enhance transfection efficiency. Conventional AuNP are usually generated by chemical reactions or gas pyrolysis requiring often cell-toxic stabilizers or coatings to conserve their characteristics. Alternatively, stabilizer- and coating-free, highly pure, colloidal AuNP can be generated by pulsed laser ablation in liquids (PLAL). Mammalian cells were transfected efficiently by addition of PLAL-AuNP, but data systematically evaluating the cell-toxic potential are lacking. Herein, the transfection efficiency and cytotoxicity of PLAL AuNP was evaluated by transfection of a mammalian cell line with a recombinant HMGB1/GFP DNA expression vector. Different methods were compared using two sizes of PLAL-AuNP, commercialized AuNP, two magnetic NP-based protocols and a conventional transfection reagent (FuGENE HD; FHD). PLAL-AuNP were generated using a Spitfire Pro femtosecond laser system delivering 120 fs laser pulses at a wavelength of 800 nm focusing the fs-laser beam on a 99.99% pure gold target placed in ddH2O. Transfection efficiencies were analyzed after 24h using fluorescence microscopy and flow cytometry. Toxicity was assessed measuring cell proliferation and percentage of necrotic, propidium iodide positive cells (PI %). The addition of PLAL-AuNP significantly enhanced transfection efficiencies (FHD: 31 %; PLAL-AuNP size-1: 46 %; size-2: 50 %) with increased PI% but no reduced cell proliferation. Commercial AuNP-transfection showed significantly lower efficiency (23 %), slightly increased PI % and reduced cell proliferation. Magnetic NP based methods were less effective but showing also lowest cytotoxicity. In conclusion, addition of PLAL-AuNP provides a novel tool for transfection efficiency enhancement with acceptable cytotoxic side-effects. © 2014 SPIE.
    view abstract10.1117/12.2038453
  • Gold nanoparticles interfere with sperm functionality by membrane adsorption without penetration
    Taylor, U. and Barchanski, A. and Petersen, S. and Kues, W.A. and Baulain, U. and Gamrad, L. and Sajti, L. and Barcikowski, S. and Rath, D.
    Nanotoxicology 8 (2014)
    To examine gold nanoparticle reprotoxicity, bovine spermatozoa were challenged with ligand-free or oligonucleotide-conjugated gold nanoparticles synthesized purely without any surfactants by laser ablation. Sperm motility declined at nanoparticle mass dose of 10 μg/ml (corresponding to ∼14 000 nanoparticles per sperm cell) regardless of surface modification. Sperm morphology and viability remained unimpaired at all concentrations. Transmission electron microscopy showed an modification dependant attachment of nanoparticles to the cell membrane of spermatozoa, but provided no evidence for nanoparticle entrance into sperm cells. A molecular examination revealed a reduction of free thiol residues on the cell membrane after nanoparticle exposure, which could explain the decrease in sperm motility. Sperm fertilising ability decreased after exposure to 10 μg/ml of ligand-free nanoparticles indicating that agglomerated ligand-free nanoparticles interfere with membrane properties necessary for fertilisation. In conclusion, nanoparticles may impair key sperm functions solely by interacting with the sperm surface membrane. © 2014 Informa UK Ltd. All rights reserved.
    view abstract10.3109/17435390.2013.859321
  • In situ non-DLVO stabilization of surfactant-free, plasmonic gold nanoparticles: Effect of Hofmeister's anions
    Merk, V. and Rehbock, C. and Becker, F. and Hagemann, U. and Nienhaus, H. and Barcikowski, S.
    Langmuir 30 (2014)
    Specific ion effects ranking in the Hofmeister sequence are ubiquitous in biochemical, industrial, and atmospheric processes. In this experimental study specific ion effects inexplicable by the classical DLVO theory have been investigated at curved water-metal interfaces of gold nanoparticles synthesized by a laser ablation process in liquid in the absence of any organic stabilizers. Notably, ion-specific differences in colloidal stability occurred in the Hückel regime at extraordinarily low salinities below 50 μM, and indications of a direct influence of ion-specific effects on the nanoparticle formation process are found. UV-vis, zeta potential, and XPS measurements help to elucidate coagulation properties, electrokinetic potential, and the oxidation state of pristine gold nanoparticles. The results clearly demonstrate that stabilization of ligand-free gold nanoparticles scales proportionally with polarizability and antiproportionally with hydration of anions located at defined positions in a direct Hofmeister sequence of anions. These specific ion effects might be due to the adsorption of chaotropic anions (Br-, SCN-, or I-) at the gold/water interface, leading to repulsive interactions between the partially oxidized gold particles during the nanoparticle formation process. On the other hand, kosmotropic anions (F - or SO4 2-) seem to destabilize the gold colloid, whereas Cl- and NO3 - give rise to an intermediate stability. Quantification of surface charge density indicated that particle stabilization is dominated by ion adsorption and not by surface oxidation. Fundamental insights into specific ion effects on ligand-free aqueous gold nanoparticles beyond purely electrostatic interactions are of paramount importance in biomedical or catalytic applications, since colloidal stability appears to depend greatly on the type of salt rather than on the amount. © 2014 American Chemical Society.
    view abstract10.1021/la404556a
  • Injection of ligand-free gold and silver nanoparticles into murine embryos does not impact pre-implantation development
    Taylor, U. and Garrels, W. and Barchanski, A. and Peterson, S. and Sajti, L. and Lucas-Hahn, A. and Gamrad, L. and Baulain, U. and Klein, S. and Kues, W.A. and Barcikowski, S. and Rath, D.
    Beilstein Journal of Nanotechnology 5 (2014)
    Intended exposure to gold and silver nanoparticles has increased exponentially over the last decade and will continue to rise due to their use in biomedical applications. In particular, reprotoxicological aspects of these particles still need to be addressed so that the potential impacts of this development on human health can be reliably estimated. Therefore, in this study the toxicity of gold and silver nanoparticles on mammalian preimplantation development was assessed by injecting nanoparticles into one blastomere of murine 2 cell-embryos, while the sister blastomere served as an internal control. After treatment, embryos were cultured and embryo development up to the blastocyst stage was assessed. Development rates did not differ between microinjected and control groups (gold nanoparticles: 67.3%, silver nanoparticles: 61.5%, sham: 66.2%, handling control: 79.4%). Real-time PCR analysis of six developmentally important genes (BAX, BCL2L2, TP53, OCT4, NANOG, DNMT3A) did not reveal an influence on gene expression in blastocysts. Contrary to silver nanoparticles, exposure to comparable Ag+-ion concentrations resulted in an immediate arrest of embryo development. In conclusion, the results do not indicate any detrimental effect of colloidal gold or silver nanoparticles on the development of murine embryos. © 2014 Taylor et al; licensee Beilstein-Institut.
    view abstract10.3762/bjnano.5.80
  • Interaction of colloidal nanoparticles with their local environment: The (ionic) nanoenvironment around nanoparticles is different from bulk and determines the physico-chemical properties of the nanoparticles
    Pfeiffer, C. and Rehbock, C. and Hühn, D. and Carrillo-Carrion, C. and De Aberasturi, D.J. and Merk, V. and Barcikowski, S. and Parak, W.J.
    Journal of the Royal Society Interface 11 (2014)
    The physico-chemical properties of colloidal nanoparticles (NPs) are influenced by their local environment, as, in turn, the local environment influences the physico-chemical properties of the NPs. In other words, the local environment around NPs has a profound impact on the NPs, and it is different from bulk due to interaction with the NP surface. So far, this important effect has not been addressed in a comprehensive way in the literature. The vicinity of NPs can be sensitively influenced by local ions and ligands, with effects already occurring at extremely low concentrations. NPs in the Hückel regime are more sensitive to fluctuations in the ionic environment, because of a larger Debye length. The local ion concentration hereby affects the colloidal stability of the NPs, as it is different from bulk owing to Debye Hückel screening caused by the charge of the NPs. This can have subtle effects, now caused by the environment to the performance of the NP, such as for example a buffering effect caused by surface reaction on ultrapure ligandfree nanogold, a size quenching effect in the presence of specific ions and a significant impact on fluorophore-labelled NPs acting as ion sensors. Thus, the aim of this review is to clarify and give an unifying view of the complex interplay between the NP's surface with their nanoenvironment. © 2014 The Author(s) Published by the Royal Society. All rights reserved.
    view abstract10.1098/rsif.2013.0931
  • Ligand-free gold atom clusters adsorbed on graphene nano sheets generated by oxidative laser fragmentation in water
    Lau, M. and Haxhiaj, I. and Wagener, P. and Intartaglia, R. and Brandi, F. and Nakamura, J. and Barcikowski, S.
    Chemical Physics Letters 610-611 (2014)
    Over three decades after the first synthesis of stabilized Au 55-clusters many scientific questions about gold cluster properties are still unsolved and ligand-free colloidal clusters are difficult to fabricate. Here we present a novel route to produce ultra-small gold particles by using a green technique, the laser ablation and fragmentation in water, without using reductive or stabilizing agents at any step of the synthesis. For fabrication only a pulsed laser, a gold-target, pure water, sodium hydroxide and hydrogen peroxide are deployed. The particles are exemplarily hybridized to graphene supports showing that these carbon-free colloidal clusters might serve as versatile building blocks. © 2014 Published by Elsevier B.V.
    view abstract10.1016/j.cplett.2014.07.047
  • Monophasic ligand-free alloy nanoparticle synthesis determinants during pulsed laser ablation of bulk alloy and consolidated microparticles in water
    Neumeister, A. and Jakobi, J. and Rehbock, C. and Moysig, J. and Barcikowski, S.
    Physical Chemistry Chemical Physics 16 (2014)
    Chemical syntheses of homogenous solid solution alloy nanoparticles of noble metals require high temperature above 100°C. Beside this, aqueous co-reduction methods lead to phase separation. In contrast, pulsed laser ablation in liquid (PLAL) allows synthesis of alloy nanoparticles with totally homogeneous ultrastructure in aqueous media at room temperature without reducing agents or organic ligands. However, to date, the dominant alloy formation process during PLAL is not fully understood. Based on the model of Ag-Au alloy, we elucidate that the underlying mechanism is not affected by post-irradiation or interactions with colloidal particles in solution but is caused directly by ablation. In this context we analyzed nanoparticles generated from alloy targets with 9 different compositions as well as pure Ag and Au references using UV-Vis spectroscopy, TEM and TEM-EDX line scans. The obtained results highlight that the total composition but not the microstructure of the applied target is the dominant parameter ruling elemental composition in the resulting solid solution alloy nanoparticles. Based on these findings, the application of pressed targets of metal powder mixtures in a continuous laser process with residence time <60 s allows economical fabrication of alloy nanoparticles ideally suited for applications in catalysis or biomedicine. © the Owner Societies 2014.
    view abstract10.1039/c4cp03316g
  • Near-field-enhanced, off-resonant laser sintering of semiconductor particles for additive manufacturing of dispersed Au-ZnO-micro/nano hybrid structures
    Lau, M. and Niemann, R.G. and Bartsch, M. and O'Neill, W. and Barcikowski, S.
    Applied Physics A: Materials Science and Processing 114 (2014)
    Off-resonant near-field enhancement by gold nanoparticles adsorbed on crystalline zinc oxide significantly increases the energy efficiency of infrared laser sintering. In detail, ten different gold mass loads on zinc oxide were exposed to 1,064 nm cw-laser radiation. Variation of scan speed, laser power, and spot size showed that the energy threshold required for sintering decreases and sintering process window widens compared to laser sintering of pure zinc oxide powder. Transmission electron microscope analysis after focused ion beam cross sectioning of the sintered particles reveals that supported gold nanoparticles homogenously resolidify in the sintered semiconductor matrix. The enhanced sintering process with ligand-free gold nanoparticles gives access to metal-semiconductor hybrid materials with potential application in light harvesting or energy conversion. © 2014 Springer-Verlag Berlin Heidelberg.
    view abstract10.1007/s00339-014-8270-1
  • Rational design of gold nanoparticle toxicology assays: A question of exposure scenario, dose and experimental setup
    Taylor, U. and Rehbock, C. and Streich, C. and Rath, D. and Barcikowski, S.
    Nanomedicine 9 (2014)
    Many studies have evaluated the toxicity of gold nanoparticles, although reliable predictions based on these results are rare. In order to overcome this problem, this article highlights strategies to improve comparability and standardization of nanotoxicological studies. To this end, it is proposed that we should adapt the nanomaterial to the addressed exposure scenario, using ligand-free nanoparticle references in order to differentiate ligand effects from size effects. Furthermore, surface-weighted particle dosing referenced to the biologically relevant parameter (e.g., cell number or organ mass) is proposed as the gold standard. In addition, it is recommended that we should shift the focus of toxicological experiments from 'live-dead' assays to the assessment of cell function, as this strategy allows observation of bioresponses at lower doses that are more relevant for in vivo scenarios. © 2014 Future Medicine Ltd.
    view abstract10.2217/nnm.14.139
  • Reprotoxicity of gold, silver, and gold-silver alloy nanoparticles on mammalian gametes
    Tiedemann, D. and Taylor, U. and Rehbock, C. and Jakobi, J. and Klein, S. and Kues, W.A. and Barcikowski, S. and Rath, D.
    Analyst 139 (2014)
    Metal and alloy nanoparticles are increasingly developed for biomedical applications, while a firm understanding of their biocompatibility is still missing. Various properties have been reported to influence the toxic potential of nanoparticles. This study aimed to assess the impact of nanoparticle size, surface ligands and chemical composition of gold, silver or gold-silver alloy nanoparticles on mammalian gametes. An in vitro assay for porcine gametes was developed, since these are delicate primary cells, for which well-established culture systems exist and functional parameters are defined. During coincubation with oocytes for 46 h neither any of the tested gold nanoparticles nor the gold-silver alloy particles with a silver molar fraction of up to 50% showed any impact on oocyte maturation. Alloy nanoparticles with 80% silver molar fraction and pure silver nanoparticles inhibited cumulus-oocyte maturation. Confocal microscopy revealed a selective uptake of gold nanoparticles by oocytes, while silver and alloy particles mainly accumulated in the cumulus cell layer surrounding the oocyte. Interestingly sperm vitality parameters (motility, membrane integrity and morphology) were not affected by any of the tested nanoparticles. Only sporadic association of nanoparticles with the sperm plasma membrane was found by transmission electron microscopy. In conclusion, mammalian oocytes were sensitive to silver containing nanoparticles. Likely, the delicate process of completing meiosis in maternal gametes features high vulnerability towards nanomaterial derived toxicity. The results imply that released Ag +-ions are responsible for the observed toxicity, but the compounding into an alloy seemed to alleviate the toxic effects to a certain extent. This journal is © The Royal Society of Chemistry 2014.
    view abstract10.1039/c3an01463k
  • Adhesion, Vitality and Osteogenic Differentiation Capacity of Adipose Derived Stem Cells Seeded on Nitinol Nanoparticle Coatings
    Strauß, S. and Neumeister, A. and Barcikowski, S. and Kracht, D. and Kuhbier, J.W. and Radtke, C. and Reimers, K. and Vogt, P.M.
    PLoS ONE 8 (2013)
    Autologous cells can be used for a bioactivation of osteoimplants to enhance osseointegration. In this regard, adipose derived stem cells (ASCs) offer interesting perspectives in implantology because they are fast and easy to isolate. However, not all materials licensed for bone implants are equally suited for cell adhesion. Surface modifications are under investigation to promote cytocompatibility and cell growth. The presented study focused on influences of a Nitinol-nanoparticle coating on ASCs. Possible toxic effects as well as influences on the osteogenic differentiation potential of ASCs were evaluated by viability assays, scanning electron microscopy, immunofluorescence and alizarin red staining. It was previously shown that Nitinol-nanoparticles exert no cell toxic effects to ASCs either in soluble form or as surface coating. Here we could demonstrate that a Nitinol-nanoparticle surface coating enhances cell adherence and growth on Nitinol-surfaces. No negative influence on the osteogenic differentiation was observed. Nitinol-nanoparticle coatings offer new possibilities in implantology research regarding bioactivation by autologous ASCs, respectively enhancement of surface attraction to cells. © 2013 Strauß et al.
    view abstract10.1371/journal.pone.0053309
  • Advanced nanoparticle generation and excitation by lasers in liquids
    Barcikowski, S. and Compagnini, G.
    Physical Chemistry Chemical Physics 15 (2013)
    Today, nanoparticles are widely implemented as functional elements onto surfaces, into volumes and as nano-hybrids, resulting for example in bioactive composites and biomolecule conjugates. However, only limited varieties of materials compatible for integration into advanced functional materials are available: nanoparticles synthesized using conventional gas phase processes are often agglomerated into micro powders that are hard to re-disperse into functional matrices. Chemical synthesis methods often lead to impurities of the nanoparticle colloids caused by additives and precursor reaction products. In the last decade, laser ablation and nanoparticle generation in liquids has proven to be a unique and efficient technique to generate, excite, fragment, and conjugate a large variety of nanostructures in a scalable and clean manner. This editorial briefly highlights selected recent advancements and critical aspects in the field of pulsed laser-based nanoparticle generation and manipulation, including exemplary strategies to harvest the unique properties of the laser-generated nanomaterials in the field of biomedicine and catalysis. The presented critical aspects address future assignments such as size control and scale-up. This journal is © 2013 the Owner Societies.
    view abstract10.1039/c2cp90132c
  • Cavitation dynamics of laser ablation of bulk and wire-shaped metals in water during nanoparticles production
    De Giacomo, A. and Dell'Aglio, M. and Santagata, A. and Gaudiuso, R. and De Pascale, O. and Wagener, P. and Messina, G.C. and Compagnini, G. and Barcikowski, S.
    Physical Chemistry Chemical Physics 15 (2013)
    Although the first nanoseconds to microseconds rule the resulting process yield of laser ablation in liquid, a comprehensive view involving combination of time-resolved measurement techniques is still lacking. In this paper, fundamental aspects of laser ablation of metals in water during the production of nanoparticles are discussed. Three fast diagnostic methods have been applied simultaneously. These are Optical Emission Spectroscopy for the plasma characterization, fast shadowgraph for plasma and cavitation bubble dynamics and laser scattering for the mechanisms of delivery of the produced materials in the liquid. Moreover, in order to validate the discussion, the effect on cavitation dynamics of the ablation of bulk and wire-shaped targets has been investigated together with the relative nanoparticles production yield. Unusual arrow-bow ejection phenomena between the cavitation bubble and the wire result in suppressed material back-deposition, causing efficient ejection of ablated matter into the liquid. The presented nanosecond and microsecond-resolved analysis allows estimating the timescale and role of the basic mechanisms involved in laser ablation in liquids as well as the thermodynamic characteristics of the processes. This journal is © 2013 the Owner Societies.
    view abstract10.1039/c2cp42649h
  • Dynamics of silver nanoparticle formation and agglomeration inside the cavitation bubble after pulsed laser ablation in liquid
    Wagener, P. and Ibrahimkutty, S. and Menzel, A. and Plech, A. and Barcikowski, S.
    Physical Chemistry Chemical Physics 15 (2013)
    The formation of nanoparticles within the laser-induced cavitation bubble is studied in situ using small angle X-ray scattering with high spatiotemporal resolution. Directly after laser ablation, two different particle fractions consisting of compact primary particles of 8-10 nm size and agglomerates of 40-60 nm size are formed. The abundance of these species is strongly influenced by the dynamics of the oscillating cavitation bubble. Primary particle mass is most abundant during maximal expansion of the first bubble and reappears a little weaker in the rebound. In contrast to this, the mass abundance of agglomerates is relatively low in the first bubble but strongly increases during first bubble collapse and following rebound. Although most of the ablated material is trapped inside the bubble and follows its oscillation, a minor fraction of both species could be detected outside the cavitation bubble even before its final collapse. This journal is © 2013 the Owner Societies.
    view abstract10.1039/c2cp42592k
  • Laser-based generation of nanocomposites without matrix-coupling agents for bioactive medical devices
    Schwenke, A. and Wagener, P. and Weiß, A. and Klimenta, K. and Wiegel, H. and Sajti, L. and Barcikowski, S.
    Chemie-Ingenieur-Technik 85 (2013)
    New production technologies are required to benefit of the full potential of nanocomposites by homogeneous dispersion of nanoparticles along the process chain. Synthesis of silver nanoparticles by laser ablation in liquid and their integration into polymers are presented. Antibacterial properties of these materials and processability into prototypes for medical devices with antibacterial protection are demonstrated. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstract10.1002/cite.201200035
  • Ligand-free gold-silver nanoparticle alloy polymer composites generated by picosecond laser ablation in liquid monomer
    Menéndez-Manjón, A. and Schwenke, A. and Steinke, T. and Meyer, M. and Giese, U. and Wagener, P. and Barcikowski, S.
    Applied Physics A: Materials Science and Processing 110 (2013)
    Polymer matrix nanocomposites filled with metallic and alloy nanoparticles add functionality in various applications such as optical devices and in the energy sector. However, matrix coupling agents or nanoparticle ligands may be unwanted additives, potentially inhibiting the resulting nanocomposite to be processed by injection molding. The generation of stabilizer-free Au, Ag, and AuAg alloy nanoparticle acrylate composites is achieved by picosecondpulsed laser ablation of the respective metal target in the liquid monomer. Complementary to laser ablation of the solid alloy, we have alloyed nanoparticles by post-irradiation of Au and Ag colloids in the liquid monomer. The optical properties of the colloidal nanoparticles are successfully transferred to the solid poly(methyl methacrylate) matrix and characterized by their plasmon resonance that can be easily tuned between 400 and 600 nm by laser alloying in the liquid monomer. © 2012 Springer-Verlag Berlin Heidelberg.
    view abstract10.1007/s00339-012-7264-0
  • Polymer-stable magnesium nanocomposites prepared by laser ablation for efficient hydrogen storage
    Makridis, S.S. and Gkanas, E.I. and Panagakos, G. and Kikkinides, E.S. and Stubos, A.K. and Wagener, P. and Barcikowski, S.
    International Journal of Hydrogen Energy 38 (2013)
    Hydrogen is a promising alternative energy carrier that can potentially facilitate the transition from fossil fuels to sources of clean energy because of its prominent advantages such as high energy density (142 MJ kg -1), great variety of potential sources (for example water, biomass, organic matter), and low environmental impact (water is the sole combustion product). However, due to its light weight, the efficient storage of hydrogen is still an issue investigated intensely. Various solid media have been considered in that respect among which magnesium hydride stands out as a candidate offering distinct advantages. Recent theoretical work indicates that MgH 2 becomes less thermodynamically stable as particle diameter decreases below 2 nm. Our DFT (density functional theory) modeling studies have shown that the smallest enthalpy change, corresponding to 2 unit-cell thickness (1.6 Å Mg/3.0Å MgH2) of the film, is 57.7 kJ/molMg. This enthalpy change is over 10 kJ/molMg smaller than that of the bulk. It is important to note that the range of enthalpy change for systems that are suitable for mobile storage applications is 15-24 kJ/molH at 298 K. The important key for the development of air-stable Mg-nanocrystals is the use of PMMA (polymethylmethacrylate) as an encapsulation agent. In our work we use laser ablation, a non-electrochemical method, for producing well-dispersed nanoparticles without the presence of any long-range aggregation. The observed improved hydrogenation characteristics of the polymer-stable Mg-nanoparticles are associated to the preparation procedure and in any case the polymer-laser ablation is a new approach for the production of air-protected and inexpensive Mg-nanoparticles. Copyright © 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
    view abstract10.1016/j.ijhydene.2013.04.031
  • Pulsed laser ablation of a continuously-fed wire in liquid flow for high-yield production of silver nanoparticles
    Messina, G.C. and Wagener, P. and Streubel, R. and De Giacomo, A. and Santagata, A. and Compagnini, G. and Barcikowski, S.
    Physical Chemistry Chemical Physics 15 (2013)
    Using wires of defined diameters instead of a planar target for pulsed laser ablation in liquid results in significant increase of ablation efficiency and nanoparticle productivity up to a factor of 15. We identified several competitive phenomena based on thermal conductivity, reflectivity and cavitation bubble shape that affect the ablation efficiency when the geometry of the target is changed. On the basis of the obtained results, this work represents an intriguing starting point for further developments related to the up-scaling of pulsed laser ablation in liquid environments at the industrial level. This journal is © 2013 the Owner Societies.
    view abstract10.1039/c2cp42626a
  • Sex selection of sperm in farm animals: Status report and developmental prospects
    Rath, D. and Barcikowski, S. and Graaf, S.D. and Garrels, W. and Grossfeld, R. and Klein, S. and Knabe, W. and Knorr, C. and Kues, W. and Meyer, H. and Michl, J. and Moench-Tegeder, G. and Rehbock, C. and Taylor, U. and Washausen, S.
    Reproduction 145 (2013)
    Pre-selection of spermatozoa based on the relative DNA difference between X- and Y-chromosome bearing populations by flow cytometry is an established method that has been introduced into commercial cattle production. Although several important improvements have increased the sort efficiency, the fertilising ability of sexed spermatozoa based on offspring per insemination is still behind farmers' expectations. The main stress factors, especially on mitochondria, that reduce the lifespan of spermatozoa are described, and new technical as well as biological solutions to maintain the natural sperm integrity and to increase the sorting efficiency are discussed. Among these methods are the identification of Y-chromosome bearing spermatozoa by bi-functionalised gold nanoparticles and triplex hybridisation in vivo as well as new laser-controlled deflection system that replaces the deflection of spermatozoa in the electrostatic field. Additionally, as well as a new nonsurgical transfer system of spermatozoa into the oviduct of cows has been developed and allows a significant reduction of spermatozoa per transfer. Altogether, the improvements made in the recent years will allow a broader use of sex-sorted spermatozoa even in those species that require more cells than cows and sheep. © 2013 Society for Reproduction and Fertility.
    view abstract10.1530/REP-12-0151
  • Size control of laser-fabricated surfactant-free gold nanoparticles with highly diluted electrolytes and their subsequent bioconjugation
    Rehbock, C. and Merk, V. and Gamrad, L. and Streubel, R. and Barcikowski, S.
    Physical Chemistry Chemical Physics 15 (2013)
    Size control of laser-fabricated surfactant-free gold nanoparticles is a challenging endeavor. In this work, we show that size control can be achieved by adding ions with low salinity during synthesis. In addition, this approach offers the opportunity to fundamentally study ion interactions with bare nanoparticle surfaces and can help to elucidate the nanoparticle formation mechanism. The studies were carried out in a flow-through reactor and in the presence of NaCl, NaBr and sodium phosphate buffer at minimal ionic strengths. A significant size quenching effect at ionic strengths from 1-50 μM was found, which allowed surfactant-free nanoparticle size control with average diameters of 6-30 nm. This effect went along with low polydispersity and minimal aggregation tendencies and was confirmed by UV-vis spectroscopy, TEM, SEM and analytical disk centrifugation. Our findings indicate that size quenching originates from an anionic electrostatic stabilization depending on the nanoparticle surface area, which may be caused by specific ion adsorption. By subsequent delayed bioconjugation in liquid-flow using bovine serum albumin as a stabilizing agent, nano-bioconjugates with good stability in cell culture media were obtained, which are applicable in toxicology and cell biology. This journal is © 2013 the Owner Societies.
    view abstract10.1039/c2cp42641b
  • Bioconjugated silicon quantum dots from one-step green synthesis
    Intartaglia, R. and Barchanski, A. and Bagga, K. and Genovese, A. and Das, G. and Wagener, P. and Di Fabrizio, E. and Diaspro, A. and Brandi, F. and Barcikowski, S.
    Nanoscale 4 (2012)
    Biofunctionalized silicon quantum dots were prepared through a one step strategy avoiding the use of chemical precursors. UV-Vis spectroscopy, Raman spectroscopy and HAADF-STEM prove oligonucleotide conjugation to the surface of silicon nanoparticle with an average size of 4 nm. The nanoparticle size results from the size-quenching effect during in situ conjugation. Photoemissive properties, conjugation efficiency and stability of these pure colloids were studied and demonstrate the bio-application potential, e.g. for nucleic acid vector delivery with semiconducting, biocompatible nanoparticles. © 2012 The Royal Society of Chemistry.
    view abstract10.1039/c2nr11763k
  • Cytotoxicity and ion release of alloy nanoparticles
    Hahn, A. and Fuhlrott, J. and Loos, A. and Barcikowski, S.
    Journal of Nanoparticle Research 14 (2012)
    It is well-known that nanoparticles could cause toxic effects in cells. Alloy nanoparticles with yet unknown health risk may be released from cardiovascular implants made of Nickel-Titanium or Cobalt-Chromium due to abrasion or production failure. We show the bio-response of human primary endothelial and smooth muscle cells exposed to different concentrations of metal and alloy nanoparticles. Nanoparticles having primary particle sizes in the range of 5-250 nm were generated using laser ablation in three different solutions avoiding artificial chemical additives, and giving access to formulations containing nanoparticles only stabilized by biological ligands. Endothelial cells are found to be more sensitive to nanoparticle exposure than smooth muscle cells. Cobalt and Nickel nanoparticles caused the highest cytotoxicity. In contrast, Titanium, Nickel- Iron, and Nickel-Titanium nanoparticles had almost no influence on cells below a nanoparticle concentration of 10 lM. Nanoparticles in cysteine dissolved almost completely, whereas less ions are released when nanoparticles were stabilized in water or citrate solution. Nanoparticles stabilized by cysteine caused less inhibitory effects on cells suggesting cysteine to form metal complexes with bioactive ions in media. © Springer Science+Business Media B.V. 2012.
    view abstract10.1007/s11051-011-0686-3
  • Design and application of a weed damage model for laser-based weed control
    Marx, C. and Barcikowski, S. and Hustedt, M. and Haferkamp, H. and Rath, T.
    Biosystems Engineering 113 (2012)
    Horticultural weed control strategies based on chemical and thermal methods are environmentally and energetically questionable. A promising alternative appears to be the use of laser technology. This study evaluates the influence of CO 2 laser radiation (10,600 nm) taking into account three laser spot diameters, three laser spot positions and six laser intensities on three growth stages of two weed species (monocotyledonous: Echinochloa crus-galli, dicotyledonous: Amaranthus retroflexus). The lethal impact of irradiation was characterised by a decrease of the weed fresh mass of 90% compared to untreated plants two weeks after irradiation. Weed-specific laser damage models were developed and validated, mapping the probabilities of success (p success) of the laser application. Selective lethal laser doses with p success = 0.95 were determined. The results showed that lethality was greatest if treatment was performed at early growth stages with high intensity. Monocotyledonous 2-leaf-plants were damaged at high energy levels, whilst 4-leaf-plants were difficult to kill. Dicotyledonous 2-leaf-plants were already damaged at moderate intensities. Thus, the damage of monocots required higher minimum laser doses than the damage of dicots. The influence of the spot position was important, as the unfocused treatment resulted in a decrease in lethality. In combination with robotics and image processing, the damage models developed here can be used to develop laser-based weed control. A model simulation of two driving concepts for the laser system showed that accurate aiming at the meristem as well as specific parameter adjustment is required for an efficient weed control. © 2012 IAgrE.
    view abstract10.1016/j.biosystemseng.2012.07.002
  • Development of a specially tailored local drug delivery system for the prevention of fibrosis after insertion of cochlear implants into the inner ear
    Bohl, A. and Rohm, H.W. and Ceschi, P. and Paasche, G. and Hahn, A. and Barcikowski, S. and Lenarz, T. and Stöver, T. and Pau, H.-W. and Schmitz, K.-P. and Sternberg, K.
    Journal of Materials Science: Materials in Medicine 23 (2012)
    A cochlear implant (CI)-associated local drug delivery system based on dexamethasone (DMS) was developed with the purpose to inhibit the growth of fibrotic tissue which influences the signal transmission from the CI to the neurons of the inner ear. For the realization of a targeted DMS delivery the following concepts were combined: modification of the silicone-based electrode carrier by incorporation of DMS and a DMS-containing polymeric coating chemically attached on the surface of the electrode carrier. It was demonstrated that the coated CI showed a high coating stability in a simulated implantation procedure. The in vitro drug release studies in a quasi-stationary model revealed a faster DMS release in the initial phase originating from the DMS-containing coatings and then a lower and sustained DMS release originating from the DMS-loaded silicone carrier. The performed in vitro biocompatibility study confirmed that the released DMS was non-toxic for cultured spiral ganglion cells. © Springer Science+Business Media, LLC 2012.
    view abstract10.1007/s10856-012-4698-z
  • Development of new processes for welding of thermal Al-Cu solar absorbers using diode lasers
    Springer, A. and Kallage, P. and Hustedt, M. and Barcikowski, S. and Wesling, V. and Haferkamp, H.
    Journal of Laser Applications 24 (2012)
    Flat-plate solar collectors are favorable devices to generate heat from the energy of the Sun. The central part of a collector, the solar absorber, is a front-coated aluminum sheet with a copper tube fixed on the back side in order to transport heated liquid. Nowadays, the absorber is often fabricated by laser welding with two flashlamp-pumped neodymium-doped yttrium aluminum garnet (Nd:YAG) lasers which provide high peak pulse powers. A disadvantage of this procedure is the high electrical energy consumption. Research on new laser welding processes is aimed to reduce the amount of energy required. Diode lasers allow processing with higher efficiency, due to a better absorption behavior of the aluminum sheet. Accordingly, two different processes have been developed. The first one, using two laser sources in pulsed mode, is similar to the industrial process, but enables an extension of the spot welds in order to increase the joint strength. In contrast, the second process requires only one laser source to weld the tube on both sides, using a scanner system which is integrated in a newly developed innovative laser processing head. By adopting these processes, significant energy savings during the production of solar absorbers can be achieved, ensuring high process reliability at the same time. © 2012 Laser Institute of America.
    view abstract10.2351/1.4736588
  • How citrate ligands affect nanoparticle adsorption to microparticle supports
    Wagener, P. and Schwenke, A. and Barcikowski, S.
    Langmuir 28 (2012)
    Residual ligands from colloidal synthesis of nanoparticles influence adsorption of nanoparticles to supports and may complicate fabrication of nanoparticle-decorated microparticles. In this work, we studied the adsorption of completely ligand-free metal nanoparticles and controlled ligand-functionalized nanoparticles to chemically inert microparticle supports. Adsorption of ligand-free silver nanoparticles to barium sulfate microparticle supports is a quantitative, nonreversible process following Freundlich adsorption isotherm. However, adsorption efficiency is very sensitive to ligand concentration applied during laser-based synthesis of silver nanoparticles: exceeding a specific threshold concentration of 50 μmol/L citrate equal to a nanoparticle ligand surface coverage of about 50%, results in an almost complete prevention of nanoparticle adsorption because of electrosteric repulsion by ligand shell. Laser-based synthesis of nanoparticle-decorated microparticles is demonstrated with a variety of metal nanoparticles (Ag, Au, Pt, Fe) and supporting microparticles (calcium phosphate, titanium dioxide, barium sulfate) with application potential in heterogeneous catalysis or biomedicine where ligand control offers extra value, like enhanced catalytic activity or biocompatibility. © 2012 American Chemical Society.
    view abstract10.1021/la204839m
  • Impact of metal nanoparticles on germ cell viability and functionality
    Taylor, U. and Barchanski, A. and Kues, W. and Barcikowski, S. and Rath, D.
    Reproduction in Domestic Animals 47 (2012)
    Metal nanoparticles play an increasing role in consumer products, biomedical applications and in the work environment. Therefore, the effects of nanomaterials need to be properly understood. This applies especially to their potential reproductive toxicology (nanoreprotoxicity), because any shortcomings in this regard would be reflected into the next generation. This review is an attempt to summarize the current knowledge regarding the effects of nanoparticles on reproductive outcomes. A comprehensive collection of significant experimental nanoreprotoxicity data is presented, which highlight how the toxic effect of nanoparticles can be influenced, not only by the particles' chemical composition, but also by particle size, surface modification, charge and to a considerable extent on the experimental set-up. The period around conception is characterized by considerable cytological and molecular restructuring and is therefore particularly sensitive to disturbances. Nanoparticles are able to penetrate through biological barriers into reproductive tissue and at least can have an impact on sperm vitality and function as well as embryo development. Particularly, further investigations are urgently needed on the repetitively shown effect of the ubiquitously used titanium dioxide nanoparticles on the development of the nervous system. It is recommended that future research focuses more on the exact mechanism behind the observed effects, because such information would facilitate the production of nanoparticles with increased biocompatibility. © 2012 Blackwell Verlag GmbH.
    view abstract10.1111/j.1439-0531.2012.02099.x
  • Impact of spacer and strand length on oligonucleotide conjugation to the surface of ligand-free laser-generated gold nanoparticles
    Barchanski, A. and Hashimoto, N. and Petersen, S. and Sajti, C.L. and Barcikowski, S.
    Bioconjugate Chemistry 23 (2012)
    Gold nanoparticles conjugated to nucleic acids are widely used for biomedical targeting and sensing applications; however, little is known about the conjugation chemistry covering the impact of steric dimension and strand orientation of single-stranded oligonucleotides (ssO) on the conjugation process and binding efficiencies. In this context, we present an extensive investigation concerning the attachment of thiolated ssO to the surface of laser-generated gold nanoparticles, altering both strand length and binding orientation by the insertion of different spacer types at either the 3′ or 5′ ssO terminus. A significant reduction of conjugation efficiency of about 30-50% is determined for spacer-prolonged bionanoconjugates due to coiling effects of the flexible ssO strand on the particle surface which increases deflection angle of oligonucleotides and limits the number of biomolecules attached to the nanoparticles. © 2012 American Chemical Society.
    view abstract10.1021/bc200462b
  • Induction of Osteogenic Differentiation of Adipose Derived Stem Cells by Microstructured Nitinol Actuator-Mediated Mechanical Stress
    Strauß, S. and Dudziak, S. and Hagemann, R. and Barcikowski, S. and Fliess, M. and Israelowitz, M. and Kracht, D. and Kuhbier, J.W. and Radtke, C. and Reimers, K. and Vogt, P.M.
    PLoS ONE 7 (2012)
    The development of large tissue engineered bone remains a challenge in vitro, therefore the use of hybrid-implants might offer a bridge between tissue engineering and dense metal or ceramic implants. Especially the combination of the pseudoelastic implant material Nitinol (NiTi) with adipose derived stem cells (ASCs) opens new opportunities, as ASCs are able to differentiate osteogenically and therefore enhance osseointegration of implants. Due to limited knowledge about the effects of NiTi-structures manufactured by selective laser melting (SLM) on ASCs the study started with an evaluation of cytocompatibility followed by the investigation of the use of SLM-generated 3-dimensional NiTi-structures preseeded with ASCs as osteoimplant model. In this study we could demonstrate for the first time that osteogenic differentiation of ASCs can be induced by implant-mediated mechanical stimulation without support of osteogenic cell culture media. By use of an innovative implant design and synthesis via SLM-technique we achieved high rates of vital cells, proper osteogenic differentiation and mechanically loadable NiTi-scaffolds could be achieved. © 2012 Strauß et al.
    view abstract10.1371/journal.pone.0051264
  • Interface of nanoparticle-coated electropolished stents
    Neumeister, A. and Bartke, D. and Bärsch, N. and Weingärtner, T. and Guetaz, L. and Montani, A. and Compagnini, G. and Barcikowski, S.
    Langmuir 28 (2012)
    Nanostructures entail a high potential for improving implant surfaces, for instance, in stent applications. The electrophoretic deposition of laser-generated colloidal nanoparticles is an appropriate tool for creating large-area nanostructures on surfaces. Until now, the bonding and characteristics of the interface between deposited nanoparticles and the substrate surface has not been known. It is investigated using X-ray photoelectron spectroscopy, Auger electron spectroscopy, and transmission electron microscopy to characterize an electropolished NiTi stent surface coated by laser-generated Au and Ti nanoparticles. The deposition of elemental Au and Ti nanoparticles is observed on the total 3D surface. Ti-coated samples are composed of Ti oxide and Ti carbide because of nanoparticle fabrication and the coating process carried out in 2-propanol. The interface between nanoparticles and the electropolished surface consists of a smooth, monotone elemental depth profile. The interface depth is higher for the Ti nanoparticle coating than for the Au nanoparticle coating. This smooth depth gradient of Ti across the coating-substrate intersection and the thicker interface layer indicate the hard bonding of Ti-based nanoparticles on the surface. Accordingly, electron microscopy reveals nanoparticles adsorbed on the surface without any sorption-blocking intermediate layer. The physicomechanical stability of the bond may benefit from such smooth depth gradients and direct, ligand-free contact. This would potentially increase the coating stability during stent application. © 2012 American Chemical Society.
    view abstract10.1021/la300308w
  • Nanocomposite fibre fabrication via in situ monomer grafting and bonding on laser-generated nanoparticles
    van't Zand, D.D. and Nachev, P. and Rosenfeld, R. and Wagener, P. and Pich, A. and klee, D. and Barcikowski, S.
    Journal of Laser Micro Nanoengineering 7 (2012)
    Bioactive nanocomposites may become an important material if both the carrier matrix and the nanoparticle are biocompatible, like is known for zinc oxide and lactones. The fabrication of such nanocomposite made of polycaprolactone nanofibres with embedded nanoparticles is studied during laser ablation in liquid monomer and polymer solution. The in situ conjugation of zinc oxide nano-particles with ε-caprolactone followed by zinc-initiated polymerization was studied. Indication for covalent bonding between the zinc oxide nanoparticles and the carboxylic units of the oligomers is observed. In addition to the study of the intended nanohybrid formation, possible formation of unintended byproducts was investigated. Laser-induced pyrolysis of solvent was studied for nanosecond, picosecond, and femtosecond laser pulse durations at the same energy input, where all pulse durations caused unintended solvent modification and picosecond pulses were most efficient for nano-particle production. Heading towards fabrication of macroscopic bioactive fibre pads, the laser-generated zinc oxide polymer nanocomposite have been successfully spun into nanofibres using electrospinning. Polymer-embedding is demonstrated at the example of macroscopic nanocomposite fibre pads with various bio-relevant nanoparticles fabricated by laser ablation of magnesium, iron, and tantalum in polycaprolactone solution.
    view abstract10.2961/jlmn.2012.01.0004
  • Nanoparticle formation in a cavitation bubble after pulsed laser ablation in liquid studied with high time resolution small angle x-ray scattering
    Ibrahimkutty, S. and Wagener, P. and Menzel, A. and Plech, A. and Barcikowski, S.
    Applied Physics Letters 101 (2012)
    We investigated nanoparticle formation after pulsed laser ablation in liquid using time-resolved small angle x-ray scattering. Laser ablation of a gold target in water induces a cavitation bubble in which two different particle species could be identified at maximum bubble extension: (i) primary particles of about 8-10 nm diameter, which show a smooth concentration gradient starting from the target and can also be found outside the cavitation bubble in the free liquid and (ii) secondary particles in the range of 45 nm diameter which have highest concentration in the upper part of the cavitation bubble but do not penetrate into the liquid. © 2012 American Institute of Physics.
    view abstract10.1063/1.4750250
  • Physical fabrication of colloidal ZnO nanoparticles combining wet-grinding and laser fragmentation
    Wagener, P. and Lau, M. and Breitung-Faes, S. and Kwade, A. and Barcikowski, S.
    Applied Physics A: Materials Science and Processing 108 (2012)
    Combination of wet-grinding and laser fragmentation is a promising approach to advance both methods: Laser fragmentation will be more efficient when combined with mechanical treatment and wet-grinding may take advance of the abrasion-free laser process to achieve fabrication of smaller particles. By mechanical pre-treatment of zinc oxide microparticles in a stirred-media mill, the starting material is activated by generation of crystallographic defects, which strongly enhance the efficiency of subsequent laser fragmentation. Picosecond-laser irradiation of mechanically treated and untreated microparticles suspended in water yielded in colloidal zinc oxide nanoparticles. Furthermore, nanoparticle productivity and properties can be controlled by variation of anionic surfactant concentration. © 2012 Springer-Verlag.
    view abstract10.1007/s00339-012-6971-x
  • Serum albumin reduces the antibacterial and cytotoxic effects of hydrogel-embedded colloidal silver nanoparticles
    Grade, S. and Eberhard, J. and Neumeister, A. and Wagener, P. and Winkel, A. and Stiesch, M. and Barcikowski, S.
    RSC Advances 2 (2012)
    Although silver nanoparticles (AgNPs) are widely used as ion-releasing antimicrobial additives in medical devices, recent reports indicate the suppression of effectiveness in the presence of blood serum proteins. Bovine serum albumin (BSA) is known to bind silver and silver ions, so that the presence of proteins may change the antibacterial or cytotoxic properties of AgNPs even when they are embedded in a solid agar hydrogel matrix. We produced ligand-free AgNPs by laser ablation in water resulting in aqueous silver mass concentrations of 0.5 to 7.1%. The AgNPs were immersed into agar in concentrations of 5-70 μg ml -1 medium. We examined the influence of 1% BSA within the hydrogel matrix on the nanoparticles' antibacterial effect on four clinically relevant bacteria strains and the cytotoxicity of colloidal AgNP was tested on fibroblasts with or without 1% BSA. The hydrogel-immobilized AgNPs showed a significant reduction of antibacterial activity in the presence of BSA. Cytotoxicity started at a colloidal AgNP concentration of 35 μg ml -1, and addition of BSA significantly reduced the effect on cell morphology and viability. Overall, in the presence of BSA, both antibacterial and cytotoxic effects of AgNPs were markedly reduced. Notably, a therapeutic AgNP window, requiring a dose at which pathogenic bacteria growth is inhibited while fibroblast viability is not affected, could only be observed in the absence of BSA. Addition of BSA reduces the antibacterial activity of AgNP to a point without significant growth inhibition of S. aureus but still observable cytotoxic effects on HGFib. Hence, the presence of a major blood serum protein significantly decreases the antimicrobial effects of AgNPs on a range of pathogenic bacteria even when the NPs are immobilized within an agar hydrogel model. © 2012 The Royal Society of Chemistry.
    view abstract10.1039/c2ra20546g
  • Synthesis of hybrid microgels by coupling of laser ablation and polymerization in aqueous medium
    Nachev, P. and Van 'T Zand, D.D. and Coger, V. and Wagener, P. and Reimers, K. and Vogt, P.M. and Barcikowski, S. and Pich, A.
    Journal of Laser Applications 24 (2012)
    Loading microgels with bioactive nanoparticles (NPs) often requires multiple synthesis and purification steps, and organic solvents or precursors that are difficult to remove from the gel. Hence, a fast and aqueous synthesis procedure would facilitate the synthesis of inorganic-organic hybrid microgels. Two microgel compounds were hybridized with laser-generated zinc oxide (ZnO) NPs prepared in a single-step procedure. ZnO NPs were formed by laser ablation in liquid, while the polymer microgels were synthesized in-situ inside the ablation chamber. Further, the authors report the preparation of two different microgel systems. The first one was produced without the use of chemical initiator forming hydrogels with ZnO NPs and diffuse morpholgy. Typical microgel colloids were also synthesized via a conventional chemical method in a preheated reaction chamber. The existence of microgel colloids partially loaded with ZnO NPs was confirmed in a transmission electron microscopy investigation. Fourier transform infrared spectroscopic measurements and dynamic light scattering verify the formation of polymer colloids. These initial results indicate the application potential of laser ablation in microgel precursor solution for the fabrication of polymeric carriers for inorganic nanoparticles. Preliminary biological tests using zinc chloride demonstrated negative dose effects on primary cell culture with zinc concentrations above 200 μM but no noticeable influence at 100 μM. © 2012 Laser Institute of America.
    view abstract10.2351/1.4730803
  • Therapeutic window of ligand-free silver nanoparticles in agar-embedded and colloidal state: In vitro bactericidal effects and cytotoxicity
    Grade, S. and Eberhard, J. and Wagener, P. and Winkel, A. and Sajti, C.L. and Barcikowski, S. and Stiesch, M.
    Advanced Engineering Materials 14 (2012)
    The inhibition of bacterial growth through effective non-toxic antimicrobial substances is of great importance for the prevention and therapy of implant infections in various medical disciplines. For the evaluation of a therapeutic window of silver nanoparticles (AgNPs), their bactericidal properties were tested in agar composites and colloids on four medical relevant bacteria. Therefore, we produced AgNPs using high-power nanosecond laser ablation in water showing a log-normal particle diameter distribution centered at 17 nm. Bacteria were incubated with AgNP concentrations ranging from 5 to 70 μg · mL -1 and the growth rate was recorded. Additionally, cytotoxic effects of AgNPs on human gingival fibroblasts were examined. The experiments demonstrated that laser-synthesized AgNPs resulted in a significant bacterial growth inhibition of more than 80% at the indicated concentrations in a solid agar model (Pseudomonas aeruginosa 10 μg · mL -1, Streptococcus salivarius 10 μg · mL -1, Escherichia coli 20 μg · mL -1, Staphylococcus aureus 70 μg · mL -1). In a planktonic bacteria model, the growth of the tested bacteria was significantly delayed by the addition of AgNPs at a concentration of 35 μg · mL -1. The cytotoxic assays showed limited adverse effects on human fibroblasts at concentrations of less than 20 μg · mL -1. The present study illustrates the strong antibacterial effects of ligand-free, laser-generated AgNPs that exhibit moderate cytotoxic effects, resulting in a therapeutically applicable concentration of AgNPs for medical purposes between 10 and 20 μg · mL -1. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstract10.1002/adem.201180016
  • Toxicity of gold nanoparticles on somatic and reproductive cells
    Taylor, U. and Barchanski, A. and Garrels, W. and Klein, S. and Kues, W. and Barcikowski, S. and Rath, D.
    Advances in Experimental Medicine and Biology 733 (2012)
    Along with the number of potential applications for gold nanoparticles (AuNP) especially for medical and scientific purposes, the interest in possible toxic effects of such particles is rising. The general perception views nanosized gold colloids as relatively inert towards biological systems. However, a closer analysis of pertinent studies reveals a more complex picture. While the chemical compound of which the nanoparticles consists plays an important role, further biocompatibility determining aspects have been made out. The vast majority of trials concerning AuNP-toxicity were performed using somatic cell culture lines. The results show a considerable dependency of toxic effects on size, zeta potential and surface functionalisation. In vivo studies on this subject are still rare. Based on the existing data it can be assumed, that a dosage of under <400 μg Au/kg showed no untoward effects. If higher amounts were applied toxicity depended on route of administration and particle size. Since nanoparticles have been shown to cross reproduction-relevant biological barriers such as the blood-testicle and the placental barrier the question of their reprotoxicity arises. Yet data concerning this subject is far from adequate. Regarding gametes, recent experiments showed a dose-dependent sensitivity of spermatozoa towards AuNP. Oocytes have not yet been tested in that respect. Interestingly, so far no effects were detected on embryos after gold nanoparticle exposure. In conclusion, the biocompatibility of gold nanoparticles depends on a range of particle specific aspects as well as the choice of target tissue. Further clarification of such matters are subject to ongoing research. © 2012 Springer Science+Business Media B.V.
    view abstract10.1007/978-94-007-2555-3_12
  • A preliminary study of bending stiffness alteration in shape changing nitinol plates for fracture fixation
    Olender, G. and Pfeifer, R. and Müller, C.W. and Gösling, T. and Barcikowski, S. and Hurschler, C.
    Annals of Biomedical Engineering 39 (2011)
    Nitinol is a promising biomaterial based on its remarkable shape changing capacity, biocompatibility, and resilient mechanical properties. Until now, very limited applications have been tested for the use of Nitinol plates for fracture fixation in orthopaedics. Newly designed fracture-fixation plates are tested by four-point bending to examine a change in equivalent bending stiffness before and after shape transformation. The goal of stiffness alterable bone plates is to optimize the healing process during osteosynthesis in situ that is customized in time of onset, percent change as well as being performed non-invasively for the patient. The equivalent bending stiffness in plates of varying thicknesses changed before and after shape transformation in the range of 24-73% (p values < 0.05 for all tests). Tests on a Nitinol plate of 3.0 mm increased in stiffness from 0.81 to 0.98 Nm2 (corresponding standard deviation 0.08 and 0.05) and shared a good correlation to results from numerical calculation. The stiffness of the tested fracture-fixation plates can be altered in a consistent matter that would be predicted by determining the change of the cross-sectional area moment of inertia. © 2011 Biomedical Engineering Society.
    view abstract10.1007/s10439-011-0257-x
  • Comparison of nanoparticle-mediated transfection methods for DNA expression plasmids: Efficiency and cytotoxicity
    Durán, M.C. and Willenbrock, S. and Barchanski, A. and Müller, J.-M.V. and Maiolini, A. and Soller, J.T. and Barcikowski, S. and Nolte, I. and Feige, K. and Murua Escobar, H.
    Journal of Nanobiotechnology 9 (2011)
    Background: Reproducibly high transfection rates with low methodology-induced cytotoxic side effects are essential to attain the required effect on targeted cells when exogenous DNA is transfected. Different approaches and modifications such as the use of nanoparticles (NPs) are being evaluated to increase transfection efficiencies. Several studies have focused on the attained transfection efficiency after NP-mediated approaches. However, data comparing toxicity of these novel approaches with conventional methods is still rare.Transfection efficiency and methodology-induced cytotoxicity were analysed after transfection with different NP-mediated and conventional approaches. Two eukaryotic DNA-expression-plasmids were used to transfect the mammalian cell line MTH53A applying six different transfection protocols: conventional transfection reagent (FuGENE HD, FHD), FHD in combination with two different sizes of stabilizer-free laser-generated AuNPs (PLAL-AuNPs_S1,_S2), FHD and commercially available AuNPs (Plano-AuNP), and two magnetic transfection protocols. 24 h post transfection efficiency of each protocol was analysed using fluorescence microscopy and GFP-based flow cytometry. Toxicity was assessed measuring cell proliferation and percentage of propidium iodide (PI%) positive cells. Expression of the respective recombinant proteins was evaluated by immunofluorescence.Results: The addition of AuNPs to the transfection protocols significantly increased transfection efficiency in the pIRES-hrGFPII-eIL-12 transfections (FHD: 16%; AuNPs mean: 28%), whereas the magnet-assisted protocols did not increase efficiency. Ligand-free PLAL-AuNPs had no significant cytotoxic effect, while the ligand-stabilized Plano-AuNPs induced a significant increase in the PI% and lower cell proliferation. For pIRES-hrGFPII-rHMGB1 transfections significantly higher transfection efficiency was observed with PLAL-AuNPs (FHD: 31%; PLAL-AuNPs_S1: 46%; PLAL-AuNPs_S2: 50%), while the magnet-assisted transfection led to significantly lower efficiencies than the FHD protocol. With PLAL-AuNPs_S1 and _S2 the PI% was significantly higher, yet no consistent effect of these NPs on cell proliferation was observed. The magnet-assisted protocols were least effective, but did result in the lowest cytotoxic effect.Conclusions: This study demonstrated that transfection efficiency of DNA-expression-plasmids was significantly improved by the addition of AuNPs. In some combinations the respective cytotoxicity was increased depending on the type of the applied AuNPs and the transfected DNA construct. Consequently, our results indicate that for routine use of these AuNPs the specific nanoparticle formulation and DNA construct combination has to be considered. © 2011 Durán et al; licensee BioMed Central Ltd.
    view abstract10.1186/1477-3155-9-47
  • Compatibilization of laser generated antibacterial Ag- and Cu-nanoparticles for perfluorinated implant materials
    Stelzig, S.H. and Menneking, C. and Hoffmann, M.S. and Eisele, K. and Barcikowski, S. and Klapper, M. and Müllen, K.
    European Polymer Journal 47 (2011)
    The production of silver and copper particles by laser ablation in an organic solvent and their in situ functionalization with amphiphilic copolymers bearing fluorinated side chains is presented. Aside the stabilization of the particles, the fluorinated side chains render the modified particles compatible with a perfluorinated matrix, which results in a homogeneous distribution of the particles in the matrix. The incorporation of silver particles in perfluorinated matrices is of special interest for the preparation of antibacterial composites, e.g. PTFE, which might be applied in antibacterial implants, e.g. antibacterial vascular prostheses. Laser ablation in liquids as a general method to produce charged nanoparticles of any metal is hence combined with sophisticated surface active compounds. © 2010 Elsevier Ltd. All rights reserved.
    view abstract10.1016/j.eurpolymj.2010.10.018
  • Delay time and concentration effects during bioconjugation of nanosecond laser-generated nanoparticles in a liquid flow
    Sajti, C.L. and Barchanski, A. and Wagener, P. and Klein, S. and Barcikowski, S.
    Journal of Physical Chemistry C 115 (2011)
    Fast ex situ functionalization of gold nanoparticles with fluorophore-labeled cell-penetrating peptides is investigated with a novel liquid flow cascade injection system. Successful conjugation is proved by various methods, such as UV-vis spectrometry and electron microscopy, whereas nanoparticle size-quenching is clearly observed. By variation of the peptide concentration introduced promptly after particle generation, gold nanoparticle bioconjugates with different degrees of cluster formation and/or aggregation and different peptide surface coverage values are obtained. The sizes of synthesized inorganic-organic gold nanoparticle bioconjugate show obvious correlation with time-delayed conjugation, giving evidence that laser-generated nanoparticles continue growing outside the cavitation bubble in the multisecond time scale until achieving their final size. Introducing 6.6 μM bioactive ligands, the highest conjugation efficiency of 93% and ? potential of 27.5 mV is reached at the shortest delay time (200 ms), resulting in 20 nm average sized bioconjugates. Finally, in a preliminary biological application, laser scanning confocal microscopy clearly revealed an amplified cellular uptake using HIV-1 transactivator peptide-conjugated gold nanoparticles compared with nonconjugated entities within embryonic fibroblasts after a short coincubation time of 1 h. The generation of high amounts of highly pure cell-penetrating nanomarkers by the nanosecond laser-assisted fast ex situ conjugation is thus a promising method to probe biological activities such as nanodrug internalization mechanisms. © 2011 American Chemical Society.
    view abstract10.1021/jp1093405
  • Design of Bi-functional bioconjugated gold nanoparticles by pulsed laser ablation with minimized degradation
    Barchanski, A. and Sajti, C.L. and Sehring, C. and Petersen, S. and Barcikowski, S.
    Journal of Laser Micro Nanoengineering 6 (2011)
    Femtosecond-pulsed laser ablation of gold is investigated in electron donor moiety containing biomolecule solutions, resulting in the controlled design of biocompatible, partially charged and electrostatic-stabilized gold nanoconjugates by in situ surface functionalization. The cell-penetrating peptide penetratin and a targeting miniStrep aptamer sequence are conjugated simultaneously to a single nanoparticle for the first time, producing highly stable gold nanoparticle bi-conjugates with defined degrees of surface coverages for each biomolecule. Ablating gold by 100 μJ laser pulses in presence of 1 μM penetratin and 4.5 μM miniStrep yields an average bioconjugate size of 10 nm and results in 61 pmol cm-2 surface coverage for the aptamer and 30 pmol cm-2 for the penetratin. Whereat, degree of surface coverage shows direct correlation to process parameters as well as to biomolecule size, concentration and steric dimension of the biomolecules used. To investigate the influence of time-delayed bioconjugation in view of more efficient up-scaling process, a fast ex situ conjugation is presented in a continuous flow chamber secondary, allowing highly controlled bioconjugation without irradiating the photo- and thermal-sensitive biomolecules and permitting the use of nanosecond laser pulses.
    view abstract10.2961/jlmn.2011.02.0006
  • Effects of metal ions on fibroblasts and spiral ganglion cells
    Paasche, G. and Ceschi, P. and Löbler, M. and Rösl, C. and Gomes, P. and Hahn, A. and Rohm, H.W. and Sternberg, K. and Lenarz, T. and Schmitz, K.-P. and Barcikowski, S. and Stöver, T.
    Journal of Neuroscience Research 89 (2011)
    Degeneration of spiral ganglion cells (SGC) after deafness and fibrous tissue growth around the electrode carrier after cochlear implantation are two of the major challenges in current cochlear implant research. Metal ions are known to possess antimicrobial and antiproliferative potential. The use of metal ions could therefore provide a way to reduce tissue growth around the electrode array after cochlear implantation. Here, we report on in vitro experiments with different concentrations of metal salts with antiproliferative and toxic effects on fibroblasts, PC-12 cells, and freshly isolated spiral ganglion cells, the target cells for electrical stimulation by a cochlear implant. Standard cell lines (NIH/3T3 and L-929 fibroblasts and PC-12 cells) and freshly isolated SGC were incubated with concentrations of metal ions between 0.3 μmol/liter and 10 mmol/liter for 48 hr. Cell survival was investigated by neutral red uptake, CellQuantiBlue assay, or counting of stained surviving neurons. Silver ions exhibited distinct thresholds for proliferating and confluent cells. For zinc ions, the effective concentration was lower for fibroblasts than for PC-12 cells. SGC showed comparable thresholds for reduced cell survival not only for silver and zinc ions but also for copper(II) ions, indicating that these ions might be promising for reducing tissue growth on the surface of CI electrode arrays. These effects were also observed when combinations of two of these ions were investigated. © 2011 Wiley-Liss, Inc.
    view abstract10.1002/jnr.22569
  • Electrochemistry-controlled metal ion release from silicone elastomer nanocomposites through combination of different metal nanoparticles
    Hahn, A. and Günther, S. and Wagener, P. and Barcikowski, S.
    Journal of Materials Chemistry 21 (2011)
    Electrochemistry-controlled metal ion release is achieved using nanoparticle mixtures embedded into a silicone matrix. Synergistic metal ion release from silicone matrix filled with silver and copper nanoparticles as well as silver and gold nanoparticles embedded into silicone is investigated in terms of qualitative and quantitative influences. Results are compared to nanoparticle composites with only one metal. The mechanism enhancing the release of the less noble metal nanoparticle is based on the ion-mediated electrochemistry rather than on contact corrosion of both elements. A retardation as well as an enhancement of metal ion release is observed allowing a time- and rate-controlled design of bioactive nanocomposites. © 2011 The Royal Society of Chemistry.
    view abstract10.1039/c0jm04480f
  • Emission data and costs for environmental measures during laser joining of metals
    Walter, J. and Hustedt, M. and Hennigs, C. and Stein, J. and Barcikowski, S.
    Journal of Laser Micro Nanoengineering 6 (2011)
    Laser welding and soldering are important joining processes in the automotive industry. Typical examples are the production of the car body of the VW Golf or the automatic gearbox of the Mercedes-Benz A-Class. Furthermore, there is a general trend to increase the use of lightweight materials (e.g. Mg, Al, alloys), and to combine different metallic materials to produce complex components (e.g. in tailored blanks). In order to ensure good practices with regard to occupational health and safety as well as environmental issues, laser joining processes have to be analyzed in detail. Avoiding and controlling emission products caused by laser processing of metals or metal composites is an important task in this context. Typically, costs for environmental measures represent a significant percentage of the total manufacturing costs related to a laser process. In this work, emission measurements of several laser welding and soldering processes for metal sheets from steel and brass are reported. Different steel grades and surface treatments of the metal sheets have been taken into account: pure, zinc-coated, PTFE-coated, oiled, cold cleaner residues. The hazardous potential of these processes has been assessed by means of analyzing the specific emissions with respect to the relevant threshold limit values (TLVs). Based on the experimental results, the processes have been classified according to measures which are required by environmental legislation. Finally, a cost calculation for measures related to emission capturing is presented. It has been shown that these environmental measures are manageable for all industrial laser processes regarded here, and the costs for these measures remain acceptable, i.e. in many cases below 8 % of the total processing costs. The results are made permanently available in an interactive internet database. Using this database, the planning of appropriate exhaust systems for laser welding and soldering is facilitated significantly.
    view abstract10.2961/jlmn.2011.02.0008
  • Golden Perspective: Application of Laser-Generated Gold Nanoparticle Conjugates in Reproductive Biology
    Barchanski, A. and Taylor, U. and Klein, S. and Petersen, S. and Rath, D. and Barcikowski, S.
    Reproduction in Domestic Animals 46 (2011)
    Contents: The current demand for female calves has grown rapidly and controlling the sex of offspring provides an economically flexible management for the livestock producer. The only functioning method of efficiently producing separate populations of X and Y sperm in mammals is based on relative DNA differentiation by high-speed flow cytometry. In this context, gold nanoparticles conjugated to sex chromosome-specific moieties display promising application as novel fluorophor-alternative for the high-throughput screening, since they feature no photo bleaching, high quantum yield, good biocompatibility and the possibility of non-destructive membrane penetration. Especially, gold nanoparticles fabricated by pulsed laser ablation are in the recent focus of interest, due to excellent biocompatibility, fabrication-dependent, tuneable particle size as well as surface charge and ease of (bio)-functionalization with a remarkably strong ligand binding. For the purpose of our studies functionalized gold nanoparticles may be used as novel markers for sex-sorting of mammalian sperm and, depending on the selected probe, also for the selection of sperm with heritable DNA-sequences interesting for animal breeding. © 2011 Blackwell Verlag GmbH.
    view abstract10.1111/j.1439-0531.2011.01844.x
  • Hydrodynamic size distribution of gold nanoparticles controlled by repetition rate during pulsed laser ablation in water
    Menéndez-Manjón, A. and Barcikowski, S.
    Applied Surface Science 257 (2011)
    Most investigations on the laser generation and fragmentation of nanoparticles focus on Feret particle size, although the hydrodynamic size of nanoparticles is of great importance, for example in biotechnology for diffusion in living cells, or in engineering, for a tuned rheology of suspensions. In this sense, the formation and fragmentation of gold colloidal nanoparticles using femtosecond laser ablation at variable pulse repetition rates (100-5000 Hz) in deionized water were investigated through their plasmon resonance and hydrodynamic diameter, measured by Dynamic Light Scattering. The increment of the repetition rate does not influence the ablation efficiency, but produces a decrease of the hydrodynamic diameter and blue-shift of the plasmon resonance of the generated gold nanoparticles. Fragmentation, induced by inter-pulse irradiation of the colloids was measured online, showing to be more effective low repetition rates. The pulse repetition rate is shown to be an appropriate laser parameter for hydrodynamic size control of nanoparticles without further influence on the production efficiency. © 2010 Elsevier B.V.
    view abstract10.1016/j.apsusc.2010.12.037
  • Impact of in situ polymer coating on particle dispersion into solid laser-generated nanocomposites
    Wagener, P. and Brandes, G. and Schwenke, A. and Barcikowski, S.
    Physical Chemistry Chemical Physics 13 (2011)
    The crucial step in the production of solid nanocomposites is the uniform embedding of nanoparticles into the polymer matrix, since the colloidal properties or specific physical properties are very sensitive to particle dispersion within the nanocomposite. Therefore, we studied a laser-based generation method of a nanocomposite which enables us to control the agglomeration of nanoparticles and to increase the single particle dispersion within polyurethane. For this purpose, we ablated targets of silver and copper inside a polymer-doped solution of tetrahydrofuran by a picosecond laser (using a pulse energy of 125 μJ at 33.3 kHz repetition rate) and hardened the resulting colloids into solid polymers. Electron microscopy of these nanocomposites revealed that primary particle size, agglomerate size and particle dispersion strongly depend on concentration of the polyurethane added before laser ablation. 0.3 wt% polyurethane is the optimal polymer concentration to produce nanocomposites with improved particle dispersion and adequate productivity. Lower polyurethane concentration results in agglomeration whereas higher concentration reduces the production rate significantly. The following evaporation step did not change the distribution of the nanocomposite inside the polyurethane matrix. Hence, the in situ coating of nanoparticles with polyurethane during laser ablation enables simple integration into the structural analogue polymer matrix without additives. Furthermore, it was possible to injection mold these in situ-stabilized nanocomposites without affecting particle dispersion. This clarifies that sufficient in situ stabilization during laser ablation in polymer solution is able to prevent agglomeration even in a hot polymer melt. © the Owner Societies 2011.
    view abstract10.1039/c0cp02262d
  • Influence of processing time on nanoparticle generation during picosecond-pulsed fundamental and second harmonic laser ablation of metals in tetrahydrofuran
    Schwenke, A. and Wagener, P. and Nolte, S. and Barcikowski, S.
    Applied Physics A: Materials Science and Processing 104 (2011)
    The influence of fundamental and second harmonic wavelength on ablation efficiency and nanoparticle properties is studied during picosecond laser ablation of silver, zinc, and magnesium in polymer-doped tetrahydrofuran. Laser ablation in stationary liquid involves simultaneously the fabrication of nanoparticles by ablation of the target material and fragmentation of dispersed nanoparticles by post irradiation. The ratio in which the laser pulse energy contributes to these processes depends on laser wavelength and colloidal properties. For plasmon absorbers (silver), using the second harmonic wavelength leads to a decrease of the nanoparticle productivity over process time along with exponential decrease in particle diameter, while using the fundamental wavelength results in a constant ablation rate and linear decrease in particle diameter. For colloids made of materials without plasmon absorption (zinc, magnesium), laser scattering is the colloidal property that limits nanoparticle productivity by Mie-scattering of dispersed nanoparticle clusters. © 2011 The Author(s).
    view abstract10.1007/s00339-011-6398-9
  • Metal ion release kinetics from nanoparticle silicone composites
    Hahn, A. and Brandes, G. and Wagener, P. and Barcikowski, S.
    Journal of Controlled Release 154 (2011)
    Metal ion release kinetics from silver and copper nanoparticle silicone composites generated by laser ablation in liquids are investigated. The metal ion transport mechanism is studied by using different model equations and their fit to experimental data. Results indicate that during the first 30 days of immersion, Fickian diffusion is the dominant transport mechanism. After this time period, the oxidation and dissolution of nanoparticles from the bulk determine the ion release. This second mechanism is very slow since the dissolution of the nanoparticle is found to be anisotropic. Silver ion release profile is best described by pseudo-first order exponential equation. Copper ion release profile is best described by a second order exponential equation. For practical purposes, the in vitro release characteristics of the bioactive metal ions are evaluated as a function of nanoparticle loading density, the chemistry and the texture of the silicone. Based on the proposed two-step release model, a prediction of the release characteristics over a time course of 84 days is possible and a long-term ion release could be demonstrated. © 2011 Elsevier B.V. All rights reserved.
    view abstract10.1016/j.jconrel.2011.05.023
  • Nano-energy research trends: Bibliometrical analysis of nanotechnology research in the energy sector
    Menéndez-Manjón, A. and Moldenhauer, K. and Wagener, P. and Barcikowski, S.
    Journal of Nanoparticle Research 13 (2011)
    Nano-energy, the part of nanotechnology dedicated to the study and improvement of the Energy Supply Sector, is a promising and perspective research field. A robust method to quantify international scientific activities in this field is the literature search. An evaluative bibliometric approach applied to the Science Citation Index has been done to retrieve a set of articles related to nano-energy and get knowledge of the direction and trends followed by this particular scientific topic. The resulting database showed an exponential increase of the number of publications issuing nano-based investigations in the energy sector in the last decade, accelerating to an annual growth rate of 1,100%. The most cited articles and the material-clustering protocol revealed that carbon-nanoelements and their application in solar energy harvesting and conversion, and energy storage devices have been principally investigated and represent the main focus in that continuously growing research field. The number of nanotechnology-related papers in the energy database increased monotonically for harvesting, conversion, and storage the last decade, being energy distribution and usage not affected. TiO2 or SnO2 nanoparticles or thin films, and nanocomposites occupied the following top positions in the investigated material ranking. This trend was constant along the decade, as confirmed by network analyses. Supported by discipline- clustering, we observed the fundamental character of the research developed between 2000 and 2009, relying mainly on material science and chemistry. Hence, further implementation of nanotechnology findings is needed to stimulate nano-based energy-focused technologies reaching widespread commercial applications. © Springer Science+Business Media B.V. 2011.
    view abstract10.1007/s11051-011-0344-9
  • Organic nanoparticles generated by combination of laser fragmentation and ultrasonication in liquid
    Wagener, P. and Jakobi, J. and Barcikowski, S.
    Journal of Laser Micro Nanoengineering 6 (2011)
    Melamincyanurate microcrystals suspended in water were converted into colloidal nanoparticles by a novel approach approach of ultrasound-assisted laser fragmentation in a free liquid jet. A crucial step within the laser-based synthesis is the sufficient stabilization of nascent nanoparticles with an adequate stabilization agent. Electron microscopy of stabilized and unstabilized nanoparticle colloids revealed that insufficient stabilized colloids contain a huge fraction of agglomerates consisting of nanoparticles adsorbed on microparticles. Those agglomerates could be destroyed by ultrasound sonication. Therefore, an implementation of ultrasonication into the laser fragmentation process enhances efficiency which was quantified by absorption spectra. By using a high-power nanosecond laser we demonstrated that the technique of laser-fragmentation in free liquid jet could be suitable for scale-up because nanoparticle properties like hydrodynamic size or zeta potential did not depend on laser power or process time and laser-fabricated nanoparticle yield continuously increases during process duration.
    view abstract10.2961/jlmn.2011.01.0013
  • Penetratin-conjugated gold nanoparticles - Design of cell-penetrating nanomarkers by femtosecond laser ablation
    Petersen, S. and Barchanski, A. and Taylor, U. and Klein, S. and Rath, D. and Barcikowski, S.
    Journal of Physical Chemistry C 115 (2011)
    Gold nanoparticles (AuNPs) are promising imaging agents for the long-term visualization and tracing of intracellular functions because they bear outstanding optical properties and are fairly easily bioconjugated. However, the design of such multifunctional nanosystems might be limited by their bioavailability. Cell-penetrating peptides (CPPs) have been shown to be efficient molecular transporters with very few indices of cytotoxicity also in conjunction with nanoparticles. In this context, the current work aims to explore the approach of in situ conjugation during laser ablation in liquids for the design of CPP-NP conjugates at the example of penetratin-conjugated AuNPs. Because penetratin is positively charged at neutral pH, the conjugation process most likely differs from the previously reported coupling of oligonucleotides with their negatively charged phosphate backbone. Results reveal that penetratin is more efficiently bound to AuNPs, increasing the pH value of the ablation media, whereas the size and morphology of the bioconjugates function in terms of the penetratin concentration during the laser process. Probable underlying processes such as size quenching, aggregation, and laser-induced partial melting are assessed by the means of transmission electron microscopy and UV-vis spectroscopy. In a preliminary biological study, laser scanning confocal and transmission electron microscopy revealed a successful uptake of penetratin-conjugated AuNPs for the first time in up to 100% of coincubated cells within 2 h. © 2010 American Chemical Society.
    view abstract10.1021/jp1093614
  • Photoluminescent zinc oxide polymer nanocomposites fabricated using picosecond laser ablation in an organic solvent
    Wagener, P. and Faramarzi, S. and Schwenke, A. and Rosenfeld, R. and Barcikowski, S.
    Applied Surface Science 257 (2011)
    Nanocomposites made of ZnO nanoparticles dispersed in thermoplastic polyurethane were synthesized using picosecond laser ablation of zinc in a polymer-doped solution of tetrahydrofuran. The pre-added polymer stabilizes the ZnO nanoparticles in situ during laser ablation by forming a polymer shell around the nanoparticles. This close-contact polymer shell has a layer thickness up to 30 nm. Analysis of ZnO polyurethane nanocomposites using optical spectroscopy, high resolution transmission electron microscopy and X-ray diffraction revealed that oxidized and crystalline ZnO nanoparticles were produced. Those nanocomposites showed a green photoluminescence emission centred at 538 nm after excitation at 350 nm, which should be attributed to oxygen defects generated during the laser formation mechanism of the monocrystalline nanoparticles. Further, the influence of pulse energy and polymer concentration on the production rate, laser fluence and energy-specific mass productivity was investigated. © 2011 Elsevier B.V.
    view abstract10.1016/j.apsusc.2011.03.097
  • Standardized emission quantification and control of costs for environmental measures
    Walter, J. and Hustedt, M. and Wesling, V. and Barcikowski, S.
    Physics Procedia 12 (2011)
    Laser welding and soldering are important industrial joining processes. As is known, LGACs (Laser Generated Air Contaminants) cause costs for environmental measures during production of complex metallic components (steel, aluminium, magnesium, alloys). The hazardous potential of such processes has been assessed by analyzing the specific emissions with respect to relevant threshold limit values (TLVs). Avoiding and controlling emissions caused by laser processing of metals or metal composites is an important task. Using the experimental results, the planning of appropriate exhaust systems for laser processing is facilitated significantly. The costs quantified for environmental measures account for significant percentages of the total manufacturing costs. © 2011 Published by Elsevier Ltd.
    view abstract10.1016/j.phpro.2011.03.005
  • Stoichiometry of alloy nanoparticles from laser ablation of PtIr in acetone and their electrophoretic deposition on PtIr electrodes
    Jakobi, J. and Menéndez-Manjón, A. and Chakravadhanula, V.S.K. and Kienle, L. and Wagener, P. and Barcikowski, S.
    Nanotechnology 22 (2011)
    Charged Pt-Ir alloy nanoparticles are generated through femtosecond laser ablation of a Pt9Ir target in acetone without using chemical precursors or stabilizing agents. Preservation of the target's stoichiometry in the colloidal nanoparticles is confirmed by transmission electron microscopy (TEM)-energy-dispersive x-ray spectroscopy (EDX), high angle annular dark field (HAADF) scanning transmission electron microscopy (STEM)-EDX elemental maps, high resolution TEM and selected area electron diffraction (SAED) measurements. Results are discussed with reference to thermophysical properties and the phase diagram. The nanoparticles show a lognormal size distribution with a mean Feret particle size of 26nm. The zeta potential of - 45mV indicates high stability of the colloid with a hydrodynamic diameter of 63nm. The charge of the particles enables electrophoretic deposition of nanoparticles, creating nanoscale roughness on three-dimensional PtIr neural electrodes within a minute. In contrast to coating with Pt or Ir oxides, this method allows modification of the surface roughness without changing the chemical composition of PtIr. © 2011 IOP Publishing Ltd.
    view abstract10.1088/0957-4484/22/14/145601
  • Transfer-matrix method for efficient ablation by pulsed laser ablation and nanoparticle generation in liquids
    Menéndez-Manjón, A. and Wagener, P. and Barcikowski, S.
    Journal of Physical Chemistry C 115 (2011)
    Comparable low nanoparticle production is a weakness of femtosecond-pulsed laser ablation in liquids, but the process ablation rate can be maximized at optimal focusing conditions and liquid levels. Refraction at the air-liquid boundary, vaporization of the liquid, self-focusing, and optical breakdown in the liquid complicate the determination of these optimal parameters. A semiempirical method has been developed, allowing an a priori determination of the appropriate experimental setup (liquid layer over the target, focal length, and lens position) for efficient ablation. The presented work can be applied with high accuracy for tightly focused beams, whereas loosely focused ultrashort lasers should be avoided to induce effective fabrication of colloids via laser ablation in liquids. © 2011 American Chemical Society.
    view abstract10.1021/jp109370q
  • Trends and current topics in the field of laser ablation and nanoparticle generation in liquids
    Barcikowski, S. and Mafuné, F.
    Journal of Physical Chemistry C 115 (2011)
    view abstract10.1021/jp111036a
  • Ablation efficiency of α-Al2O3 in liquid phase and ambient air by nanosecond laser irradiation
    Sajti, C.L. and Sattari, R. and Chichkov, B. and Barcikowski, S.
    Applied Physics A: Materials Science and Processing 100 (2010)
    Ablation efficiency and influences of laser parameters on a material removal rate by a nanosecond laser irradiation of α-Al2O 3 are studied in gas and liquid phases. The laser ablation in the air yields maximum material removal rate of 12 ng/pulse using a 4.6-mJ pulse energy at 4-kHz repetition rate, compared to 88 ng/pulse in the water flow. Using a specific interpulse distance and a laser repetition rate further increase material removal rate by factor of 3 and 65, respectively, owing to an optimized lattice temperature and laser pulse interactions with the generated cavitation bubble. For the ablation in the air, these parameters do not significantly affect the ablation efficiency. © 2010 The Author(s).
    view abstract10.1007/s00339-010-5572-9
  • Biocompatibility of nanoactuators: Stem cell growth on laser-generated nickel-titanium shape memory alloy nanoparticles
    Barcikowski, S. and Hahn, A. and Guggenheim, M. and Reimers, K. and Ostendorf, A.
    Journal of Nanoparticle Research 12 (2010)
    Nanoactuators made from nanoparticulate NiTi shape memory alloy show potential in the mechanical stimulation of bone tissue formation from stem cells. We demonstrate the fabrication of Ni, Ti, and NiTi shape memory alloy nanoparticles and their biocompatibility to human adipose-derived stem cells. The stoichiometry and phase transformation property of the bulk alloy is preserved during attrition by femtosecond laser ablation in liquid, giving access to colloidal nanoactuators. No adverse effect on cell growth and attachment is observed in proliferation assay and environmental electron scanning microscopy, making this material attractive for mechanical stimulation of stem cells.
    view abstract10.1007/s11051-009-9834-4
  • First on-line analysis of petroleum from single inclusion using ultrafast laser ablation
    Volk, H. and Fuentes, D. and Fuerbach, A. and Miese, C. and Koehler, W. and Bärsch, N. and Barcikowski, S.
    Organic Geochemistry 41 (2010)
    For many years, geochemical analysis of petroleum from single inclusions has been a challenging objective for fluid inclusion studies. In this study, individual petroleum inclusions have been selectively opened and analysed, for the first time, by coupling an on-line femtosecond laser with a gas chromatograph-mass spectrometer (GC-MS). GC-MS chromatograms show straight chained, branched and cyclic alkanes and aromatic hydrocarbons with carbon numbers ranging from 4 (iso-butane) to 19 (pristane). The distribution of these compounds is similar to that observed by on-line bulk crushing, and pyrolysis artefacts such as alkenes and ketones were not detected. Hydrocarbons with higher carbon numbers appear to have remained in the extraction chamber, a limitation that may be overcome by improvements to the inlet system. This pilot study proves that ultrashort laser pulses can be used to liberate unaltered oil from individual inclusions, thereby creating exciting opportunities for further research aimed at determining the nature of different hydrocarbon palaeo-fluids trapped within single minerals. © 2009 Elsevier Ltd.
    view abstract10.1016/j.orggeochem.2009.05.006
  • Functionality of laser-sintered shape memory micro-actuators
    Dudziak, S. and Gieseke, M. and Haferkamp, H. and Barcikowski, S. and Kracht, D.
    Physics Procedia 5 (2010)
    NiTi shape memory alloys are considered to be difficult to machine. Dimensional accuracy can hardly be met especially in micro-machining. Being a non-contact tool and therefore independent from machining forces, the laser is a promising alternative for manufacturing NiTi micro-parts. This paper presents research results on powder bed-based laser sintering of fine NiTi powders. Structures with a minimum width of approximately 50 |um can be generated without losing the special shape memory properties. The structures "remember" the shape which was set in the laser process. We show that phase transformation temperature can be influenced by process parameters. © 2010 Published by Elsevier B.V.
    view abstract10.1016/j.phpro.2010.08.088
  • Gram scale synthesis of pure ceramic nanoparticles by laser ablation in liquid
    Sajti, C.L. and Sattari, R. and Chichkov, B.N. and Barcikowski, S.
    Journal of Physical Chemistry C 114 (2010)
    Scale-up criteria of laser ablation in the liquid phase with nanosecond pulses is studied for efficient generation of pure ceramic nanoparticles in an aqueous environment. Besides high laser fluence and low height of the applied liquid layer, specific pulse overlap and defined laser repetition rate are required for significant enhancement in nanoparticle productivity. The ablation rate increases by 350% by reducing the liquid film from 8 mm to 2.5 mm owing to reduced absorption and scattering of the incident laser beam by previously ablated nanoparticles. The controlled interpulse distance yields a further increase in material removal rate by another 300% compared to machining in the pulse overlap mode. The residual cavitation bubble from the previous laser pulse and the dispersed nanoparticle interaction with the following laser pulse and optimized temperature gradient in the lattice of the target are assumed to alter productivity. This hypothesis is confirmed by varying the repetition rate with equal laser fluence and pulse overlap, which causes a drastic rise in nanoparticle productivity by a factor of 65. A maximum corundum nanoparticle productivity of 1.3 g/h with Feret particle size of 30 nm is gained by 18.5 W of focused laser power at 4 kHz of repetition rate, providing 125 μm interpulse distance and liquid flow. © 2010 American Chemical Society.
    view abstract10.1021/jp906960g
  • In-situ bioconjugation in stationary media and in liquid flow by femtosecond laser ablation
    Sajti, C.L. and Petersen, S. and Menéndez-Manjón, A. and Barcikowski, S.
    Applied Physics A: Materials Science and Processing 101 (2010)
    In-situ functionalization of gold nanoparticles with fluorophore-tagged oligonucleotides is studied by comparing femtosecond laser ablation in stationary liquid and in biomolecule flow. Femtosecond laser pulses induce significant degradation to sensitive biomolecules when ablating gold in a stationary solution of oligonucleotides. Contrary, in-situ conjugation of nanoparticles in biomolecule flow considerably reduces the degree of degradation studied by gel electrophoresis and UV-Vis spectrometry. Ablating gold with 100 μJ femtosecond laser pulses DNA sequence does not degrade, while the degree of fluorophore tag degradation was 84% in stationary solution compared to 5% for 1 mL/min liquid flow. It is concluded that femtosecond laser-induced degradation of biomolecules is triggered by absorption of nanoparticle conjugates suspended in the colloid and not by ablation of the target. Quenching of nanoparticle size appears from 0.5 μM biomolecule concentration for 0.3 μg/s nanoparticle productivity indicating the successful surface functionalization. Finally, increasing the liquid flow rate from stationary to 450 mL/min enhances nanoparticle productivity from 0.2 μg/s to 1.5 μg/s, as increasing liquid flow allows removal of light absorbing nanoparticles from the ablation zone, avoiding attenuation of subsequent laser photons. © 2010 The Author(s).
    view abstract10.1007/s00339-010-5813-y
  • Influence of beam intensity profile on the aerodynamic particle size distributions generated by femtosecond laser ablation
    Menéndez-Manjn, A. and Barcikowski, S. and Shafeev, G.A. and Mazhukin, V.I. and Chichkov, B.N.
    Laser and Particle Beams 28 (2010)
    The dependence of nanoparticle size distributions on laser intensity profile was determined during infrared femtosecond laser ablation of silver targets in air. Laser parameters were adjusted to ablate at the same peak fluence with spatially homogeneous (flat-top) and inhomogeneous (Gaussian) intensity distributions formed by diffractive optical elements. Aerodynamic particle size was measured online by an electric low-pressure cascade impactor. Narrower size distributions were detected for the flat-top intensity profile in the fluence range from 0.6 to 4.4J/cm2, while the Gaussian beam produced broad and bimodal distributions. The aerodynamic number frequency of the primary nanoparticulate fraction (40nm) was equal to the number frequency of the submicron agglomerate fraction (200nm) at laser fluence of 1J/cm 2. The Feret diameter of primary particles was 80nm. Geometrical interpretation of the irradiated spots at the corresponding laser fluence regimes explains the formation of bimodal (submicron and nanoparticulate) size distribution in the case of Gaussian beams. The bimodality is attributed to different thermalization pathways during laser ablation. Copyright © 2010 Cambridge University Press.
    view abstract10.1017/S0263034609990553
  • Influence of water temperature on the hydrodynamic diameter of gold nanoparticles from laser ablation
    Menéndez-Manjón, A. and Chichkov, B.N. and Barcikowski, S.
    Journal of Physical Chemistry C 114 (2010)
    Defined hydrodynamic properties of nanoparticle colloids are required for applications in dosimetry, rheology, or biosensing studies. During the generation of nanoparticles by laser ablation of a solid target in liquids, the temperature of the liquid increases, which may effect cavitation bubble and particle formation. We demonstrate that this temperature variation influences the hydrodynamic diameter of the resulting colloidal nanoparticles when a gold target is ablated by an IR femtosecond laser in water at different stabilized liquid temperatures in the range of 283-353 K. The maximum hydrodynamic diameter was observed at 330 K, the temperature at which the compressibility of water reaches its minimum. The formation of particles by condensation of ablated species in the liquid matrix or inside the confined cavitation bubble is discussed, as well as the influence of the physical properties of the liquid that vary with temperature, such as viscosity and compressibility. The reduction of the hydrodynamic particle diameter at the higher compressible state of water indicates that a lower number of agglomerates are dispersed in the liquid, reducing the polydispersity index of the gold colloid. © 2010 American Chemical Society.
    view abstract10.1021/jp909897v
  • Laser ablation-based one-step generation and bio-functionalization of gold nanoparticles conjugated with aptamers
    Walter, J.G. and Petersen, S. and Stahl, F. and Scheper, T. and Barcikowski, S.
    Journal of Nanobiotechnology 8 (2010)
    Background: Bio-conjugated nanoparticles are important analytical tools with emerging biological and medical applications. In this context, in situ conjugation of nanoparticles with biomolecules via laser ablation in an aqueous media is a highly promising one-step method for the production of functional nanoparticles resulting in highly efficient conjugation. Increased yields are required, particularly considering the conjugation of cost-intensive biomolecules like RNA aptamers.Results: Using a DNA aptamer directed against streptavidin, in situ conjugation results in nanoparticles with diameters of approximately 9 nm exhibiting a high aptamer surface density (98 aptamers per nanoparticle) and a maximal conjugation efficiency of 40.3%. We have demonstrated the functionality of the aptamer-conjugated nanoparticles using three independent analytical methods, including an agglomeration-based colorimetric assay, and solid-phase assays proving high aptamer activity. To demonstrate the general applicability of the in situ conjugation of gold nanoparticles with aptamers, we have transferred the method to an RNA aptamer directed against prostate-specific membrane antigen (PSMA). Successful detection of PSMA in human prostate cancer tissue was achieved utilizing tissue microarrays.Conclusions: In comparison to the conventional generation of bio-conjugated gold nanoparticles using chemical synthesis and subsequent bio-functionalization, the laser-ablation-based in situ conjugation is a rapid, one-step production method. Due to high conjugation efficiency and productivity, in situ conjugation can be easily used for high throughput generation of gold nanoparticles conjugated with valuable biomolecules like aptamers. © 2010 Walter et al; licensee BioMed Central Ltd.
    view abstract10.1186/1477-3155-8-21
  • Laser fragmentation of organic microparticles into colloidal nanoparticles in a free liquid jet
    Wagener, P. and Barcikowski, S.
    Applied Physics A: Materials Science and Processing 101 (2010)
    We present a novel approach for laser fragmentation of melamine cyanurate microcrystals suspended in liquid into colloidal nanoparticles. Laser fragmentation is done by irradiating a liquid jet of melamine cyanurate suspended in water with intense picosecond pulses. The free liquid jet is generated by a nozzle with small diameter and provides a thin liquid filament (d fil< 1 mm) perpendicular to the focused laser beam. This geometry allows tight focusing resulting in high intensities without the danger of damaging an optical element like windows necessary in conventional flow cells or cuvettes. It reduces losses of excitation light by avoiding scattering or absorption in front of the focus. We stabilized the nanoparticles electrosterically in-situ with neutral and polyelectrolytic polymers preventing agglomeration and precipitation. The threshold for sufficient stabilization of laser-fragmented nanoparticles (d hydrodyn≈200 nm) is reached at a mass fraction of 0.25 wt% dextrin as a neutral polymer and 0.01 wt% polyacrylic acid as a polyelectrolytic polymer. Hydrodynamic size and zeta-potential of the nanoparticles can be controlled by mass fraction of the stabilization agent. © 2010 The Author(s).
    view abstract10.1007/s00339-010-5814-x
  • Laserfragmentierung von anorganischen und organischen mikropartikel- suspensionen zu nanopartikel-kolloiden
    Schnoor, A. and Petersen, S. and Barcikowski, S.
    Chemie-Ingenieur-Technik 82 (2010)
    view abstract10.1002/cite.200900099
  • Magnetic alloy nanoparticles from laser ablation in cyclopentanone and their embedding into a photoresist
    Jakobi, J. and Petersen, S. and Menéndez-Manjón, A. and Wagener, P. and Barcikowski, S.
    Langmuir 26 (2010)
    The generation of nonoxidized magnetic alloy nanoparticles is still a challenge using conventional chemical reduction methods. However, because these nanoparticles are currently attracting much attention, alternative methods are required. In this context, the applicability of femtosecond laser ablation, which has evolved as a powerful tool for the generation of colloidal metal nanoparticles, has been investigated using the example of Ni48Fe 52 and Sm2Co17 ablation in cyclopentanone. Besides stability and size measurements, the focus has been placed on the analysis of the elemental composition of nanoparticles, which proved the preservation of the stoichiometry of the target in Ni-Fe nanoparticles but not in Sm-Co. It is assumed that this is due to a greater difference in the heat of evaporation of the bulk alloy components in Sm-Co than in Ni-Fe. Hence, the successful generation of magnetic alloy nanoparticles is possible for alloys composed of elements with similar heats of evaporation. This one-step approach allows the fabrication of nanomagnetic polymer composites (e.g., with application prospects in microtechnology such as microactuators). © 2010 American Chemical Society.
    view abstract10.1021/la101014g
  • Nonendosomal cellular uptake of ligand-free, positively charged gold nanoparticles
    Taylor, U. and Klein, S. and Petersen, S. and Kues, W. and Barcikowski, S. and Rath, D.
    Cytometry Part A 77 (2010)
    Gold nanoparticles (GNPs) have interesting optical properties, such as exceptionally high quantum yields and virtually limitless photostability. Therefore, they show the potential for applications as biomarkers especially suitable for in vivo and long-term studies. The generation of GNPs using pulsed laser light rather than chemical means provides nanoparticles, which are remarkably stable in a variety of media without the need of stabilizing agents or ligands. This stabilization is achieved by partial oxidation of the gold surface resulting in positively charged GNPs. However, little is known about cellular uptake of such ligand-free nanoparticles, their intracellular fate, or cell viability after nanoparticle contact. The current work is aimed to explore the response of a bovine cell line to GNP exposure mainly using laser scanning confocal microscopy (LSCM) supported by other techniques. Cultured bovine immortalized cells (GM7373) were coincubated with GNP (average diameter 15 nm, 50 μM Au) for 2, 24, and 48 h. The detection of GNP-associated light scattering by the LSCM facilitated a clear distinction between GNP-containing cells and the negative controls. After 48 h, 75% of cells had visibly incorporated nanoparticles. No colocalization was detected with either Rab5a or Lamp1-positive structures, i.e., endosomes or lysosomes, respectivley. However, transmission electron microscope analysis of GNP-coincubated cells indicated the nanoparticles to be positioned within electron-dense structures. Coincubation at 4°C did not inhibit nanoparticle uptake, suggesting diffusion as possible entrance mechanism. Although the assessment of cell morphology, membrane integrity, and apoptosis revealed no GNP-related loss of cell viability at a gold concentration of 25 μM or below, a cytotoxic effect was observed in a proliferation assay after exposing low cell numbers to 50 μM Au and above. In conclusion, this study confirmed the cellular uptake of ligand-free gold nanoparticles during coincubation apparently without using endocytic pathways. © 2010 International Society for Advancement of Cytometry.
    view abstract10.1002/cyto.a.20846
  • Pulsed laser ablation of zinc in tetrahydrofuran: Bypassing the cavitation bubble
    Wagener, P. and Schwenke, A. and Chichkov, B.N. and Barcikowski, S.
    Journal of Physical Chemistry C 114 (2010)
    We applied a high-power (25 W) picosecond-pulsed laser system in combination with fast scanner optics for pulsed laser ablation in liquids in order to generate zinc/zinc oxide nanoparticles in tetrahydrofuran with optimized efficiency. Systematic variation of repetition rate and interpulse distance of subsequent laser pulses strongly affects the ablation efficiency. Shielding of subsequent laser pulses by induced cavitation bubbles could be minimized by these parameters. The analysis of experimental data results in a time constant of 55 μs concerning the cavitation bubble decay and a nonspherical shape with a lateral elongation of 120 μm after 100 μs. Regarding these parameters allows temporal and spatial bypassing of the cavitation bubble to enhance ablation efficiency and nanoparticle productivity. Furthermore, there is a nonlinear dependency of ablation efficiency on interpulse distance even if an effect coupled by cavitation bubbles can be excluded. We interpret this as a competition between two ablation mechanisms including thermal vaporization and phase explosion. For that purpose, we assume a transient preheating of the target by previous pulse, which leads to less efficient heat conduction that favors phase explosion instead of thermal vaporization. Calculations of 1D-heat conduction and analysis of generated nanoparticles support that interpretation. We were able to model the shape of the cavitation bubble and the experimental data by an adopted fit function. © 2010 American Chemical Society.
    view abstract10.1021/jp911243a
  • Pulsed Nd:YAG laser cutting of NiTi shape memory alloys - Influence of process parameters
    Pfeifer, R. and Herzog, D. and Hustedt, M. and Barcikowski, S.
    Journal of Materials Processing Technology 210 (2010)
    Shape memory alloys (SMAs), in particular Nitinol (NiTi), are of increasing interest in research and industry due to their outstanding properties, e.g. the shape memory effect (SME) and high biocompatibility. Obviously, it is necessary to machine these elements from NiTi sheet materials using suitable processing methods that provide high precision and retain the shape memory effect. Pulsed Nd:YAG laser cutting of 1 mm thick NiTi shape memory alloys for medical applications (SMA-implants) has been investigated. Due to the local energy input only small heat-affected zones (HAZ) occur and the shape memory properties remain. The influence of key parameters like pulse energy, pulse width, and spot overlap on the cut geometry, roughness and HAZ is shown. © 2010 Elsevier B.V. All rights reserved.
    view abstract10.1016/j.jmatprotec.2010.07.004
  • Quantification of colloidal and intracellular gold nanomarkers down to the single particle level using confocal microscopy
    Klein, S. and Petersen, S. and Taylor, U. and Rath, D. and Barcikowski, S.
    Progress in Biomedical Optics and Imaging - Proceedings of SPIE 7573 (2010)
    The high quantum yield and exclusively photo-stable excitation of gold nanoparticles combined with their bio-inert characteristics make them ideal cellular markers. The aim of the study was to visualise gold nanoparticles size-dependently as colloid and in cells after co-incubation. We show the quantification of colloidal gold particles by standard confocal microscopy down to the single particle level. A calibration is demonstrated for pixel numbers in dilution series of uncoated gold nanoparticles. We give implications for practical use of advanced cellular imaging in cultured cells. © 2010 Copyright SPIE - The International Society for Optical Engineering.
    view abstract10.1117/12.840985
  • Quantitative visualization of colloidal and intracellular gold nanoparticles by confocal microscopy
    Klein, S. and Petersen, S. and Taylor, U. and Rath, D. and Barcikowski, S.
    Journal of Biomedical Optics 15 (2010)
    Gold nanoparticles (AuNPs) have the potential to become a versatile biomarker. For further use of AuNPs labeled with functionalized molecules, their visualization in biological systems by routine laboratory tools such as light microscopy is crucial. However, the size far below the diffraction limit affords specialized parameters for microscopical detection, which stimulated the current study, aimed to determine from which size onward AuNPs, either in dispersion or cell-associated, can be reliably detected by standard confocal microscopy. First, gold colloids of size-restricted fractions are examined in dispersion. At a minimum particle size of 60 nm, detection appears to be reliable. Particle counts in dilution series confirm these results by revealing single particle detection of 60-nm colloids. Second, AuNPs are visualized and quantified in cells, which interestingly cause a phase shift in the reflection of AuNPs. Gold mass spectroscopy confirms the number of AuNPs counted microscopically inside cells. Furthermore, it demonstrates for the first time a very high diffusion rate of 15-nm particles into the cells. In conclusion, the results back the suitability of confocal microscopy for the quantitative tracking of colloidal and intracellular gold nanoparticles sized 60 nm. © 2010 Society of Photo-Optical Instrumentation Engineers.
    view abstract10.1117/1.3461170
  • Reduced wear and adhesion forces by laser dispersing of ceramics
    Nölke, C. and Claußen, S. and Dudziak, S. and Haferkamp, H. and Barcikowski, S.
    Physics Procedia 5 (2010)
    Laser dispersing offers a great potential to fabricate layers or tracks with tailored properties threat duce abrasive or adhesive wear at the surface of highly stressed components. Different ceramic powder materials like aluminum nitride, aluminum oxide and titanium carbide have been embedded in the surface of tool steels using laser dispersing. The created layers were investigated regarding their elemental composition, dimension, particle distribution and hardness curve.
    view abstract10.1016/j.phpro.2010.08.165
  • Softlithographic, partial integration of surface-active nanoparticles in a PDMS matrix for microfluidic biodevices
    Demming, S. and Hahn, A. and Edlich, A. and Franco-Lara, E. and Krull, R. and Barcikowski, S. and Büttgenbach, S.
    Physica Status Solidi (A) Applications and Materials Science 207 (2010)
    The mergence of microfluidics and nanocomposite materials and their in situ structuring leads to a higher integration level within microsystems technology. Nanoparticles (Cu and Ag) produced via laser radiation were suspended in Poly(dimethylsiloxane) to permanently modify surface material. A microstructuring process was implemented which allows the incorporation of these nanomaterials globally or partially at defined locations within a microbioreactor (MBR) for the determination of their antiseptic and toxic effects on the growth of biomass. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstract10.1002/pssa.200983311
  • Therapeutic window for bioactive nanocomposites fabricated by laser ablation in polymer-doped organic liquids
    Hahn, A. and Stöver, T. and Paasche, G. and Löbler, M. and Sternberg, K. and Rohm, H. and Barcikowski, S.
    Advanced Engineering Materials 12 (2010)
    Polymeric nanomaterials are gaining increased interest in medical applications due to the sustained release ofbioactive agents. Within this study nanomaterials are fabricated using laser ablation of silver and copper in polymer-doped organic liquids thus allowing to produce customized drug release systems. A strategy is shown to determine the therapeutic window for cells relevant for cochlear implant electrodes, defined by the viability of L929 fibroblasts, PC12 neuronal cells, and spiral ganglion cells on different concentrations ofsilver and copper ions. The distribution ofnanoparticles within the silicone polymer matrix is determined using transmission electron microscopy. Hexane doped with 1% silicone resin is found to be an appropriate liquid matrix to fabricate a nanocomposite with a constant ion release rate. Silver ions of 10 μmol L-1 or copper ions of 100 μmol L -1 cause a suppression of tissue growth without inhibiting neuronal cell growth. The copper nanoparticle content of 0.1 wt% of the silicone composite releases ion concentrations which fit the therapeutic window. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA.
    view abstract10.1002/adem.200980071
  • catalysts

  • colloids

  • laser

  • laser ablation

  • medical applications

  • nanocomposites

  • nanoparticles

  • polymers

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