TY - JOUR A1 - Heinrich, Thomas A1 - Traulsen, Christoph Hans-Henning A1 - Holzweber, Markus A1 - Richter, S. A1 - Kunz, V. A1 - Kastner, S.K. A1 - Krabbenborg, S.O. A1 - Huskens, J. A1 - Unger, Wolfgang A1 - Schalley, C.A. T1 - Coupled molecular switching processes in ordered mono- and multilayers of stimulus-responsive rotaxanes on gold surfaces N2 - Interfaces provide the structural basis for function as, for example, encountered in nature in the membrane-embedded photosystem or in technology in solar cells. Synthetic functional multilayers of molecules cooperating in a coupled manner can be fabricated on surfaces through layer-by-layer self-assembly. Ordered arrays of stimulus-responsive rotaxanes undergoing well-controlled axle shuttling are excellent candidates for coupled mechanical motion. Such stimulus-responsive surfaces may help integrate synthetic molecular machines in larger systems exhibiting even macroscopic effects or generating mechanical work from chemical energy through cooperative action. The present work demonstrates the successful deposition of ordered mono- and multilayers of chemically switchable rotaxanes on gold surfaces. Rotaxane mono- and multilayers are shown to reversibly switch in a coupled manner between two ordered states as revealed by linear dichroism effects in angle-resolved NEXAFS spectra. Such a concerted switching process is observed only when the surfaces are well packed, while less densely packed surfaces lacking lateral order do not exhibit such effects. KW - Molecular machine KW - Rotaxane KW - LBL growth KW - XPS KW - NEXAFS KW - SIMS PY - 2015 DO - https://doi.org/10.1021/ja512654d SN - 0002-7863 SN - 1520-5126 VL - 137 IS - 13 SP - 4382 EP - 4390 PB - American Chemical Society CY - Washington, DC, USA AN - OPUS4-33077 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Traulsen, C. H.-H. A1 - Kunz, V. A1 - Heinrich, Thomas A1 - Richter, S. A1 - Holzweber, Markus A1 - Schulz, A. A1 - von Krbek, L. K. S. A1 - Scheuschner, U. T. J. A1 - Poppenberg, J. A1 - Unger, Wolfgang A1 - Schalley, C. A. T1 - Synthesis and coordinative layer-by-layer deposition of pyridine-functionalized gold nanoparticles and tetralactam macrocycles on silicon substrates N2 - Coordination chemistry was applied to deposit pyridine-functionalized gold nanoparticles on silicon substrates. The particles were synthesized through the Brust/Schiffrin route with a subsequent ligand exchange reaction yielding well-defined particles of two different sizes. Multilayer deposition was carried out on a pyridine-terminated SAM, anchored on a hydroxyl-terminated silicon surface. Analogously, Hunter/Vögtle-type tetralactam macrocycle multilayers were deposited as well as mixed layers containing both either in an alternating sequence or as a macrocycle multilayer with a terminating nanoparticle layer. These composite layers were examined with respect to their ability to bind squaraine axles in the macrocycle cavities. The amount of guest bound is higher for the composite layer with alternating macrocycles and nanoparticles. KW - Layer-by-layer deposition KW - Functionalized Au nanoparticles KW - SEM KW - TEM KW - DLS KW - XPS KW - NEXAFS KW - ToF-SIMS KW - IR KW - UV-vis PY - 2013 DO - https://doi.org/10.1021/la403222x SN - 0743-7463 SN - 1520-5827 VL - 29 IS - 46 SP - 14284 EP - 14292 PB - American Chemical Society CY - Washington, DC AN - OPUS4-29699 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sieg, H. A1 - Braeuning, C. A1 - Kunz, B. M. A1 - Daher, H. A1 - Kästner, C. A1 - Krause, B.-C. A1 - Meyer, T. A1 - Jalili, P. A1 - Kogeveen, K. A1 - Böhmert, L. A1 - Lichtenstein, D. A1 - Burel, A. A1 - Chevance, S. A1 - Jungnickel, H. A1 - Tentschert, J. A1 - Laux, P. A1 - Braeuning, A. A1 - Gauffre, F. A1 - Fessard, V. A1 - Meijer, J. A1 - Estrela-Lopis, I. A1 - Thünemann, Andreas A1 - Luch, A. A1 - Lampen, A. T1 - Uptake and molecular impact of aluminum-containing nanomaterials on human intestinal caco-2 cells N2 - Aluminum (Al) is one of the most common elements in the earth crust and increasingly used in food, consumer products and packaging. Its hazard potential for humans is still not completely understood. Besides the metallic form, Al also exists as mineral, including the insoluble oxide, and in soluble ionic forms. Representatives of these three species, namely a metallic and an oxidic species of Al-containing nanoparticles and soluble aluminum chloride, were applied to human intestinal cell lines as models for the intestinal barrier. We characterized physicochemical particle parameters, protein corona composition, ion release and cellular uptake. Different in vitro assays were performed to determine potential effects and molecular modes of Action related to the individual chemical species. For a deeper insight into signaling processes, microarray transcriptome analyses followed by bioinformatic data analysis were employed. The particulate Al species showed different solubility in biological media. Metallic Al nanoparticles released more ions than Al2O3 nanoparticles, while AlCl3 showed a mixture of dissolved and agglomerated particulate entities in biological media. The protein corona composition differed between both nanoparticle species. Cellular uptake, investigated in transwell experiments, occurred predominantly in particulate form, whereas ionic Al was not taken up by intestinal cell lines. Transcellular transport was not observed. None of the Al species showed cytotoxic effects up to 200 mg Al/mL. The transcriptome analysis indicated mainly effects on oxidative stress pathways, xenobiotic metabolism and metal homeostasis. We have shown for the first time that intestinal cellular uptake of Al occurs preferably in the particle form, while toxicological effects appear to be ion-related. KW - Small-angle x-ray scattering KW - SAXS KW - Nanopatricle PY - 2018 DO - https://doi.org/10.1080/17435390.2018.1504999 SN - 1743-5390 VL - 12 IS - 9 SP - 992 EP - 1013 PB - Taylor & Francis AN - OPUS4-47432 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Holzweber, Markus A1 - Heinrich, T. A1 - Kunz, V. A1 - Richter, S. A1 - Traulsen, C.H.-H. A1 - Schalley, C.A. A1 - Unger, Wolfgang T1 - Principal component analysis (PCA)-assisted time-of-flight secondary-ion mass spectrometry (ToF-SIMS): a versatile method for the investigation of self-assembled monolayers and multilayers as precursors for the bottom-up approach of nanoscaled devices N2 - The production of high-quality self-assembled monolayers (SAMs) followed by layer-by-layer (LbL) self-assembly of macrocycles is essential for nanotechnology applications based on functional surface films. To help interpret the large amount of data generated by a standard ToF-SIMS measurement, principal component analysis (PCA) was used. For two examples, the advantages of a combination of ToF-SIMS and PCA for quality control and for the optimization of layer-by-layer self-assembly are shown. The first example investigates how different cleaning methods influence the quality of SAM template formation. The second example focuses on the LbL self-assembly of macrocycles and the corresponding stepwise surface modification. KW - ToF-SIMS KW - Principal component analysis KW - Self assembled monolayer KW - Layer by layer PY - 2014 DO - https://doi.org/10.1021/ac500059a SN - 0003-2700 SN - 1520-6882 VL - 86 IS - 12 SP - 5740 EP - 5748 PB - American Chemical Society CY - Washington, DC AN - OPUS4-30963 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Marcoulaki, E. A1 - M. López de Ipina, J. A1 - Vercauteren, S. A1 - Bouillard, J. A1 - Himly, M. A1 - Lynch, I. A1 - Witters, H. A1 - Shandilya, N. A1 - van Duuren-Stuurman, B. A1 - Kunz, Valentin A1 - Unger, Wolfgang A1 - Hodoroaba, Vasile-Dan A1 - Bard, D. A1 - Evans, G. A1 - Jensen, K. A. A1 - Pilou, M. A1 - Viitanen, A.-K. A1 - Bochon, A. A1 - Duschl, A. A1 - Geppert, M. A1 - Persson, K. A1 - Votgreave, I. A1 - Niga, P. A1 - Gini, M. A1 - Eleftheriadis, K. A1 - Scalbi, S. A1 - Caillard, B. A1 - Arevalillo, A. A1 - Frejafon, E. A1 - Aguerre-Chariol, O. A1 - Dulio, V. T1 - Blueprint for a self-sustained European Centre for service provision in safe and sustainable innovation for nanotechnology N2 - The coming years are expected to bring rapid changes in the nanotechnology regulatory landscape, with the establishment of a new framework for nano-risk governance, in silico approaches for characterisation and Risk assessment of nanomaterials, and novel procedures for the early identification and management of nanomaterial risks. In this context, Safe(r)-by-Design (SbD) emerges as a powerful preventive approach to support the development of safe and sustainable (SSbD) nanotechnology-based products and processes throughout the life cycle. This paper summarises the work undertaken to develop a blueprint for the deployment and operation of a permanent European Centre of collaborating laboratories and research organisations supporting safe Innovation in nanotechnologies. The proposed entity, referred to as “the Centre”, will establish a ‘one-stop shop’ for nanosafety-related services and a central contact point for addressing stakeholder questions about nanosafety. Its operation will rely on significant business, legal and market knowledge, as well as other tools developed and acquired through the EU-funded EC4SafeNano project and subsequent ongoing activities. The proposed blueprint adopts a demand-driven service update scheme to allow the necessary vigilance and flexibility to identify opportunities and adjust its activities and services in the rapidly evolving regulatory and nano risk governance landscape. The proposed Centre will play a major role as a conduit to transfer scientific knowledge between the Research and commercial laboratories or consultants able to provide high quality nanosafety services, and the end-users of such services (e.g., industry, SMEs, consultancy firms, and regulatory authorities). The Centre will harmonise service provision, and bring novel risk assessment and management approaches, e.g. in silico methodologies, closer to practice, notably through SbD/SSbD, and decisively support safe and sustainable innovation of industrial production in the nanotechnology industry according to the European Chemicals Strategy for Sustainability. KW - Nanotechnology KW - European Centre KW - Nano-safety KW - Nanomaterials KW - analytical service PY - 2021 DO - https://doi.org/10.1016/j.impact.2021.100337 VL - 23 SP - 100337 PB - Elsevier B.V. AN - OPUS4-52942 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kunz, C. A1 - Büttner, T.N. A1 - Naumann, B. A1 - Boehm, A.V. A1 - Gnecco, E. A1 - Bonse, Jörn A1 - Neumann, C. A1 - Turchanin, A. A1 - Müller, F.A. A1 - Gräf, S. T1 - Large-area fabrication of low- and high-spatial-frequency laser-induced periodic surface structures on carbon fibers N2 - The formation and properties of laser-induced periodic surface structures (LIPSS) were investigated on carbon fibers under irradiation of fs-laser pulses characterized by a pulse duration τ = 300 fs and a laser wavelength λ = 1025 nm. The LIPSS were fabricated in an air environment at normal incidence with different values of the laser peak fluence and number of pulses per spot. The morphology of the generated structures was characterized by using scanning electron microscopy, atomic force microscopy and Fast-Fourier transform analyses. Moreover, the material structure and the surface chemistry of the carbon fibers before and after laser irradiation was analyzed by micro Raman spectroscopy and X-ray photoelectron spectroscopy. Large areas in the cm2 range of carbon fiber arrangements were successfully processed with homogenously distributed high- and low-spatial frequency LIPSS. Beyond those distinct nanostructures, hybrid structures were realized for the very first time by a superposition of both types of LIPSS in a two-step process. The findings facilitate the fabrication of tailored LIPSS-based surface structures on carbon fibers that could be of particular interest for e.g. fiber reinforced polymers and concretes. KW - Fs-Laser KW - Laser-induced periodic surface structures (LIPSS) KW - Carbon fibers KW - Large area structuring PY - 2018 UR - https://www.sciencedirect.com/science/article/pii/S0008622318302781 DO - https://doi.org/10.1016/j.carbon.2018.03.035 SN - 0008-6223 SN - 1873-3891 VL - 133 SP - 176 EP - 185 PB - Elsevier Ltd. AN - OPUS4-44625 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -