TY - JOUR A1 - Haase, A. A1 - Arlinghaus, H. F. A1 - Tentschert, J. A1 - Jungnickel, H. A1 - Graf, P. A1 - Mantion, Alexandre A1 - Draude, F. A1 - Galla, S. A1 - Plendl, J. A1 - Goetz, M.E. A1 - Masic, A. A1 - Meier, W. A1 - Thünemann, Andreas A1 - Taubert, A. A1 - Luch, A. T1 - Application of laser postionization secondary neutral mass spectrometry / time-of-flight secondary ion mass spectrometry in nanotoxicology: Visualization of nanosilver in human macrophages and cellular responses N2 - Silver nanoparticles (SNP) are the subject of worldwide commercialization because of their antimicrobial effects. Yet only little data on their mode of action exist. Further, only few techniques allow for visualization and quantification of unlabeled nanoparticles inside cells. To study SNP of different sizes and coatings within human macrophages, we introduce a novel laser postionization secondary neutral mass spectrometry (Laser-SNMS) approach and prove this method superior to the widely applied confocal Raman and transmission electron microscopy. With time-of-flight secondary ion mass spectrometry (TOF-SIMS) we further demonstrate characteristic fingerprints in the lipid pattern of the cellular membrane indicative of oxidative stress and membrane fluidity changes. Increases of protein carbonyl and heme oxygenase-1 levels in treated cells confirm the presence of oxidative stress biochemically. Intriguingly, affected phagocytosis reveals as highly sensitive end point of SNP-mediated adversity in macrophages. The cellular responses monitored are hierarchically linked, but follow individual kinetics and are partially reversible. KW - Nanosilver KW - Laser-SNMS KW - TOF-SIMS KW - Confocal Raman microscopy KW - Oxidative stress KW - Protein carbonyls PY - 2011 DO - https://doi.org/10.1021/nn200163w SN - 1936-0851 VL - 5 IS - 4 SP - 3059 EP - 3068 PB - ACS Publ. CY - Washington, DC, USA AN - OPUS4-23656 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Draude, F. A1 - Galla, S. A1 - Pelster, A. A1 - Tentschert, J. A1 - Jungnickel, H. A1 - Haase, A. A1 - Mantion, Alexandre A1 - Thünemann, Andreas A1 - Taubert, A. A1 - Luch, A. A1 - Arlinghaus, H. F. T1 - ToF-SIMS and laser-SNMS analysis of macrophages after exposure to silver nanoparticles N2 - Silver nanoparticles (SNPs) are among the most commercialized nanoparticles because of their antibacterial effects. Besides being employed, e.g. as a coating material for sterile surfaces in household articles and appliances, the particles are also used in a broad range of medical applications. Their antibacterial properties make SNPs especially useful for wound disinfection or as a coating material for prostheses and surgical instruments. Because of their optical characteristics, the particles are of increasing interest in biodetection as well. Despite the widespread use of SNPs, there is little knowledge of their toxicity. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and laser post-ionization secondary neutral mass spectrometry (Laser-SNMS) were used to investigate the effects of SNPs on human macrophages derived from THP-1 cells in vitro. For this purpose, macrophages were exposed to SNPs. The SNP concentration ranges were chosen with regard to functional impairments of the macrophages. To optimize the analysis of the macrophages, a special silicon wafer sandwich preparation technique was employed; ToF-SIMS was employed to characterize fragments originating from macrophage cell membranes. With the use of this optimized sample preparation method, the SNP-exposed macrophages were analyzed with ToF-SIMS and with Laser-SNMS. With Laser-SNMS, the three-dimensional distribution of SNPs in cells could be readily detected with very high efficiency, sensitivity, and submicron lateral resolution. We found an accumulation of SNPs directly beneath the cell membrane in a nanoparticular state as well as agglomerations of SNPs inside the cells. KW - Laser-SNMS KW - ToF-SIMS KW - Life sciences KW - Imaging KW - Nanoparticles KW - Three-dimensional depth profiling KW - Silver nanoparticle PY - 2013 DO - https://doi.org/10.1002/sia.4902 SN - 0142-2421 SN - 1096-9918 VL - 45 IS - 1 SP - 286 EP - 289 PB - Wiley CY - Chichester AN - OPUS4-27585 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tentschert, J. A1 - Draude, F. A1 - Jungnickel, H. A1 - Haase, A. A1 - Mantion, Alexandre A1 - Galla, S. A1 - Thünemann, Andreas A1 - Taubert, A. A1 - Luch, A. A1 - Arlinghaus, H. F. T1 - TOF-SIMS analysis of cell membrane changes in functional impaired human macrophages upon nanosilver treatment N2 - Silver nanoparticles (SNP) are among the most commercialized nanoparticles. Here, we show that peptide-coated SNP cause functional impairment of human macrophages. A dose-dependent inhibition of phagocytosis is observed after nanoparticle treatment, and pretreatment of cells with N-acetyl cysteine (NAC) can counteract the phagocytosis disturbances caused by SNP. Using the surface-sensitive mode of time-of-flight secondary ion mass spectrometry, in combination with multivariate statistical methods, we studied the composition of cell membranes in human macrophages upon exposure to SNP with and without NAC preconditioning. This method revealed characteristic changes in the lipid pattern of the cellular membrane outer leaflet in those cells challenged by SNP. Statistical analyses resulted in 19 characteristic ions, which can be used to distinguish between NAC pretreated and untreated macrophages. The present study discusses the assignments of surface cell membrane phospholipids for the identified ions and the resulting changes in the phospholipid pattern of treated cells. We conclude that the adverse effects in human macrophages caused by SNP can be partially reversed through NAC administration. Some alterations, however, remained. KW - Silver nanoparticles KW - Lipidomics KW - N-acetyl cysteine KW - Phagocytosis KW - Oxidative stress KW - Reference material PY - 2013 DO - https://doi.org/10.1002/sia.5155 SN - 0142-2421 SN - 1096-9918 VL - 45 IS - 1 SP - 483 EP - 485 PB - Wiley CY - Chichester AN - OPUS4-27586 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Brandl, F. A1 - Lederle, F. A1 - Härter, C. A1 - Thünemann, Andreas A1 - Beuermann, S. T1 - From gaseous vinylidene fluoride to electroactive poly(vinylidene fluoride) – Inducing β-phase by formation of block copolymers and composite materials N2 - Polymeric core-shell particles were synthesized in a semi-batch emulsion polymerization process. The shell of the particles consist of PVDF with a high amount of beta-phase. Small-angle X-ray scattering (SAXS) was used to quantify the size of the cores of the particles and the thickness of the shell. T2 - Macromolecular Colloquium Freiburg CY - Freiburg, Germany DA - 20.02.2019 KW - Small-angle x-ray scattering KW - SAXS KW - Nanoparticle KW - Polymer PY - 2019 AN - OPUS4-47467 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Haase, A. A1 - Tentschert, J. A1 - Jungnickel, H. A1 - Graf, P. A1 - Mantion, Alexandre A1 - Draude, F. A1 - Plendl, J. A1 - Goetz, M.E. A1 - Galla, S. A1 - Masic, A. A1 - Thünemann, Andreas A1 - Taubert, A. A1 - Arlinghaus, H. F. A1 - Luch, A. T1 - Toxicity of silver nanoparticles in human macrophages: uptake, intracellular distribution and cellular responses N2 - Silver nanoparticles (SNP) are among the most commercialized nanoparticles worldwide. They can be found in many diverse products, mostly because of their antibacterial properties. Despite its widespread use only little data on possible adverse health effects exist. It is difficult to compare biological data from different studies due to the great variety in sizes, coatings or shapes of the particles. Here, we applied a novel synthesis approach to obtain SNP, which are covalently stabilized by a small peptide. This enables a tight control of both size and shape. We applied these SNP in two different sizes of 20 or 40 nm (Ag20Pep and Ag40Pep) and analyzed responses of THP-1-derived human macrophages. Similar gold nanoparticles with the same coating (Au20Pep) were used for comparison and found to be non-toxic. We assessed the cytotoxicity of particles and confirmed their cellular uptake via transmission electron microscopy and confocal Raman microscopy. Importantly a majority of the SNP could be detected as individual particles spread throughout the cells. Furthermore we studied several types of oxidative stress related responses such as induction of heme oxygenase I or formation of protein carbonyls. In summary, our data demonstrate that even low doses of SNP exerted adverse effects in human macrophages. KW - Silver nanoparticles KW - Neurotoxicology KW - Protein carbonyls KW - ROS PY - 2011 DO - https://doi.org/10.1088/1742-6596/304/1/012030 SN - 1742-6588 SN - 1742-6596 VL - 304 SP - 012030-1 - 012030-14 PB - IOP Publ. CY - Bristol, UK AN - OPUS4-24035 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Obeid, R. A1 - Maltseva, Elena A1 - Thünemann, Andreas A1 - Tanaka, F. A1 - Winnik, F. M. T1 - Temperature response of self-assembled micelles of telechelic hydrophobically modified Poly(2-alkyl-2-oxazoline)s in water N2 - Hydrophobically end-modified (HM) poly(2-ethyl-2-oxazolines) (PEtOx) and poly(2-isopropyl-2-oxazolines) (PiPrOx) bearing an n-octadecyl chain on both termini or on one chain end only were prepared by cationic ring-opening polymerization of 2-ethyl-2-oxazoline and 2-isopropyl-2-oxazoline, respectively, and subsequent end-group modification. The polymers had a molar mass (Mn) ranging from 7000 to 13000 g mol-1, a size distribution Mw/Mn < 1.20, and end-group functionality > 0.97. All polymers, except the semitelechelic sample C18-PiPrOx-OH 13K (Mn = 13000 g mol-1), formed core-shell micelles in cold water with a hydrodynamic radius (RH), measured by dynamic light scattering, between 7 and 12 nm and a core of radius (Rc), determined by analysis of small-angle X-ray scattering (SAXS) data, of ~1.3 nm. Aqueous solutions of all polymers underwent a heat-induced phase transition detected by an increase in solution turbidity at a temperature (Tcp, cloud point) ranging from 32 to 62 °C, depending on polymer structure and size. Temperature-dependent light scattering (LS) measurements and fluorescence depolarization studies with the probe diphenylhexatriene (DPH) revealed that extensive intermicellar bridging takes place in solutions heated in the vicinity of Tcp leading to large assemblies (RH ≥ 1 µm). Further heating caused these assemblies to shrink into objects with RH ~ 300-700 nm, depending on the size and structure of the polymer. The formation of H-bonds between water molecules and the main-chain amide nitrogen atoms imparts distinct features to the flower/star micelles formed by telechelic/semitelechelic PiPrOx and PEtOx, compared to the micelles formed by other hydrophobically end-modified water-soluble polymers, such as poly(ethylene oxide) or poly(N-isopropylacrylamide). PY - 2009 DO - https://doi.org/10.1021/ma802592f SN - 0024-9297 SN - 1520-5835 VL - 42 IS - 6 SP - 2204 EP - 2214 PB - American Chemical Society CY - Washington, DC AN - OPUS4-19115 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - INPR A1 - Pauw, Brian Richard A1 - Smales, Glen Jacob A1 - Anker, A. S. A1 - Balazs, D. M. A1 - Beyer, F. L. A1 - Bienert, Ralf A1 - Bouwman, W. G. A1 - Breßler, Ingo A1 - Breternitz, J. A1 - Brok, E. S. A1 - Bryant, G. A1 - Clulow, A. J. A1 - Crater, E. R. A1 - De Geuser, F. A1 - Giudice, A. D. A1 - Deumer, J. A1 - Disch, S. A1 - Dutt, S. A1 - Frank, K. A1 - Fratini, E. A1 - Gilbert, E. P. A1 - Hahn, Marc Benjamin A1 - Hallett, J. A1 - Hohenschutz, Max A1 - Hollamby, M. J. A1 - Huband, S. A1 - Ilavsky, J. A1 - Jochum, J. K. A1 - Juelsholt, M. A1 - Mansel, B. W. A1 - Penttilä, P. A1 - Pittkowski, R. K. A1 - Portale, G. A1 - Pozzo, L. D. A1 - Ricardo de Abreu Furtado Garcia, P. A1 - Rochels, L. A1 - Rosalie, Julian M. A1 - Saloga, P. E. J. A1 - Seibt, S. A1 - Smith, A. J. A1 - Smith, G. N. A1 - Annadurai, V. A1 - Spiering, G. A. A1 - Stawski, Tomasz A1 - Taché, O. A1 - Thünemann, Andreas A1 - Toth, K. A1 - Whitten, A. E. A1 - Wuttke, J. T1 - The human factor - Results of a small-angle scattering data analysis round robin N2 - A Round Robin study has been carried out to estimate the impact of the human element in small-angle scattering data analysis. Four corrected datasets were provided to participants ready for analysis. All datasets were measured on samples containing spherical scatterers, with two datasets in dilute dispersions, and two from powders. Most of the 46 participants correctly identified the number of populations in the dilute dispersions, with half of the population mean entries within 1.5 % and half of the population width entries within 40 %, respectively. Due to the added complexity of the structure factor, much fewer people submitted answers on the powder datasets. For those that did, half of the entries for the means and widths were within 44 % and 86 % respectively. This Round Robin experiment highlights several causes for the discrepancies, for which solutions are proposed. KW - Round robin KW - Sall-angle scattering KW - Nanostructure quantification KW - Nanostructure KW - SAXS KW - MOUSE KW - X-ray scattering KW - Size distribution KW - Nanoparticles PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-571342 DO - https://doi.org/10.48550/arXiv.2303.03772 SP - 1 EP - 23 PB - Cornell University CY - Ithaca, NY AN - OPUS4-57134 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Pauw, Brian Richard A1 - Smales, Glen Jacob A1 - Anker, A. S. A1 - Annadurai, V. A1 - Balazs, D. M. A1 - Bienert, Ralf A1 - Bouwman, W. G. A1 - Breßler, Ingo A1 - Breternitz, J. A1 - Brok, E. S. A1 - Bryant, G. A1 - Clulow, A. J. A1 - Crater, E. R. A1 - De Geuser, F. A1 - Del Giudice, A. A1 - Deumer, J. A1 - Disch, S. A1 - Dutt, S. A1 - Frank, K. A1 - Fratini, E. A1 - Garcia, P. R. A. F. A1 - Gilbert, E. P. A1 - Hahn, Marc Benjamin A1 - Hallett, J. A1 - Hohenschutz, M. A1 - Hollamby, M. A1 - Huband, S. A1 - Ilavsky, J. A1 - Jochum, J. K. A1 - Juelsholt, M. A1 - Mansel, B. W. A1 - Penttilä, P. A1 - Pittkowski, R. K. A1 - Portale, G. A1 - Pozzo, L. D. A1 - Rochels, L. A1 - Rosalie, Julian M. A1 - Saloga, Patrick E. J. A1 - Seibt, S. A1 - Smith, A. J. A1 - Smith, G. N. A1 - Spiering, G. A. A1 - Stawski, Tomasz M. A1 - Taché, O. A1 - Thünemann, Andreas A1 - Toth, K. A1 - Whitten, A. E. A1 - Wuttke, J. T1 - The human factor - Results of a small-angle scattering data analysis round robin N2 - A round-robin study has been carried out to estimate the impact of the human element in small-angle scattering data analysis. Four corrected datasets were provided to participants ready for analysis. All datasets were measured on samples containing spherical scatterers, with two datasets in dilute dispersions and two from powders. Most of the 46 participants correctly identified the number of populations in the dilute dispersions, with half of the population mean entries within 1.5% and half of the population width entries within 40%. Due to the added complexity of the structure factor, far fewer people submitted answers on the powder datasets. For those that did, half of the entries for the means and widths were within 44 and 86%, respectively. This round-robin experiment highlights several causes for the discrepancies, for which solutions are proposed. KW - Round Robin KW - Data analysis KW - Small-angle scattering KW - Nanomaterials KW - Interlaboratory comparability KW - Nanostructure quantification KW - Methodology KW - MOUSE PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-587091 DO - https://doi.org/10.1107/S1600576723008324 SN - 1600-5767 VL - 56 IS - 6 SP - 1618 EP - 1629 PB - Wiley-Blackwell CY - Oxford AN - OPUS4-58709 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lutz, J.-F. A1 - Kubowicz, St. A1 - Baussard, J.-F. A1 - Thünemann, Andreas A1 - v. Berlepsch, H. A1 - Laschewsky, A. T1 - Multicompartment Micelles Obtained via the Self-Assembly of a Well-Defined Triblock Macrosurfactant Prepared by RAFT Polymerization KW - Micelles KW - Living polymerization KW - RAFT KW - Block copolymers PY - 2005 SN - 0032-3934 VL - 46 IS - 2 SP - 297 EP - 298 PB - American Chemical Society CY - Newark, NJ AN - OPUS4-10534 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kubowicz, St. A1 - Baussard, J.-F. A1 - Lutz, J.-F. A1 - Thünemann, Andreas A1 - v. Berlepsch, H. A1 - Laschewsky, A. T1 - Multicompartment Micelles Formed by Self-Assembly of Linear ABC Triblock Copolymers in Aqueous Medium KW - Small-angle x-ray scattering KW - Micelles PY - 2005 DO - https://doi.org/10.1002/anie.200500584 SN - 1433-7851 SN - 1521-3773 SN - 0570-0833 VL - 44 SP - 5262 EP - 5265 PB - Wiley-VCH CY - Weinheim AN - OPUS4-10537 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lindner, A. A1 - Menzel, Michael A1 - Renz, F. A1 - Kurth, D.G. A1 - Thünemann, Andreas T1 - Metallosupramolecular coordination polyelectrolytes investigated by Mössbauer spectroscopy N2 - Metallosupramolecular coordination polyelectrolytes (MEPEs) based on rigid and flexible ditopic bis-terpyridine ligands and Fe(II) ions are investigated by Mössbauer spectroscopy. We demonstrate the influence of mechanical stress induced by grinding on the structure of MEPE as well as the ability of MEPE to self-repair through recrystallisation. KW - Metallosupramolecular coordination polyelectrolyte KW - Bis-terpyridine KW - Mössbauer spectroscopy KW - Supramolecular chemistry PY - 2005 UR - http://www.edoc.mpg.de/298371 SN - 0304-3843 SN - 1572-9540 VL - 166 IS - 1-4 SP - 465 EP - 468 PB - Kluwer CY - Dordrecht AN - OPUS4-15729 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Renz, F. A1 - Jung, S. A1 - Klein, M. A1 - Menzel, Michael A1 - Thünemann, Andreas T1 - Molecular switching complexes with iron and tin as central atom N2 - The precursor [FeIII(L)Cl] (LH1.5) and several reactive groups for surface anchoring, full surface shielding can be reached, which leads to reduced protein adsorption of albumin and fibrinogen. In addition, adherent thrombocytes were not activated. This could be clearly shown by immunostaining adherent proteins and analyzing the thrombocyte covered area. The presented work provides an important strategy for the development of application relevant hemocompatible 3D structured materials. KW - Nanotechnology KW - thrombocyte adhesion KW - biomedical applications PY - 2014 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-308196 DO - https://doi.org/10.1039/c4tb00184b SN - 2050-750X SN - 2050-7518 VL - 2 IS - 23 SP - 3626 EP - 3635 PB - Royal Soc. of Chemistry CY - Cambridge AN - OPUS4-30819 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Liebig, F. A1 - Thünemann, Andreas A1 - Koetz, J. T1 - Ostwald Ripening Growth Mechanism of Gold Nanotriangles in Vesicular Template Phases N2 - The mechanism of nanotriangle formation in multivesicular vesicles (MMV) is investigated by using time-dependent SAXS measurements in combination with UV−vis spectroscopy, light, and transmission electron microscopy. In the first time period 6.5 nm sized spherical gold nanoparticles are formed inside of the vesicles, which build up soft nanoparticle aggregates. In situ SAXS experiments show a linear increase of the volume and molar mass of nanotriangles in the second time period. The volume growth rate of the triangles is 16.1 nm3/min, and the growth rate in the vertical direction is only 0.02 nm/min. Therefore, flat nanotriangles with a thickness of 7 nm and a diameter of 23 nm are formed. This process can be described by a diffusionlimited Ostwald ripening growth mechanism. TEM micrographs visualize soft coral-like structures with thin nanoplatelets at the periphery of the aggregates, which disaggregate in the third time period into nanotriangles and spherical particles. The 16 times faster growth of nanotriangles in the lateral than that in the vertical direction is related to the adsorption of symmetry breaking components, i.e., AOT and the polyampholyte PalPhBisCarb, on the {111} facets of the gold nanoplatelets in combination with confinement effects of the vesicular template phase. KW - Gold KW - Nanoparticle KW - Small-angle x-ray scattering KW - SAXS KW - Kinetics PY - 2016 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-379261 DO - https://doi.org/10.1021/acs.langmuir.6b02662 SN - 0743-7463 VL - 32 IS - 42 SP - 10928 EP - 10935 PB - American Chemical Society AN - OPUS4-37926 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Heinke, D. A1 - Gehrke, N. A1 - Ludwig, F. A1 - Steinhoff, U. A1 - Pankhurst, Q. A. A1 - Lüdtke-Buzug, K. A1 - Thünemann, Andreas A1 - Johansson, Ch. T1 - NanoMag - Standardization of Analysis Methods for Magnetic Nanoparticles N2 - The NanoMag project brings together various leading experts in magnetic nanoparticle synthesis as well as nanoparticle analysis and characterization from research institutes, companies, universities and metrology institutes that will perform cutting-edge research and develop applications in the field of magnetic particles. This work is supported by the European Commission Framework Programme7 under the NanoMag project [grant agreement no 604448]. T2 - 2015 5th International Workshop on Magnetic Particle Imaging (IWMPI) CY - Istanbul, Turkey DA - 26.03.2015 KW - nanoparticles PY - 2015 UR - http://www.nanomag-project.eu/ SN - 978-1-4799-7269-2 SN - 978-1-4799-7271-5 DO - https://doi.org/10.1109/IWMPI.2015.7107065 VL - 2015 SP - P39 PB - IEEE AN - OPUS4-37324 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Liebig, F. A1 - Sarhan, R. M. A1 - Schmitt, C. N. Z. A1 - Thünemann, Andreas A1 - Prietzel, C. A1 - Bargheer, M. A1 - Koetz, J. T1 - Gold Nanotriangles with Crumble Topping and their Influence on Catalysis and Surface‐Enhanced Raman Spectroscopy N2 - By adding hyaluronic acid (HA) to dioctyl sodium sulfosuccinate (AOT)‐stabilized gold nanotriangles (AuNTs) with an average thickness of 7.5±1 nm and an edge length of about 175±17 nm, the AOT bilayer is replaced by a polymeric HA‐layer leading to biocompatible nanoplatelets. The subsequent reduction process of tetrachloroauric acid in the HA‐shell surrounding the AuNTs leads to the formation of spherical gold nanoparticles on the platelet surface. With increasing tetrachloroauric acid concentration, the decoration with gold nanoparticles can be tuned. SAXS measurements reveal an increase of the platelet thickness up to around 14.5 nm, twice the initial value of bare AuNTs. HRTEM micrographs show welding phenomena between densely packed particles on the platelet surface, leading to a crumble formation while preserving the original crystal structure. Crumbles crystallized on top of the platelets enhance the Raman signal by a factor of around 20, and intensify the plasmon‐driven dimerization of 4‐nitrothiophenol (4‐NTP) to 4,4′‐dimercaptoazobenzene in a yield of up to 50 %. The resulting crumbled nanotriangles, with a biopolymer shell and the absorption maximum in the second window for in vivo imaging, are promising candidates for biomedical sensing. KW - SAXS KW - Small-angle X-ray scattering KW - Nanoparticle KW - Gold PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-503977 DO - https://doi.org/10.1002/cplu.201900745 VL - 85 IS - 3 SP - 519 EP - 526 PB - Wiley-VCH Verlag CY - Weinheim AN - OPUS4-50397 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Chowdhary, S. A1 - Schmidt, R. F. A1 - Sahoo, A. K. A1 - tom Dieck, T. A1 - Hohmann, T. A1 - Schade, B. A1 - Brademann-Jock, Kerstin A1 - Thünemann, Andreas A1 - Netz, R. R. A1 - Gradzielski, M. A1 - Koksch, B. T1 - Rational design of amphiphilic fluorinated peptides: evaluation of self-assembly properties and hydrogel formation N2 - Advanced peptide-based nanomaterials composed of self-assembling peptides (SAPs) are of emerging interest in pharmaceutical and biomedical applications. The introduction of fluorine into peptides, in fact, offers unique opportunities to tune their biophysical properties and intermolecular interactions. In particular, the degree of fluorination plays a crucial role in peptide engineering as it can be used to control the characteristics of fluorine-specific interactions and, thus, peptide conformation and self-assembly. Here, we designed and explored a series of amphipathic peptides by incorporating the fluorinated amino acids (2S)-4-monofluoroethylglycine (MfeGly), (2S)-4,4-difluoroethylglycine (DfeGly) and (2S)-4,4,4-trifluoroethylglycine (TfeGly) as hydrophobic components. This approach enabled studying the impact of fluorination on secondary structure formation and peptide self-assembly on a systematic basis. We show that the interplay between polarity and hydrophobicity, both induced differentially by varying degrees of side chain fluorination, does affect peptide folding significantly. A greater degree of fluorination promotes peptide fibrillation and subsequent formation of physical hydrogels in physiological conditions. Molecular simulations revealed the key role played by electrostatically driven intra-chain and inter-chain contact pairs that are modulated by side chain fluorination and give insights into the different self-organization behaviour of selected peptides. Our study provides a systematic report about the distinct features of fluorinated oligomeric peptides with potential applications as peptide-based biomaterials. KW - Small-angle X-ray scattering KW - SAXS KW - Amyloid PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-553504 DO - https://doi.org/10.1039/D2NR01648F SN - 2040-3364 VL - 14 IS - 28 SP - 10176 EP - 10189 PB - Royal Society of Chemistry AN - OPUS4-55350 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lutz, J.-F. A1 - Nehring, R. A1 - Thünemann, Andreas T1 - Solution Self-Assembly of Synthetic Copolymers bearing Complementary Nucleic Acid Funtionalities KW - DNA KW - Living polymerization KW - ATRP KW - Copolymers PY - 2005 SN - 0032-3934 VL - 46 IS - 2 SP - 397 EP - 398 PB - American Chemical Society CY - Newark, NJ AN - OPUS4-10535 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lutz, J.-F. A1 - Thünemann, Andreas A1 - Rurack, Knut T1 - DNA-like "Melting" of Adenine- and Thymine-Functionalized Synthetic Copolymers KW - Polymers KW - Micelles KW - Amyloid beta-peptide KW - Proteins KW - Secondary structure PY - 2005 SN - 0024-9297 SN - 1520-5835 VL - 38 IS - 20 SP - 8124 EP - 8126 PB - American Chemical Society CY - Washington, DC AN - OPUS4-11068 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lutz, J.-F. A1 - Thünemann, Andreas A1 - Nehring, R. T1 - Preparation by Controlled Radical Polymerization and Self-Assembly via Base-Recognition of Synthetic Polymers Bearing Complementary Nucleobases N2 - The radical polymerization of three monomers bearing nucleobases 1-(4-vinylbenzyl)thymine (VBT), 1-(4-vinylbenzyl)uracil (VBU) and 9-(4-vinylbenzyl)adenine (VBA) was investigated. The corresponding homopolymers could be prepared in high yields via conventional radical polymerization. However, the resulting polymers were found to be only soluble in a few polar solvents. On the other hand, copolymers of dodecyl methacrylate (DMA) with either VBT or VBA could be prepared via both free radical polymerization and atom transfer radical polymerization and could be dissolved in a large variety of organic solvents. Moreover, the formed complementary copolymers P(VBT-co-DMA) and P(VBA-co-DMA) were found to self-assemble in dilute solutions in dioxane or chloroform via base recognition, as evidenced by a significant hypochromicity effect in UV spectroscopy. Nevertheless, at higher concentrations in chloroform, both dynamic light scattering and optical microscopy indicate that P(VBT-co-DMA), P(VBA-co-DMA), or P(VBT-co-DMA)/P(VBA-co-DMA) mixtures spontaneously self-assemble into micron size spherical aggregates. 1H NMR and FTIR studies confirmed that the self-assembly process is driven in all cases via H-bond formation. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4805-4818, 2005 KW - ATRP KW - Living polymerization KW - Nucleic acids KW - Polymersomes KW - Self-assembly PY - 2005 DO - https://doi.org/10.1002/pola.20976 SN - 0360-6376 SN - 0887-624X VL - 43 IS - 20 SP - 4805 EP - 4818 PB - Wiley CY - Hoboken, NJ AN - OPUS4-10842 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lutz, J.-F. A1 - Pfeifer, S. A1 - Chanana, M. A1 - Thünemann, Andreas A1 - Bienert, Ralf T1 - H-Bonding-Directed Self-Assembly of Synthetic Copolymers Containing Nucleobases: Organization and Colloidal Fusion in a Noncompetitive Solvent N2 - The self-organization of random copolymers composed of a nucleobase monomer (either 1-(4-vinylbenzyl)thymine or 9-(4-vinylbenzyl)adenine) and dodecyl methacrylate (DMA) was studied in dilute chloroform solutions. The balance between the molar fractions of the nucleobase monomer (leading to intermolecular H-bonding) and DMA (soluble moiety in chloroform) in the polymer chains was found to be the parameter that principally influences the self-organization. DMA-rich copolymers are molecularly soluble in chloroform, whereas nucleobase-rich copolymers are insoluble in this solvent. Copolymers possessing an equimolar comonomer composition self-assemble into micrometer-sized particles physically cross-linked by intermolecular H-bonds (either thymine-thymine or adenine-adenine interactions, depending on the studied copolymer). Nevertheless, when mixed together, thymine- and adenine-based colloids fuse into thermodynamically stable microspheres cross linked by adenine-thymine interactions. KW - Synthetic polymers KW - Self-organization KW - H-bonding KW - Nucleobases KW - Confocal fluorescence microscopy PY - 2006 DO - https://doi.org/10.1021/la061382a SN - 0743-7463 SN - 1520-5827 VL - 22 IS - 17 SP - 7411 EP - 7415 PB - American Chemical Society CY - Washington, DC AN - OPUS4-12637 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -