TY - VIDEO A1 - Pauw, Brian Richard T1 - Just a minute: X-ray scattering N2 - An extremely brief summary of what X-ray scattering can do for you (X-ray scattering encompasses small-angle X-ray scattering (SAXS), and wide-angle X-ray scattering (WAXS/XRD), amongst others). See my other videos for more detailed explanations on sample selection, data correction, data analysis, etc. KW - X-ray scattering KW - Introduction KW - Materials science KW - Nanostructure investigation KW - MOUSE PY - 2022 UR - https://www.youtube.com/watch?v=jWWNQyaCTHA DO - https://doi.org/10.26272/opus4-55768 PB - YouTube, LLC CY - San Bruno, CA, USA AN - OPUS4-55768 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Guitton-Spassky, Tiffany A1 - Schade, Boris A1 - Zoister, Christian A1 - Veronese, Eleonora A1 - Rosati, Marta A1 - Baldelli Bombelli, Francesca A1 - Cavallo, Gabriella A1 - Thünemann, Andreas A1 - Ghermezcheshme, Hassan A1 - Makki, Hesam A1 - Netz, Roland R. A1 - Ludwig, Kai A1 - Metrangolo, Pierangelo A1 - Singh, Abhishek Kumar A1 - Haag, Rainer T1 - Fluorinated Hexosome Carriers for Enhanced Solubility of Drugs N2 - Designing nanomaterials for drug encapsulation is a crucial, yet challenging, aspect for pharmaceutical development. An important step is synthesizing amphiphiles that form stable supramolecular systems for efficient drug loading. In the case of fluorinated drugs, these have superior properties and also a tendency toward reduced water solubility. For the first time, we report here fluorinated hexosome carriers made from nonionic dendritic amphiphiles, capable of encapsulating the fluorinated drug Leflunomide with high efficiency (62 ± 3%) and increasing its solubility by 12-fold. We synthesized amphiphiles with varying tail groups (fluorinated/alkylated), and their supramolecular self-assembly was investigated using cryogenic transmission electron microscopy and small-angle X-ray scattering. Furthermore, Leflunomide and its equivalent nonfluorinated counterpart were encapsulated within fluorinated and nonfluorinated assemblies. Self-assembly and encapsulation mechanisms were well supported by coarse-grained molecular simulations, yielding a fundamental understanding of the new systems. KW - PEFAS KW - Small-angle X-ray scattering KW - SAXS KW - Reference method PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-632002 DO - https://doi.org/10.1021/jacsau.5c00198 SN - 2691-3704 VL - 5 IS - 5 SP - 2223 EP - 2236 PB - American Chemical Society (ACS) CY - Washington, DC AN - OPUS4-63200 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zhang, Qiang A1 - Heuchel, Matthias A1 - Thünemann, Andreas A1 - Machatscheck, Rainhard T1 - The role of diffusion in the hydrolytic degradation of poly(lactic-co-glycolic acid): A molecular perspective N2 - This research emphasizes the importance of internal surface erosion as a key factor in the hydrolytic degradation of PLGA (poly(D,L-lactic-co-glycolic acid)) providing an alternative view of the established surface and bulk erosion degradation modes. Using molecular dynamics (MD) simulations, this study reveals the role of water and oligomer diffusion during the degradation of PLGA and highlights the importance of water channels formed as the overall water content increases. We found that these continuous water channels play a crucial role in accelerating the transport of water and the release of degradation products from the polymer matrix, as the diffusion coefficients of water and small oligomers exhibit significant differences spanning 2 to 3 orders of magnitude between the water and polymer phases. Water follows a different diffusion mechanism than polymer fragments. The diffusion rate of the fragments up to a size of octamers was found to be size-dependent and reasonably well approximated by a 1/N behavior, in line with the Rouse model. KW - Small-angle X-ray scattering KW - SAXS KW - Nanostructure KW - PLGA PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-621250 DO - https://doi.org/10.1016/j.polymdegradstab.2024.111119 VL - 232 SP - 1 EP - 12 PB - Elsevier Ltd. AN - OPUS4-62125 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lange, Alyna A1 - Holtzheimer, Lea A1 - Clarke, Coby A1 - Thünemann, Andreas A1 - Taubert, Andreas T1 - Complex Self-Organization in n-Alkylammonium Sulfobetaine Zwitterions with High Thermal Stabilities and High Expansion Coefficients N2 - Sulfobetaine zwitterions made from n-alkyl dimethylamines and butanesultone yield a series of n-alkylammonium sulfobetaine zwitterions with complex self-organization behavior. The compounds are thermally quite stable and the length of the alkyl chain directly affects all phase transition temperatures of the compounds: the longer the alkyl chain, the higher the transition temperature. All compounds exhibit lamellar order and the different phases are characterized by a lower temperature orthorhombic and a higher temperature hexagonal in-plane order. The phase transition from the orthorhombic to the hexagonal phase is always associated with an increase of the long period. The phase transition is also associated with a rather high thermal expansion coefficient. KW - SAXS KW - Small-angle X-ray scattering KW - Nanostructure PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-626276 DO - https://doi.org/10.1021/acs.langmuir.4c02892 SN - 1520-5827 VL - 41 SP - 4422 EP - 4434 PB - American Chemical Society (ACS) AN - OPUS4-62627 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kieserling, Helena A1 - Sieg, Holger A1 - Heilscher, Jasmin A1 - Drusch, Stephan A1 - Braeuning, Albert A1 - Thünemann, Andreas A1 - Rohn, Sascha T1 - Towards Understanding Particle-Protein Complexes: Physicochemical, Structural, and Cellbiological Characterization of β-Lactoglobulin Interactions with Silica, Polylactic Acid, and Polyethylene Terephthalate Nanoparticles N2 - Nanoplastic particles and their additives are increasingly present in the food chain, interacting with biomacromolecules with not yet known consequences. A protein corona forms around the particles in these usually complex matrices, primarily with a first contact at surface-active proteins. However, systematic studies on the interactions between the particles and proteins –especially regarding protein affinity and structural changes due to surface properties like polarity – are limited. It is also unclear whether the protein corona can "mask" the particles, mimic protein properties, and induce cytotoxic effects when internalized by mammalian cells. This study aimed at investigating the physicochemical properties of model particle-protein complexes, the structural changes of adsorbed proteins, and their effects on Caco-2 cells. Whey protein β-lactoglobulin (β-Lg) was used as a well-characterized model protein and studied in a mixture with nanoparticles of varying polarity, specifically silica, polylactic acid (PLA), and polyethylene terephthalate (PET). The physicochemical analyses included measurements of the hydrodynamic diameter and the zeta potential, while the protein conformational changes were analyzed using Fourier-transform-infrared spectroscopy (FTIR) and intrinsic fluorescence. Cellular uptake in Caco-2 cells was assessed through flow cytometry, cell viability was measured using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium-bromide (MTT) assay, and cellular impedance was analyzed with xCELLigence® technology. The results indicated that β-Lg had the highest affinity for hydrophilic silica particles, forming silica-β-Lg complexes and large aggregates through electrostatic interactions. The affinity decreased for PLA and was lowest for hydrophobic PET, which formed smaller complexes. Adsorption onto silica caused partial unfolding and refolding of β-Lg. The silica-β-Lg complexes were internalized by Caco-2 cells, impairing cell proliferation. In contrast, PLA- and PET-protein complexes were not internalized, though PLA complexes slightly reduced cell viability. This study enhances our understanding of protein adsorption on nanoparticles and its potential biological effects. KW - Nanoplastics KW - Microplastics KW - Reference materials KW - Scattering KW - DLS PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-630093 DO - https://doi.org/10.1016/j.colsurfb.2025.114702 SN - 1873-4367 VL - 253 SP - 1 EP - 12 PB - Elsevier BV CY - Amsterdam AN - OPUS4-63009 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mikhlin, Yuri A1 - Muzikansky, Anya A1 - Zysler, Melina A1 - Thünemann, Andreas A1 - Zitoun, David T1 - Emerging electrochemistry of high-concentration colloids: Redox-activity, wide potential window and electrophoretic transport of iron oxide nanoparticles N2 - High-concentration, steric stabilizer free colloids and particularly their electrochemical behavior remains almost unexplored. Herein, we report on the electrochemistry (cyclic voltammetry, impedance spectroscopy, etc.) of highly concentrated aqueous colloidal dispersion up to 800 g/L of citrate-capped ∼11 nm Fe3-xO4 nanoparticles (NPs) without background electrolyte on glassy carbon electrodes. X-ray photoelectron spectroscopy was applied to analyze the reaction products. Solid-state Fe(II)/Fe(III) conversion was concluded to determine the cathodic and anodic faradaic reactions of the particles, with the currents depending on approximately square root of the concentration. The electrochemical reactions are coupled with the electrophoretic transfer of the negatively charged NPs on toward the anode, with the ohmic-type behavior in the bulk demonstrated by the nearly linear voltametric cathodic curves and frequency-independent impedance above ∼10–100 Hz. Accumulation and clogging of the NPs retards diffusion near anode. Hydrogen and especially oxygen evolution are arrested, and very large oxidation overpotentials result in extraordinary wide, up to 12 V, electrochemical window of water stability. The findings shed light onto basic features of the electrochemistry of high-concentration colloids without added electrolyte and their potential applications in redox flow batteries, electrophoretic deposition and beyond. KW - Nanoplastics KW - SAXS KW - Small-angle X-ray scattering PY - 2026 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-644340 DO - https://doi.org/10.1016/j.jcis.2025.139247 SN - 0021-9797 VL - 703 SP - 1 EP - 18 PB - Elsevier Inc. AN - OPUS4-64434 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Chowdhary, S. A1 - Moschner, J. A1 - Mikolajczak, D. J. A1 - Becker, M. A1 - Thünemann, Andreas A1 - Kästner, Claudia A1 - Klemczak, D. A1 - Stegemann, A.-K. A1 - Böttcher, C. A1 - Metrangolo, P. A1 - Netz, R. R. A1 - Koksch, B. T1 - The Impact of Halogenated Phenylalanine Derivatives on NFGAIL Amyloid Formation N2 - The hexapeptide hIAPP22–27 (NFGAIL) is known as a crucial amyloid core sequence of the human islet amyloid polypeptide (hIAPP) whose aggregates can be used to better understand the wild‐type hIAPP′s toxicity to β‐cell death. In amyloid research, the role of hydrophobic and aromatic‐aromatic interactions as potential driving forces during the aggregation process is controversially discussed not only in case of NFGAIL, but also for amyloidogenic peptides in general. We have used halogenation of the aromatic residue as a strategy to modulate hydrophobic and aromatic‐aromatic interactions and prepared a library of NFGAIL variants containing fluorinated and iodinated phenylalanine analogues. We used thioflavin T staining, transmission electron microscopy (TEM) and small‐angle X‐ray scattering (SAXS) to study the impact of side‐chain halogenation on NFGAIL amyloid formation kinetics. Our data revealed a synergy between aggregation behavior and hydrophobicity of the phenylalanine residue. This study introduces systematic fluorination as a toolbox to further investigate the nature of the amyloid self‐assembly process. KW - Small-angle X-ray scattering KW - SAXS KW - Nanoparticle KW - Nanostructure KW - Peptide KW - Amyloid PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-518632 DO - https://doi.org/10.1002/cbic.202000373 VL - 21 IS - 24 SP - 3544 EP - 3554 PB - Wiley CY - Weinheim AN - OPUS4-51863 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 - Saloga, Patrick E. J. A1 - Smales, Glen Jacob A1 - Clark, Adam H. A1 - Thünemann, Andreas T1 - Zinc Phosphate Nanoparticles Produced in Saliva N2 - This paper reports the formation of zinc phosphate nanoparticles from the artificial digestion of zinc chloride. Initially, the formation of amorphous primary particles with a mean radius of 1.1 nm is observed, alongside the formation of larger, protein stabilized aggregates. These aggregates, with a radius of gyration of 37 nm, are observed after 5 minutes of exposure to artificial saliva and are shown to be colloidally stable for a minimum time of two weeks. The initially formed primary particles are thought to consist of amorphous zinc phosphate, which is then transformed into crystalline Zn3(PO4)2·4H2O over the course of two weeks. Our results demonstrate that the interaction of inorganic salts with bodily fluids can induce the formation of de novo nanoparticles, which in turn, provides insights into how zinc‐enriched foods may also facilitate the formation of nanoparticles upon contact with saliva. As such, this may be considered as an undesirable (bio)mineralization. KW - SAXS KW - Digestion KW - Zinc phosphate PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-514239 DO - https://doi.org/10.1002/ejic.202000521 IS - 38 SP - 3654 EP - 3661 PB - Wiley-VCH Verlag GmbH & Co. KGaA CY - Weinheim AN - OPUS4-51423 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 - Navarro, L. A1 - Thünemann, Andreas A1 - Yokosawa, T. A1 - Spiecker, E. A1 - Klinger, D. T1 - Regioselective Seeded Polymerization in Block Copolymer Nanoparticles: Post-Assembly Control of Colloidal Features N2 - Post-assembly modifications are efficient tools to adjust colloidal features of block copolymer (BCP) particles. However, existing methods often address particle shape, morphology, and chemical functionality individually. For simultaneous control, we transferred the concept of seeded polymerization to phase separated BCP particles. Key to our approach is the regioselective polymerization of (functional) monomers inside specific BCP domains. This was demonstrated in striped PS-b-P2VP ellipsoids. Here, polymerization of styrene preferably occurs in PS domains and increases PS lamellar thickness up to 5-fold. The resulting asymmetric lamellar morphology also changes the particle shape, i.e., increases the aspect ratio. Using 4-vinylbenzyl azide as co-monomer, azides as chemical functionalities can be added selectively to the PS domains. Overall, our simple and versatile method gives access to various multifunctional BCP colloids from a single batch of pre-formed particles. KW - Small-angle X-ray scattering KW - SAXS KW - Nanostructure KW - Polymer KW - Nanoparticle PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-557246 DO - https://doi.org/10.1002/anie.202208084 SN - 1433-7851 VL - 61 IS - 35 SP - 1 EP - 11 PB - Wiley CY - Weinheim AN - OPUS4-55724 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Paul, M. B. A1 - Fahrenson, C. A1 - Givelet, L. A1 - Herrmann, T. A1 - Loescher, K. A1 - Böhmert, L. A1 - Thünemann, Andreas A1 - Braeuning, A. A1 - Sieg, H. T1 - Beyond microplastics ‑ investigation on health impacts of submicron and nanoplastic particles after oral uptake in vitro N2 - The continuously increasing use of plastics is supposed to result in a rising exposure of MNPs to humans. Available data on human health risks of microplastics after oral uptake increased immensely in the past years and indicates very likely only low risks after oral consumption. Concerning nanoplastics, uptake, transport and potential adverse effects after oral uptake are less well understood. This study aims to investigate differences between microplastic particles and particles in the submicron- and nanoscaled size derived from food-relevant polymers with a particle size range consistent with higher potential for cellular uptake, fate, and effects when applied to human intestinal and liver cells. This work includes the development of cellular and subcellular detection methods for synthetic polymeric particles in the micro- and nanometer-range, using Scanning Electron Microscopy, Small-Angle X-ray and Dynamic Light Scattering methods, Asymmetric Flow Field Flow Fractionation, octanol-water fractionation, fluorescence microscopy and flow cytometry. Polylactic acid (250 nm and 2 μm (polydisperse)), melamine formaldehyde (366 nm) and polymethylmethacrylate (25 nm) were thoroughly characterized. The submicro- and nanoplastic test particles showed an increased uptake and transport quantity through intestinal cells. Both types of particles resulted in observed differences of uptake behavior, most likely influenced by different lipophilicity, which varied between the polymeric test materials. Toxic effects were detected after 24 h only in overload situations for the particles in the submicrometer range. This study provides further evidence for gastrointestinal uptake of submicro- and nanoplastics and points towards differences regarding bioavailability between microplastics and smaller plastic particles that may result following the ingestion of contaminated food and beverages. Furthermore, the results reinforce the importance for studying nanoplastics of different materials of varying size, surface properties, polymer composition and hydrophobicity. KW - Small-angle X-ray scattering KW - SAXS KW - nanoparticle PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-550741 DO - https://doi.org/10.1186/s43591-022-00036-0 VL - 2 SP - 1 EP - 19 PB - Springer Nature AN - OPUS4-55074 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Navarro, L. A1 - Thünemann, Andreas A1 - Klinger, D. T1 - Solvent Annealing of Striped Ellipsoidal Block Copolymer Particles: Reversible Control over Lamellae Asymmetry, Aspect Ratio, and Particle Surface N2 - Solvent annealing is a versatile tool to adjust the shape and morphology of block copolymer (BCP) particles. During this process, polar solvents are often used for block-selective swelling. However, such water-miscible solvents can induce (partial) solubilization of one block in the surrounding aqueous medium, thus, causing complex structural variations and even particle disassembly. To reduce the complexity in morphology control, we focused on toluene as a nonpolar polystyrene-selective solvent for the annealing of striped polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) ellipsoids. The selective stretching of PS chains produces unique asymmetric lamellae structures, which translate to an increase in the particle aspect ratio after toluene evaporation. Complete reversibility is achieved by changing to chloroform as a nonselective solvent. Moreover, surfactants can be used to tune block-selective wetting of the particle surface during the annealing; for example, a PS shell can protect the internal lamellae structure from disassembly. Overall, this versatile postassembly process enables the tailoring of the structural features of striped colloidal ellipsoids by only using commercial BCPs and solvents. KW - Small-angle X-ray scattering KW - SAXS KW - Nanoparticle KW - Polymer PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-543731 DO - https://doi.org/10.1021/acsmacrolett.1c00665 VL - 11 IS - 3 SP - 319 EP - 335 PB - American Chemical Society AN - OPUS4-54373 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Voss, L. A1 - Hoche, E. A1 - Stock, V. A1 - Böhmert, L. A1 - Braeuning, A. A1 - Thünemann, Andreas A1 - Sieg, H. T1 - Intestinal and hepatic effects of iron oxide nanoparticles N2 - Iron oxide nanoparticles gain increasing attention due to their broad industrial use. However, safety concerns exist since their effects on human cells are still under investigation. The presence of iron oxide nanoparticles in the food pigment E172 has been shown recently. Here, we studied four iron oxide nanoparticles, one food pigment E172 and the ionic control FeSO4 regarding dissolution in biological media, uptake and transport, and cellular effects in vitro in human intestinal Caco-2 and HepaRG hepatocarcinoma cells. The iron oxide nanoparticles passed the gastrointestinal passage without dissolution and reached the intestine in the form of particles. Minor uptake was seen into Caco-2 cells but almost no transport to the basolateral site was detected for any of the tested particles. HepaRG cells showed higher particle uptake. Caco-2 cells showed no alterations in reactive oxygen species production, apoptosis, or mitochondrial membrane potential, whereas two particles induced apoptosis in HepaRG cells, and one altered mitochondrial membrane potential at non-cytotoxic concentrations. No correlation between physicochemical particle characteristics and cellular effects was observed, thus emphasizing the Need for case-by-case assessment of iron oxide nanoparticles. KW - Nanoparticles PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-521651 DO - https://doi.org/10.1007/s00204-020-02960-7 VL - 95 IS - 3 SP - 895 EP - 905 PB - Springer AN - OPUS4-52165 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Saloga, Patrick E. J. A1 - Rybak, Tina A1 - Thünemann, Andreas T1 - Microwave-Assisted Synthesis of ZnO Nanoparticles: Phase Transfer to Water N2 - Herein, a simple one-pot procedure is reported to obtain aqueous zinc oxide (ZnO) nanoparticle dispersions from ZnO nanoparticles dispersed in cyclohexane. In the process, polyoxyethylene (20) sorbitan monooleate (polysorbate 80, Tween 80) functions as a phase transfer agent and colloidal stabilizer. The particles grow in a defined manner during the transfer, presumably via coalescence. The final particle radii are tuneable in the range from 2.3 ± 0.1 nm to 5.7 ± 0.1 nm depending on the incubation time of the dispersion at 90 °C. Small-angle X-ray scattering is employed to determine the particle radius distributions before and after phase transfer. The larger ZnO particle radii are associated with a redshift of the optical bandgap and luminescence emission, as expected for semiconductor nanoparticles. The particles presented here exhibit a relative size distribution width of 20%, rendering them attractive for applications in, e.g., biology or catalysis. The latter application is demonstrated at the photocatalytic degradation of methylene blue dye. KW - SAXS KW - Small-angle X-ray scattering KW - nanoparticle PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-551502 DO - https://doi.org/10.1002/adem.202101276 VL - 24 IS - 6 SP - 1 EP - 7 PB - Wiley AN - OPUS4-55150 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Paul, Maxi B. A1 - Böhmert, Linda A1 - Thünemann, Andreas A1 - Loeschner, Katrin A1 - Givelet, Lucas A1 - Fahrenson, Christoph A1 - Braeuning, Albert A1 - Sieg, Holger T1 - Influence of artificial digestion on characteristics and intestinal cellular effects of micro-, submicro- and nanoplastics N2 - The production of plastics is rising since they have been invented. Micro, submicro- and nanoplastics are produced intentionally or generated by environmental processes, and constitute ubiquitous contaminants which are ingested orally by consumers. Reported health concerns include intestinal translocation, inflammatory response, oxidative stress and cytotoxicity. Every digestive milieu in the gastrointestinal tract does have an influence on the properties of particles and can cause changes in their effect on biological systems. In this study, we subjected plastic particles of different materials (polylactic acid, polymethylmethacrylate, melamine formaldehyde) and sizes (micro- to nano-range) to a complex artificial digestion model consisting of three intestinal fluid simulants (saliva, gastric and intestinal juice). We monitored the impact of the digestion process on the particles by performing Dynamic Light Scattering, Scanning Electron Microscopy and Asymmetric Flow Field-Flow Fractionation. An in vitro model of the intestinal epithelial barrier was used to monitor cellular effects and translocation behavior of (un)digested particles. In conclusion, artificial digestion decreased cellular interaction and slightly increased transport of all particles across the intestinal barrier. The interaction with organic matter resulted in clear differences in the agglomeration behavior. Moreover, we provide evidence for polymer-, size- and surface-dependent cellular effects of the test particles. KW - Toxicology KW - Nanoparticles KW - Dynamic Light Scattering KW - Nanoplastics KW - Microplastics KW - Reference Method KW - Reference Material PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-593947 DO - https://doi.org/10.1016/j.fct.2023.114423 SN - 0278-6915 VL - 184 SP - 1 EP - 16 PB - Elsevier B.V. AN - OPUS4-59394 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sieg, Holger A1 - Schaar, Caroline A1 - Fouquet, Nicole A1 - Böhmert, Linda A1 - Thünemann, Andreas A1 - Braeuning, Albert T1 - Particulate iron oxide food colorants (E 172) during artificial digestion and their uptake and impact on intestinal cells N2 - Iron oxide of various structures is frequently used as food colorant (E 172). The spectrum of colors ranges from yellow over orange, red, and brown to black, depending on the chemical structure of the material. E 172 is mostly sold as solid powder. Recent studies have demonstrated the presence of nanoscaled particles in E 172 samples, often to a very high extent. This makes it necessary to investigate the fate of these particles after oral uptake. In this study, 7 differently structured commercially available E 172 food colorants (2 x Yellow FeO(OH), 2 x Red Fe2O3, 1 x Orange Fe2O3 + FeO(OH) and 2 x Black Fe3O4) were investigated for particle dissolution, ion release, cellular uptake, crossing of the intestinal barrier and toxicological impact on intestinal cells. Dissolution was analyzed in water, cell culture medium and artificial digestion fluids. Small-angle X-ray scattering (SAXS) was employed for determination of the specific surface area of the colorants in the digestion fluids. Cellular uptake, transport and toxicological effects were studied using human differentiated Caco-2 cells as an in vitro model of the intestinal barrier. For all materials, a strong interaction with the intestinal cells was observed, albeit there was only a limited dissolution, and no toxic in vitro effects on human cells were recorded. KW - Toxicology KW - Nanoparticles KW - Small-angle X-ray scattering KW - SAXS PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-593935 DO - https://doi.org/10.1016/j.tiv.2024.105772 VL - 96 SP - 1 EP - 12 PB - Elsevier BV AN - OPUS4-59393 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hildebrandt, Jana A1 - Taubert, Andreas A1 - Thünemann, Andreas T1 - Synthesis and Characterization of Ultra‐Small Gold Nanoparticles in the Ionic Liquid 1‐Ethyl‐3‐methylimidazolium Dicyanamide, [Emim][DCA] N2 - AbstractWe report on gold clusters with around 62 gold atoms and a diameter of 1.15±0.10 nm. Dispersions of the clusters are long‐term stable for two years at ambient conditions. The synthesis was performed by mixing tetrachloroauric acid (HAuCl4 ⋅ 3 H2O) with the ionic liquid 1‐ethyl‐3‐methylimidazolium dicyanamide ([Emim][DCA]) at temperatures of 20 to 80 °C. Characterization was performed with small‐angle X‐ray scattering (SAXS), UV‐Vis spectroscopy, and MALDI‐TOF mass spectrometry. A three‐stage model is proposed for the formation of the clusters, in which cluster growth from gold nuclei takes place according to the Lifshitz‐Slyozov‐Wagner (LSW) model followed by oriented attachment to form colloidal stable clusters. KW - Reference materials KW - SAXS KW - Gold KW - Nanoparticle KW - Small-angle X-ray scattering KW - Ionic liquid PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-588203 DO - https://doi.org/10.1002/open.202300106 SN - 2191-1363 VL - 44 SP - 1 EP - 19 PB - Wiley AN - OPUS4-58820 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hildebrandt, Jana A1 - Thünemann, Andreas T1 - Aqueous Dispersions of Polypropylene: Toward Reference Materials for Characterizing Nanoplastics N2 - Microplastics and nanoplastics pollute the natural environment all over the world, but the full extent of the hazards posed by this waste is unclear. While research on microplastics is well advanced, little work has been done on nanoplastics. This discrepancy is mainly due to the lacking ability to detect nanoplastics in biologically and environmentally relevant matrices. Nanoplastics reference materials can help the development of suitable methods for identifying and quantifying nanoplastics in nature. The aim is to synthesize nanoplastics made from one of the most commonly used plastics, namely polypropylene. An easy way to produce long-term stable aqueous dispersions of polypropylene nanoparticles (nano polypropylene) is reported. The nanoplastic particles, prepared by mechanical breakdown, show a mean hydrodynamic diameter of D h = 180.5 ± 5.8 nm and a polydispersity index of PDI = 0.084 ± 0.02. No surfactant is needed to obtain dispersion which is stable for more than 6 months. The colloidal stability of the surfactant-free nano polypropylene dispersions is explained by their low zeta potential of 𝜻 = −43 ± 2 mV. KW - Nanoparticles KW - Reference Material KW - Nanoplastics PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-571799 DO - https://doi.org/10.1002/marc.202200874 SN - 1022-1336 VL - 44 IS - 6 SP - 1 EP - 15 PB - Wiley-VCH CY - Weinheim AN - OPUS4-57179 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Iannuzzi, Maurizio T1 - Rational design of polyfluorinated peptide-based materials: Self-assembly of an amphiphilic motif N2 - Generation of a pH sensitive amphiphilic block oligopeptide containing the bioactive function RGD and a library of derivatives varying the length of the hydrophobic core and the degree of side chain fluorination. Peptide rational design enables us to obtain desired features (pH sensitivity etc.). The introduction of fluorine alters a wide range of peptide properties such as secondary structure propensity, folding, thermal and metabolic stability and proteolytic resistance. The RGD function is highly effective at promoting the attachment of numerous cell types to a plethora of materials. This small sequence is the principal integrin-binding domain present within ECM proteins such as fiobronectin, vibronectin and fibrinogen. For this reason, RGD containing peptides offer several advantages for biomaterials applications. The use of RGD compared with native ECM proteins, minimized the risk of immune reactivity or pathogen transfer. Herein in this work, we present the peptide motif X6RGD and its fluoro-derivates for prospective receptor-specific drug delivery in cancer theraphy. Overall, our results demonstrate that high degree of fluorination achieved triggers a selective modification of peptide self-assembly dramatically improving the structural properties, the carrier suitability, enzimatic degradation profiles and cytotoxic features of the fluoropeptide conjugate(s). T2 - 37th European Peptide Symposium CY - Florence, Italy DA - 25.08.2024 KW - Small-angle X-ray scattering KW - SAXS KW - Nanostructure PY - 2024 DO - https://doi.org/10.17952/37EPS.2024.P1302 AN - OPUS4-62139 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Hörmann, Anja Franziska T1 - STOP and Scatter N2 - We present first X-ray scattering results for the Horizon Europe project "Surface Transfer of Pathogens" (STOP) and an outlook regarding X-ray scattering methods on thin films, which are under development at the MOUSE. T2 - M17 full project meeting - Surface Transfer of Pathogens (STOP) CY - EMPA, St. Gallen, Switzerland DA - 18.01.2024 KW - X-ray Scattering KW - Grazing incidence PY - 2024 AN - OPUS4-62723 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Hörmann, Anja Franziska T1 - Next Level Grazing Incidence: Let the Standardization Begin N2 - Reproducibility of experiments is something most natural scientists would consider important. However, how do we know experiments are comparable between instruments without explicitly disclosing, tracking and discussing instrument calibration and data processing methods? At SXNS17 we would like to introduce our standardization initiative to the Grazing Incidence Small-Angle Scattering (GISAS) community and gather initial feedback and perhaps contributors before we proceed further. From the point of view of development of a new lab GISAXS setup at BAM (Berlin, Germany), we propose a draft autoalignment and calibration routine. Together with the GISAS community, we would like to further develop this routine into a standard. On that basis, agreed-upon methods for data treatment could be the next step for the future and perhaps an organization like the Open Reflectometry Standards Organisation . We begin with a survey of hardware in use around the world, an area we are not planning to address in terms of standardization but which nonetheless provides the practical background for our efforts. We assume availability of pitch, roll, y and z motions, those may be present in the form of a stack of stages, a hexapod, or even a robot arm. All of these can be used for GISAS, but specifications such as backlash direction and minimum incremental motion need to be considered when it comes to resolution and repeatability of experiments. We ask for your help in gathering information on sample stages and holders and would like to present the results at the International Small-Angle Scattering Conference (SAS2024) in November 2024. We believe this an important step to ensure any developed standard can work for everyone in the end. Inspired by work for Grazing Incidence X-ray Diffraction one of our goals is to estimate and propagate uncertainties from stage motions to scattering vector q (compare for Small-Angle X-ray Scattering). Further ideas for standardization include the use of reflectometry in choosing angles of incidence and, perhaps more importantly, data corrections. T2 - Surface X-ray and Neutron Scattering 17 (SXNS17) CY - EPN, Grenoble, France DA - 15.07.2024 KW - Grazing incidence scattering KW - Sample alignment KW - Community survey KW - Calibration PY - 2024 AN - OPUS4-62724 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -