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 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 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 - Pauw, Brian Richard A1 - Smith, A. J. A1 - Snow, T. A1 - Shebanova, O. A1 - Sutter, J. P. A1 - Ilavsky, J. A1 - Hermida-Merino, D. A1 - Smales, Glen Jacob A1 - Terrill, N. J. A1 - Thünemann, Andreas A1 - Bras, W. T1 - Extending synchrotron SAXS instrument ranges through addition of a portable, inexpensive USAXS module with vertical rotation axes N2 - Ultra-SAXS can enhance the capabilities of existing synchrotron SAXS/WAXS beamlines. A compact ultra-SAXS module has been developed, which extends the measurable q-range with 0.0015 ≤ q (nm−1) ≤ 0.2, allowing structural dimensions in the range 30 ≤ D (nm) ≤ 4000 to be probed in addition to the range covered by a high-end SAXS/WAXS instrument. By shifting the module components in and out on their respective motor stages, SAXS/WAXS measurements can be easily and rapidly interleaved with USAXS measurements. The use of vertical crystal rotation axes (horizontal diffraction) greatly simplifies the construction, at minimal cost to efficiency. In this paper, the design considerations, realization and synchrotron findings are presented. Measurements of silica spheres, an alumina membrane, and a porous carbon catalyst are provided as application examples. KW - X-ray scattering KW - Microstructure KW - Instrumentation KW - SAXS KW - USAXS KW - Nanostructure KW - Combined techniques PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-524919 DO - https://doi.org/10.1107/S1600577521003313 SN - 1600-5775 VL - 28 IS - 3 SP - 824 EP - 833 PB - Wiley CY - Oxford AN - OPUS4-52491 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - INPR A1 - Pauw, Brian Richard A1 - Smith, A. J. A1 - Snow, T. A1 - Shebanova, O. A1 - Sutter, J. P. A1 - Ilavsky, J. A1 - Hermida-Merino, D. A1 - Smales, Glen Jacob A1 - Terrill, N. J. A1 - Thünemann, Andreas A1 - Bras, W. T1 - Extending SAXS instrument ranges through addition of a portable, inexpensive USAXS module N2 - Ultra-SAXS can enhance the capabilities of existing SAXS/WAXS beamlines and laboratory instruments. A compact Ultra-SAXS module has been developed, which extends the measurable q-range with 0:0015 < q 1/nm) < 0:2, allowing structural dimensions between 30 < D(nm) < 4000 to be probed in addition to the range covered by a high-end SAXS/WAXS instrument. By shifting the module components in and out on their respective motor stages, SAXS/WAXS measurements can be easily and rapidly interleaved with USAXS measurements. KW - Small-angle scattering PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-504867 DO - https://doi.org/10.48550/arXiv.1904.00080 SN - 2331-8422 SP - 1 EP - 25 PB - Cornell University CY - Ithaca, NY AN - OPUS4-50486 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Foroutan, F. A1 - Kyffin, B. A. A1 - Nikolaou, A. A1 - Merino-Gutierrez, J. A1 - Abrahams, I. A1 - Kanwal, N. A1 - Knowles, J. C. A1 - Smith, A. J. A1 - Smales, Glen Jacob A1 - Carta, D. T1 - Highly porous phosphate-based glasses for controlled delivery of antibacterial Cu ions prepared via sol–gel chemistry N2 - Mesoporous glasses are a promising class of bioresorbable biomaterials characterized by high surface area and extended porosity in the range of 2 to 50 nm. These peculiar properties make them ideal materials for the controlled release of therapeutic ions and molecules. Whilst mesoporous silicate-based glasses (MSG) have been widely investigated, much less work has been done on mesoporous phosphate-based glasses (MPG). In the present study, MPG in the P2O5–CaO–Na2O system, undoped and doped with 1, 3, and 5 mol% of Cu ions were synthesized via a combination of the sol–gel method and supramolecular templating. The non-ionic triblock copolymer Pluronic P123 was used as a templating agent. The porous structure was studied via a combination of Scanning Electron Microscopy (SEM), Small-Angle X-ray Scattering (SAXS), and N2 adsorption–desorption analysis at 77 K. The structure of the phosphate network was investigated via solid state 31P Magic Angle Spinning Nuclear Magnetic Resonance (31P MAS-NMR) and Fourier Transform Infrared (FTIR) spectroscopy. Degradation studies, performed in water via Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES), showed that phosphates, Ca2+, Na+ and Cu ions are released in a controlled manner over a 7 days period. The controlled release of Cu, proportional to the copper loading, imbues antibacterial properties to MPG. A significant statistical reduction of Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) bacterial viability was observed over a 3 days period. E. coli appeared to be more resistant than S. aureus to the antibacterial effect of copper. This study shows that copper doped MPG have great potential as bioresorbable materials for controlled delivery of antibacterial ions. KW - Bioresorbable Biomaterials KW - Mesoporous phosphate-based glasses KW - Synthesis KW - Degradation studies KW - X-ray scattering KW - MOUSE KW - Antibacterial properties KW - Aantimicrobial PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-578101 DO - https://doi.org/10.1039/D3RA02958A VL - 13 IS - 29 SP - 19662 EP - 19673 PB - Royal Society of Chemistry AN - OPUS4-57810 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sprachmann, J. A1 - Grabicki, N. A1 - Möckel, Anna A1 - Maltitz, J. A1 - del Refugio Monroy Gómez, J. A1 - Smales, Glen Jacob A1 - Dumele, O. T1 - Substituted Benzophenone Imines for COF Synthesis via Formal Transimination N2 - Covalent organic frameworks (COFs) are a prominent class of organic materials constructed from versatile building blocks via reversible reactions. The quality of imine-linked COFs can be improved by using amine monomers protected with benzophenone forming benzophenone imines. Here, we present a study on substituted benzophenones in COF synthesis via formal transimination. 12 para-substituted N-aryl benzophenone imines, with a range of electron-rich to electron-poor substituents, were prepared and their hydrolysis kinetics were studied spectroscopically. All substituted benzophenone imines can be employed in COF synthesis and lead to COFs with high crystallinity and high porosity. The substituents act innocent to COF formation as the substituted benzophenones are cleaved off. Imines can be tailored to their synthetic demands and utilized in COF formation. This concept can make access to previously unattainable, synthetically complex COF monomers feasible. KW - Materials Chemistry KW - Metals and Alloys KW - Surfaces, Coatings and Films KW - General Chemistry KW - Ceramics and Composites KW - Electronic, Optical and Magnetic Materials KW - Catalysis PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-586449 DO - https://doi.org/10.1039/D3CC03735E SN - 1359-7345 SP - 1 EP - 4 PB - Royal Society of Chemistry (RSC) AN - OPUS4-58644 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Aliyah, K. A1 - Prehal, C. A1 - Diercks, J. S. A1 - Diklić, N. A1 - Xu, L. A1 - Ünsal, S. A1 - Appel, C. A1 - Pauw, Brian Richard A1 - Smales, Glen Jacob A1 - Guizar-Sicairos, M. A1 - Herranz, J. A1 - Gubler, L. A1 - Büchi, F. N. A1 - Eller, J. T1 - Quantification of PEFC Catalyst Layer Saturation via In Silico, Ex Situ, and In Situ Small-Angle X-ray Scattering N2 - The complex nature of liquid water saturation of polymer electrolyte fuel cell (PEFC) catalyst layers (CLs) greatly affects the device performance. To investigate this problem, we present a method to quantify the presence of liquid water in a PEFC CL using small-angle X-ray scattering (SAXS). This method leverages the differences in electron densities between the solid catalyst matrix and the liquid water filled pores of the CL under both dry and wet conditions. This approach is validated using ex situ wetting experiments, which aid the study of the transient saturation of a CL in a flow cell configuration in situ. The azimuthally integrated scattering data are fitted using 3D morphology models of the CL under dry conditions. Different wetting scenarios are realized in silico, and the corresponding SAXS data are numerically simulated by a direct 3D Fourier transformation. The simulated SAXS profiles of the different wetting scenarios are used to interpret the measured SAXS data which allows the derivation of the most probable wetting mechanism within a flow cell electrode. KW - Polymer electrolyte fuel cell KW - Water management KW - Catalyst layer KW - Representative morphology modeling KW - Small-angle X-ray scattering KW - MOUSE KW - SAXS PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-575973 DO - https://doi.org/10.1021/acsami.3c00420 SN - 1944-8244 VL - 15 IS - 22 SP - 26538 EP - 26553 PB - ACS Publications AN - OPUS4-57597 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Chen, Z. A1 - Perez, J. P. H. A1 - Smales, Glen Jacob A1 - Blukis, R. A1 - Pauw, Brian Richard A1 - Stammeier, J. A. A1 - Radnik, Jörg A1 - Smith, A. J. A1 - Benning, L. G. T1 - Impact of organic phosphates on the structure and composition of short-range ordered iron nanophases N2 - Organic phosphates (OP) are important nutrient components for living cells in natural environments, where they readily interact with ubiquitous iron phases such as hydrous ferric oxide, ferrihydrite (FHY). FHY partakes in many key bio(geo)chemical reactions including iron-mediated carbon storage in soils, or iron-storage in living organisms. However, it is still unknown how OP affects the formation, structure and properties of FHY. Here, we document how β-glycerophosphate (GP), a model OP ligand, affects the structure and properties of GP–FHY nanoparticles synthesized by coprecipitation at variable nominal molar P/Fe ratios (0.01 to 0.5). All GP–FHY precipitates were characterized by a maximum solid P/Fe ratio of 0.22, irrespective of the nominal P/Fe ratio. With increasing nominal P/Fe ratio, the specific surface area of the GP–FHY precipitates decreased sharply from 290 to 3 m2 g−1, accompanied by the collapse of their pore structure. The Fe–P local bonding environment gradually transitioned from a bidentate binuclear geometry at low P/Fe ratios to monodentate mononuclear geometry at high P/Fe ratios. This transition was accompanied by a decrease in coordination number of edge-sharing Fe polyhedra, and the loss of the corner-sharing Fe polyhedra. We show that Fe(III) polymerization is impeded by GP, and that the GP–FHY structure is highly dependent on the P/Fe ratio. We discuss the role that natural OP-bearing Fe(III) nanophases have in biogeochemical reactions between Fe–P and C species in aquatic systems. KW - Organic phosphates KW - Iron nanophases KW - Scattering KW - Diffraction KW - Nanomaterials KW - Coprecipitation KW - Carbon storage PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-599399 DO - https://doi.org/10.1039/d3na01045g SN - 2516-0230 SP - 1 EP - 13 PB - Royal Society of Chemistry (RSC) CY - Cambridge AN - OPUS4-59939 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Huang, J. A1 - Tarábek, J. A1 - Kulkarni, R. A1 - Wang, Cui A1 - Dračínský, M. A1 - Smales, Glen Jacob A1 - Pauw, Brian Richard A1 - Resch-Genger, Ute A1 - Bojdys, M. J. T1 - A π-conjugated, covalent phosphinine framework N2 - Structural modularity of polymer frameworks is a key advantage of covalent organic polymers, however, only C, N, O, Si and S have found their way into their building blocks so far. Here, we expand the toolbox available to polymer and materials chemists by one additional nonmetal, phosphorus. Starting with a building block that contains a λ⁵‐phosphinine (C₅P) moiety, we evaluate a number of polymerisation protocols, finally obtaining a π‐conjugated, covalent phosphinine‐based framework (CPF‐1) via Suzuki‐Miyaura coupling. CPF‐1 is a weakly porous polymer glass (72.4 m2 g‐1 N2 BET at 77 K) with green fluorescence (λmax 546 nm) and extremely high thermal stability. The polymer catalyzes hydrogen evolution from water under UV and visible light irradiation without the need for additional co‐catalyst at a rate of 33.3 μmol h‐¹ g‐¹. Our results demonstrate for the first time the incorporation of the phosphinine motif into a complex polymer framework. Phosphinine‐based frameworks show promising electronic and optical properties that might spark future interest in their applications in light‐emitting devices and heterogeneous catalysis. KW - Phosphinine KW - Fully aromatic frameworks KW - Suzuki-Miyaura coupling KW - Polymers KW - Fluorescence KW - Small-angle scattering PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-485330 DO - https://doi.org/10.1002/chem.201900281 SP - 2 EP - 10 PB - Wiley VCH-Verlag CY - Weinheim AN - OPUS4-48533 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Falqueto, J. B. A1 - Clark, A. H. A1 - Štefančič, A. A1 - Smales, Glen Jacob A1 - Vaz, C. A. F. A1 - Schuler, A. J. A1 - Bocchi, N. A1 - Kazzi, M. E. T1 - High performance doped Li-rich Li1+xMn2–xO4 cathodes nanoparticles synthesized by facile, fast, and efficient microwave-assisted hydrothermal route N2 - Li-rich nanoparticles of Li1+xMn2–xO4 doped with Al, Co, or Ni are successfully synthesized using a facile, fast, and efficient microwave-assisted hydrothermal route. Synchrotron X-ray diffraction confirms the formation of the crystalline cubic spinel phase type. X-ray absorption spectroscopy analysis at the Co and Ni K- and L-edges verifies that the dopants are within the Li1+xMn2–xO4 spinel structure and are inactive during cycling in the bulk and at the surface. Moreover, we demonstrate that nanocrystallinity and cationic doping play an important role in improving the electrochemical performance with respect to LiMn2O4 microparticles. They significantly reduce the charge-transfer resistance, lower the first cycle irreversible capacity loss to 6%, and achieve a capacity retention between 85 and 90% after 380 cycles, with excellent Coulombic efficiency close to 99% without compromising the specific charge at a 5C cycling rate. Furthermore, the Mn K- and L-edges attest that after long cycling, the Mn oxidation state in the bulk differs from that at the surface caused by the Mn disproportion reaction; however, the cationic doping helps mitigate the Mn dissolution with respect to the undoped Li1+xMn2–xO4 nanoparticles, as indicated by inductively coupled plasma atomic emission spectrometry. KW - XAS KW - SAXS KW - Li-ion battery KW - Cathode material KW - Spinel KW - The MOUSE PY - 2022 DO - https://doi.org/10.1021/acsaem.2c00902 SN - 2574-0962 VL - 5 IS - 7 SP - 8357 EP - 8370 PB - ACS Publ. CY - Washington, DC AN - OPUS4-55359 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sprachmann, J. A1 - Wachsmuth, T. A1 - Bhosale, M. A1 - Burmeister, D. A1 - Smales, Glen Jacob A1 - Schmidt, M. A1 - Kochovski, Z. A1 - Grabicki, N. A1 - Wessling, R. A1 - List-Kratochvil, E. J. W. A1 - Esser, B. A1 - Dumele, O. T1 - Antiaromatic Covalent Organic Frameworks Based on Dibenzopentalenes N2 - Despite their inherent instability, 4n π systems have recently received significant attention due to their unique optical and electronic properties. In dibenzopentalene (DBP), benzanellation stabilizes the highly antiaromatic pentalene core, without compromising its amphoteric redox behavior or small HOMO−LUMO energy gap. However, incorporating such molecules in organic devices as discrete small molecules or amorphous polymers can limit the performance (e.g., due to solubility in the battery electrolyte solution or low internal surface area). Covalent organic frameworks (COFs), on the contrary, are highly ordered, porous, and crystalline materials that can provide a platform to align molecules with specific properties in a well-defined, ordered environment. We synthesized the first antiaromatic framework materials and obtained a series of three highly crystalline and porous COFs based on DBP. Potential applications of such antiaromatic bulk materials were explored: COF films show a conductivity of 4 × 10−8 S cm−1 upon doping and exhibit photoconductivity upon irradiation with visible light. Application as positive electrode materials in Li-organic batteries demonstrates a significant enhancement of performance when the antiaromaticity of the DBP unit in the COF is exploited in its redox activity with a discharge capacity of 26 mA h g−1 at a potential of 3.9 V vs. Li/Li+ . This work showcases antiaromaticity as a new design principle for functional framework materials. KW - SAXS KW - MOUSE KW - Covalent Organic Frameworks KW - Batteries PY - 2023 DO - https://doi.org/10.1021/jacs.2c10501 SP - 1 EP - 12 PB - ACS Publications AN - OPUS4-56958 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Berry, Charlotte A. A1 - Reinart, Katre A1 - Smales, Glen J. A1 - Wilkinson, Holly N. A1 - Hardman, Matthew J. A1 - Marchesini, Sofia A1 - Lee, William A1 - Nery, Eveliny Tomás A1 - Moghaddam, Zarrin A1 - Hoxha, Agron A1 - Felipe-Sotelo, Mónica A1 - Gutierrez-Merino, Jorge A1 - Carta, Daniela T1 - Hierarchically porous copper and gallium loaded sol–gel phosphate glasses for enhancement of wound closure N2 - In this work, we have developed hierarchically porous phosphate-based glasses (PPGs) as novel materials capable of promoting wound closure and simultaneously delivering antibacterial effects at the glass-biological tissue interface. PPGs are characterised by extended porosity, which enhances the controlled release of therapeutic ions, whilst facilitating cell infiltration and tissue growth. Two series of PPGs in the systems P2O5–CaO–Na2O–CuO and P2O5–CaO–Na2O–Ga2O3 with (CuO and Ga2O3 0, 1, 5 and 10 mol%) were manufactured using a supramolecular sol–gel synthesis strategy. Significant wound healing promotion (up to 97%) was demonstrated using a human ex vivo wound model. A statistically significant reduction of the bacterial strains Staphylococcus aureus and Escherichia coli was observed in both series of PPGs, particularly those containing copper. All PPGs exhibited good cytocompatibility on keratinocytes (HaCaTs), and analysis of PPG dissolution products over a 7-day period demonstrated controlled release of phosphate anions and Ca, Na, Cu, and Ga cations. These findings indicate that Cu- and Ga-loaded PPGs are promising materials for applications in soft tissue regeneration given their antibacterial capabilities, in vitro biocompatibility with keratinocytes and ex vivo wound healing properties at the biomaterial-human tissue interface. KW - Porous glass KW - Phosphates KW - Wound healing materials KW - Antibacterial KW - X-ray scattering KW - MOUSE PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-650867 DO - https://doi.org/10.1039/d5tb01945a SN - 2050-750X VL - 13 IS - 48 SP - 15662 EP - 15677 PB - Royal Society of Chemistry (RSC) AN - OPUS4-65086 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Henning, L. M. A1 - Müller, J. T. A1 - Smales, Glen Jacob A1 - Pauw, Brian Richard A1 - Schmidt, J. A1 - Bekheet, M. F. A1 - Gurlo, A. A1 - Simon, U. T1 - Hierarchically porous and mechanically stable monoliths from ordered mesoporous silica and their water filtration potential N2 - Mechanically stable structures with interconnected hierarchical porosity combine the benefits of both small and large pores, such as high surface area, pore volume, and good mass transport capabilities. Hence, lightweight micro-/meso-/macroporous monoliths are prepared from ordered mesoporous silica COK-12 by means of spark plasma sintering (SPS, S-sintering) and compared to conventionally (C-) sintered monoliths. A multi-scale model is developed to fit the small angle X-ray scattering data and obtain information on the hexagonal lattice parameters, pore sizes from the macro to the micro range, as well as the dimensions of the silica population. For both sintering techniques, the overall mesoporosity, hexagonal pore ordering, and amorphous character are preserved. The monoliths' porosity (77–49%), mesopore size (6.2–5.2 nm), pore volume (0.50–0.22 g cm-3 ), and specific surface area (451–180 m2 g-1) decrease with increasing processing temperature and pressure. While the difference in porosity is enhanced, the structural parameters between the C-and S-sintered monoliths are largely converging at 900 C, except for the mesopore size and lattice parameter, whose dimensions are more extensively preserved in the S-sintered monoliths, however, coming along with larger deviations from the theoretical lattice. Their higher mechanical properties (biaxial strength up to 49 MPa, 724 MPa HV 9.807 N) at comparable porosities and ability to withstand ultrasonic treatment and dead-end filtration up to 7 bar allow S-sintered monoliths to reach a high permeance (2634 L m-2 h-1 bar-1), permeability (1.25 x 10^-14 m2), and ability to reduce the chemical oxygen demand by 90% during filtration of a surfactant-stabilized oil in water emulsion, while indicating reasonable resistance towards fouling. KW - SAXS KW - Hierarchically porous KW - Silica KW - Water filtration PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-555928 DO - https://doi.org/10.1039/D2NA00368F SN - 2516-0230 SP - 1 EP - 17 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-55592 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Emamverdi, Farnaz A1 - Yin, Huajie A1 - Smales, Glen Jacob A1 - Harrison, W. J. A1 - Budd, P. M. A1 - Böhning, Martin A1 - Schönhals, Andreas T1 - Polymers of intrinsic microporosity - Molecular mobility and physical aging revisited by dielectric spectroscopy and X‑ray scattering N2 - Polymers of intrinsic microporosity (PIMs) are promising candidates for the active layer in gas separation membranes due to their high permeability and reasonable permselectivity. These appealing properties originate from a microporous structure as a result of inefficient segment packing in the condensed state due to a combination of a ladder-like rigid backbone and sites of contortion. However, this class of polymers suffers from a significant decrease in the permeability with time due to physical aging, whereby typically, the permselectivity increases. The initial microporous structures approach a denser state via local rearrangements, leading to the reduction of the permeability. Hence, a detailed characterization of the molecular mobility in such materials can provide valuable information on physical aging. In this work, the dielectric behavior of PIM-1 films and their behavior upon heating (aging) were revisited by isothermal frequency scans during different heating/cooling cycles over a broad temperature range between 133 and 523 K (−140 to 250 °C). In addition, the obtained results were compared with data of samples that were annealed at ambient temperatures over different time scales. Multiple dielectric processes were observed: several relaxation processes due to local fluctuations and a Maxwell−Wagner−Sillars polarization effect related to the microporosity. The temperature dependence of the rates of all processes follows the Arrhenius law where the estimated activation energy depends on the nature of the process. The influence of the thermal history (aging) on the processes is discussed in detail. KW - Polymers of intrinsic microporosity PY - 2022 DO - https://doi.org/10.1021/acs.macromol.2c00934 VL - 55 SP - 7340 EP - 7350 PB - American Chemical Society CY - Washington, DC AN - OPUS4-55485 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Müller, W. A1 - Schweins, R. A1 - Nöcker, B. A1 - Kohlbrecher, J. A1 - Smales, Glen Jacob A1 - Huber, K. T1 - Comparative study of the co-assembly behaviour of 3-chloro-4-hydroxy-phenylazo dyes with DTAB N2 - The co-assembly of three one-fold negatively charged 3-chloro-4-hydroxy-phenylazo dyes (Yellow, Blue and Red) with the cationic surfactant dodecyltrimethylammoniumbromide (DTAB) was studied to probe dye–DTAB binding stoichiometry and assembly morphology. For each dye, phase separation was observed above a given dye : DTAB ratio with the ratio depending on the dye. While Yellow and DTAB showed liquid/liquid phase separation above Yellow : DTAB = 1 : 1.67, crystalline dye–DTAB complexes were observed for Blue–DTAB and Red–DTAB above Blue : DTAB = 1 : 2.56 and Red : DTAB = 1 : 2.94 respecively. In homogeneous solution, UV/vis spectroscopic investigations suggest stochiometries of Yellow : DTAB = 1 : 2, Blue : DTAB = 1 : 3 and Red : DTAB = 1 : 4. It was concluded, that Yellow exhibits the highest dye : DTAB binding stoichiometry in both, dye–surfactant complexes in the 2-phase region and in solution, whereas the lowest dye : DTAB binding stoichiometry was observed for Red–DTAB in both cases. The observed stoichiometries are inversely correlated to the impact dye addition has on the morphology of DTAB micelles. Generally, addition of dye to DTAB micelles leads to a reduction in spontaneous curvature of these micelles and to the formation of triaxial ellipsoidal or cylindrical micelles from oblate ellipsoidal DTAB micelles. At a DTAB concentration of 30 mM and a dye concentration of 5 mM, this effect was most pronounced for Red and least pronounced for Yellow, whilst Blue showed an intermediate effect. KW - Dye KW - DTAB KW - SAXS KW - Small-angle X-ray scattering KW - X-ray scattering KW - Data analysis KW - Micelle PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-576978 DO - https://doi.org/10.1039/D3SM00501A SN - 1744-683X VL - 19 IS - 24 SP - 4588 EP - 4598 PB - Royal Society of Chemistry AN - OPUS4-57697 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wang, Z. A1 - Villa Santos, C. A1 - Legrand, A. A1 - Haase, F. A1 - Hara, Y. A1 - Kanamori, K. A1 - Aoyama, T. A1 - Urayama, K. A1 - Doherty, C. M. A1 - Smales, Glen Jacob A1 - Pauw, Brian Richard A1 - Colon, Y. J. A1 - Furukawa, S. T1 - Multiscale structural control of linked metal–organic polyhedra gel by aging-induced linkage-reorganization N2 - Assembly of permanently porous metal–organic polyhedra/cages (MOPs) with bifunctional linkers leads to soft supramolecular networks featuring both porosity and processability. However, the amorphous nature of such soft materials complicates their characterization and thus limits rational structural control. Here we demonstrate that aging is an effective strategy to control the hierarchical network of supramolecular gels, which are assembled from organic ligands as linkers and MOPs as junctions. Normally, the initial gel formation by rapid gelation leads to a kinetically trapped structure with low controllability. Through a controlled post-synthetic aging process, we show that it is possible to tune the network of the linked MOP gel over multiple length scales. This process allows control on the molecular-scale rearrangement of interlinking MOPs, mesoscale fusion of colloidal particles and macroscale densification of the whole colloidal network. In this work we elucidate the relationships between the gel properties, such as porosity and rheology, and their hierarchical structures, which suggest that porosity measurement of the dried gels can be used as a powerful tool to characterize the microscale structural transition of their corresponding gels. This aging strategy can be applied in other supramolecular polymer systems particularly containing kinetically controlled structures and shows an opportunity to engineer the structure and the permanent porosity of amorphous materials for further applications. KW - SAXS KW - Metal-organic polyhedra KW - Structural control PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-532309 DO - https://doi.org/10.1039/d1sc02883a SN - 1478-6524 SN - 1742-2183 VL - 12 IS - 38 SP - NIL_1 EP - NIL_9 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-53230 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Friberg, I. A1 - Clark, A. H. A1 - Ho, P. A1 - Sadokhina, N. A1 - Smales, Glen Jacob A1 - Woo, J. A1 - Auray, X. A1 - Ferri, D. A1 - Nachtegaal, M. A1 - Krocher, O. A1 - Olsson, L. T1 - Structure and performance of zeolite supported Pd for complete methane oxidation N2 - The influence of zeolite support materials and their impact on CH4 oxidation activity was studied utilizing Pd supported on H-beta and H-SSZ-13. A correlation between CH4 oxidation activity, Si/Al ratio (SAR), the type of zeolite framework, reduction-oxidation behaviour, and Pd species present was found by combining catalytic activity measurements with a variety of characterization methods (operando XAS, NH3-TPD, SAXS, STEM and NaCl titration). Operando XAS analysis indicated that catalysts with high CH4 oxidation activity experienced rapid transitions between metallic- and oxidized-Pd states when switching between rich and lean conditions. This behaviour was exhibited by catalysts with dispersed Pd particles. By contrast, the formation of ion-exchanged Pd2+ and large Pd particles appeared to have a detrimental effect on the oxidation-reduction behaviour and the conversion of CH4. The formation of ion-exchanged Pd2+ and large Pd particles was limited by using a highly siliceous beta zeolite support with a low capacity for cation exchange. The same effect was also found using a small-pore SSZ-13 zeolite due to the lower mobility of Pd species. It was found that the zeolite support material should be carefully selected so that the well-dispersed Pd particles remain, and the formation of ion-exchanged Pd2+ is minimized. KW - SAXS KW - Zeolites KW - Methane Oxidation KW - XAS KW - Catalysis PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-529606 DO - https://doi.org/10.1016/j.cattod.2020.11.026 VL - 382 SP - 3 EP - 12 PB - Elsevier B.V. AN - OPUS4-52960 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hunter, R. D. A1 - Rowlandson, J. L. A1 - Smales, Glen Jacob A1 - Pauw, Brian Richard A1 - Ting, V. P. A1 - Kulak, A. A1 - Schnepp, Z. T1 - The effect of precursor structure on porous carbons produced by iron-catalyzed graphitization of biomass N2 - This paper reports a systematic study into the effect of different biomass-derived precursors on the structure and porosity of carbons prepared via catalytic graphitization. Glucose, starch and cellulose are combined with iron nitrate and heated under a nitrogen atmosphere to produce Fe3C nanoparticles, which catalyze the conversion of amorphous carbon to graphitic nanostructures. The choice of organic precursor provides a means of controlling the catalyst particle size, which has a direct effect on the porosity of the material. Cellulose and glucose produce mesoporous carbons, while starch produces a mixture of micro- and mesopores under the same conditions and proceeds via a much slower graphitization step, generating a mixture of graphitic nanostructures and turbostratic carbon. Porous carbons are critical to energy applications such as batteries and electrocatalytic processes. For These applications, a simple and sustainable route to those carbons is essential. Therefore, the ability to control the precise structure of a biomass-derived carbon simply through the choice of precursor will enable the production of a new generation of energy materials. KW - SAXS KW - Porous carbons KW - Graphitization KW - Iron nanoparticles KW - Catalysis KW - Gas sorption PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-515531 DO - https://doi.org/10.1039/d0ma00692k VL - Royal Society of Chemistry SP - 1 EP - 11 AN - OPUS4-51553 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dal Molin, E. S. A1 - Henning, L. M. A1 - Müller, J. T. A1 - Smales, Glen Jacob A1 - Pauw, Brian Richard A1 - Bekheet, M. F. A1 - Gurlo, A. A1 - Simon, U. T1 - Robocasting of ordered mesoporous silica‐based monoliths: Rheological, textural, and mechanical characterization N2 - Hierarchically porous, high‐surface‐area silica materials are excellent candidates for multiple applications like catalysis and environmental remediation. Shaping these materials with additive manufacturing (AM) techniques, like robocasting, could enable their use with the benefit of on‐demand, customized shaping and maximizing performance. Herein, ordered mesoporous silica COK‐12 slurries were robocasted into monoliths, containing different ratios of uncalcined COK‐12 and sodium bentonite (0–25 wt.%). The rheology of the mixed slurries is characterized by lower flow indexes (0.69 vs. 0.32) and higher yield stresses (96 vs. 259 Pa) compared to pure COK‐12 ones. Monoliths were printed in woodpile structures and calcined at 600°C. Micro‐CT measurements showed a linear shrinkage of 25% after calcination. Mechanical characterization showed increased uniaxial strength (0.20 ± 0.07 to 1.0 ± 0.3 MPa) with increasing binder/solids ratio from 13 to 25%. The amorphous, mesoporous structure of COK‐12 was retained. The structures exhibited open porosities of 52 ± 4% and showed higher specific mesopore volumes, and increased average mesopore size (6 vs. 8 nm) compared to COK‐12. Small‐angle x‐ray scattering analysis revealed an increased lattice parameter (10.3 vs. 11.0 nm) and reduced wall thickness (3.1 nm vs. 4.1 nm) of the COK‐12 in the monoliths. These properties indicate suitability for their application as porous supports and adsorbents. KW - Industrial and Manufacturing Engineering KW - Additive manufacturing KW - OMS KW - Porous materials KW - Robocasting KW - X-ray scattering KW - MOUSE PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-582503 DO - https://doi.org/10.1002/nano.202300109 VL - 4 IS - 11-12 SP - 615 EP - 631 PB - Wiley-VCH GmbH AN - OPUS4-58250 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Foroutan, Farzad A1 - Abrahams, Isaac A1 - Smales, Glen Jacob A1 - Kanwal, Nasima A1 - di Pasquale, Roberto A1 - Knowles, Jonathan C. A1 - Smith, Andrew J. A1 - Carta, Daniela T1 - A sol-gel templating route for the synthesis of hierarchical porous calcium phosphate glasses containing zinc N2 - Hierarchical porous phosphate-based glasses (PPG) have great potential in biomedicine. Micropores (pore size <2 nm) increase the surface area, mesopores (pore size 2–50 nm) facilitate the absorption and diffusion of therapeutic ions and molecules making them ideal controlled delivery systems, while macropores (pore size >50 nm) facilitate the movement and diffusion of cells and fluids. In addition, the bioresorbability of PPG allows for their complete solubility in body fluid, alongside simultaneous formation of new tissue. Making PPG via the traditional melt-quenching (MQ) synthesis method used for phosphate-based glasses (PG), is not straightforward. Hence, we present here a route for preparing such glasses using a combination of sol-gel (SG) and templating methods. Hierarchical PPG in the P₂O₅–CaO–Na₂O system with the addition of 1, 3 and 5 mol % of Zn²⁺ were prepared with pore dimensions ranging from the micro-to the macro scales using Pluronic 123 (P123) as a surfactant. The presence of micropores (0.30–0.46 nm), mesopores (1.75–9.35 nm) and macropores (163–207 nm) was assessed via synchrotron-based Small-Angle X-ray Scattering (SAXS), with the presence of the latter two confirmed by Scanning Electron Microscopy (SEM). Structural characterisation performed using ³¹P solid state magic angle spinning nuclear magnetic resonance (MAS NMR) and Fourier Transform Infrared (FTIR) spectroscopies shows the presence of Q², Q¹ and Q⁰ phosphate species with a predominance of Q¹ species in all compositions. Dissolution studies in deionised (DI) water confirm that controlled release of phosphates, Ca²⁺, Na⁺ and Zn²⁺ is achieved over a period of 7 days. In particular, the release of Zn²⁺ is proportional to its loading, making its delivery particularly easy to control. KW - Sol-gel KW - Phosphate-based glasses KW - Mesoporous materials KW - Hierarchical porosity PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-613698 DO - https://doi.org/10.1016/j.ceramint.2024.07.180 SN - 0272-8842 VL - 50 IS - 20, Part A SP - 38174 EP - 38182 PB - Elsevier CY - Amsterdam AN - OPUS4-61369 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Smales, Glen Jacob A1 - Sprachmann, J. T1 - Datasets of Antiaromatic COFs associated with the publication "Antiaromatic Covalent Organic Frameworks Based on Dibenzopentalenes" N2 - X-ray scattering and sorption data associated with the publication "Antiaromatic Covalent Organic Frameworks Based on Dibenzopentalenes". X-ray scattering data is provided for COF and POP materials, including data from stability tests, as three-column ascii files with columns q (nm-1), I (m-1) and uncertainty on I, as well as being provided in 2θ. KW - X-ray scattering KW - SAXS KW - Covalent Organic Frameworks KW - Antiaromaticity KW - MOUSE PY - 2023 DO - https://doi.org/10.5281/zenodo.7509377 PB - Zenodo CY - Geneva AN - OPUS4-56868 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - INPR A1 - Smales, Glen J. A1 - Appel, Paul A1 - Breßler, Ingo A1 - Chambers, Aaron A1 - Dumele, Oliver A1 - Ebisch, Maximilian A1 - Frontzek, Julius A1 - del Refugio Monroy, José A1 - Rosalie, Julian M. A1 - Pauw, Brian R. T1 - DACHS and RoWaN: The Automated and Traceable Synthesis of ZIF-8 N2 - Automated synthesis and open-data practices are increasingly seen as key enablers of transparent, traceable, and reproducible science. By combining automation with structured, metadata-rich documentation, it becomes possible to systematically com- pare synthesis strategies and link outcomes to detailed parameters. In this work, we implement such an approach to study the synthesis of ZIF-8, comparing hand and automation-assisted methods under controlled conditions. Using over 100 synthesis experiments, we assess the repeatability of particle size and yield, and explore how variations in mixing and injection influence outcomes. This study demonstrates how traceable synthesis workflows can support repeatability and comparison across synthe- sis strategies. The DACHS (Database for Automation, Characterization and Holistic Synthesis) framework underpins this work, providing a lightweight infrastructure for transparent synthesis data capture. KW - Automation KW - MOFs KW - SAXS PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-645861 DO - https://doi.org/10.26434/chemrxiv-2025-7fgg0 SP - 1 EP - 32 PB - Cambridge AN - OPUS4-64586 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Adamski, Paweł A1 - Zgrzebnicki, Michał A1 - Albrecht, Aleksander A1 - Jurkowski, Artur A1 - Wojciechowska, Agnieszka A1 - Ekiert, Ewa A1 - Sielicki, Krzysztof A1 - Mijowska, Ewa A1 - Smales, Glen J. A1 - Maximenko, Alexey A1 - Moszyński, Dariusz T1 - Ammonia synthesis over γ-Al2O3 supported Co-Mo catalysts N2 - Novel ammonia synthesis catalysts are sought due to energetic transformation and increasing environmental consciousness. Materials containing cobalt and molybdenum are showing state-of-art activities in ammonia synthesis. The application of γ-alumina support was proposed to enhance the properties of Co-Mo nanoparticles. The wet impregnation of the support was conducted under reduced pressure. The active catalysts were obtained by ammonolysis of precursors. The chemical and phase composition, as well as morphology, porosity, and surface composition of precursors and catalysts, were characterized. The Co-Mo nanoparticles phase composition as well as their size and dispersion were determined using X-ray absorption spectroscopy utilizing synchrotron radiation, electron microscopy, and X-ray scattering. The catalytic activity was tested in the ammonia synthesis process under atmospheric pressure. The activity and stability of the supported catalysts were compared with unsupported cobalt molybdenum nitride Co3Mo3N, revealing the superiority of the present approach. KW - Ammonia synthesis KW - Supported catalyst KW - Cobalt molybdenum nitrides KW - Scattering KW - X-ray scattering KW - Gamma-alumina KW - Stability PY - 2025 DO - https://doi.org/10.1016/j.mcat.2025.114907 SN - 2468-8231 VL - 575 SP - 1 EP - 9 PB - Elsevier B.V. AN - OPUS4-64827 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - del Rocío Silva-Calpa, Leydi A1 - de Souza Bernardes, Andrelaine A1 - de Avillez, Roberto Ribeiro A1 - Smales, Glen J. A1 - Camarena, Mariella Alzamora A1 - Ramos Moreira, Carla A1 - Zaitsev, Volodymyr A1 - Archanjo, Braulio Soares A1 - Letichevsky, Sonia T1 - From support to shell: An innovative design of air-stable nano zero-valent iron–nickel catalysts via structural self-assembly N2 - This work presents the design of air-stable core–shell zero-valent iron–nickel nanofilaments supported on silica and zeolite, developed to overcome the oxidation limitations of nano zero-valent iron in environmental catalysis. The nanofilaments feature ∼ 100 nm iron–nickel cores surrounded by ultrafine iron-rich threads embedded with aluminates and silicates, originating from partial support dissolution during synthesis. By varying the iron reduction time, three catalysts were prepared: one on silica reduced for 30 min, and two on zeolite reduced for 30 and 15 min. They were thoroughly characterized using nitrogen physisorption, X-ray diffraction, electron microscopy with elemental analysis, Mössbauer spectroscopy, and small-angle X-ray scattering. The zeolite-supported catalyst reduced for 15 min showed the highest activity for hexavalent chromium reduction (rate constant 8.054 min−1), attributed to a higher fraction of reactive iron–nickel phases formed under shorter reduction. Its tailored core–shell structure improves air stability and surface reactivity, highlighting its potential as a next-generation zero-valent iron nanocatalyst for aqueous remediation KW - nanofilaments KW - Core–shell nanostructures KW - Air-stable nanomaterials KW - Structure-controlled FeNi nanoparticles KW - Hexavalent chromium reduction KW - X-ray scattering KW - MOUSE PY - 2025 DO - https://doi.org/10.1016/j.mtcomm.2025.114142 SN - 2352-4928 VL - 49 SP - 1 EP - 15677 PB - Elsevier Ltd. AN - OPUS4-65087 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 - Wolf, J. A1 - Stawski, Tomasz A1 - Smales, Glen Jacob A1 - Thünemann, Andreas A1 - Emmerling, Franziska T1 - Towards automation of the polyol process for the synthesis of silver nanoparticles N2 - Metal nanoparticles have a substantial impact across diferent felds of science, such as photochemistry, energy conversion, and medicine. Among the commonly used nanoparticles, silver nanoparticles are of special interest due to their antibacterial properties and applications in sensing and catalysis. However, many of the methods used to synthesize silver nanoparticles often do not result in well-defned products, the main obstacles being high polydispersity or a lack of particle size tunability. We describe an automated approach to on-demand synthesis of adjustable particles with mean radii of 3 and 5 nm using the polyol route. The polyol process is a promising route for silver nanoparticles e.g., to be used as reference materials. We characterised the as-synthesized nanoparticles using small-angle X-ray scattering, dynamic light scattering and further methods, showing that automated synthesis can yield colloids with reproducible and tuneable properties. KW - Sillver KW - Nanoparticles KW - Automated synthesis KW - Chemputer KW - Scattering KW - SAXS PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-546803 DO - https://doi.org/10.1038/s41598-022-09774-w VL - 12 IS - 1 SP - 1 EP - 9 PB - Nature Springer AN - OPUS4-54680 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Karafiludis, Stephanos A1 - de Oliveira Guilherme Buzanich, Ana A1 - Heinekamp, Christian A1 - Smales, Glen Jacob A1 - Hodoroaba, Vasile-Dan A1 - ten Elshof, J. E. A1 - Emmerling, Franziska A1 - Stawski, Tomasz T1 - Template-free synthesis of mesoporous, amorphous transition metal phosphate materials N2 - We present how mesoporosity can be engineered in transition metal phosphate (TMPs) materials in a template-free manner. The method involves a transformation of a precursor metal phosphate phase, called M-struvite (NH4MPO4·6H2O, M = Mg2+, Ni2+, Co2+, NixCo1-x2+). It relies on the thermal decomposition of crystalline M-struvite precursors to an amorphous and simultaneously mesoporous phase, which forms while degassing of NH3 and H2O. The temporal evolution of mesoporous frameworks and the response of the metal coordination environment were followed with in-situ and ex-situ scattering and diffraction, as well as X -ray spectroscopy. Despite sharing the same precursor struvite structure, different amorphous and mesoporous structures were obtained depending on the involved transition metal. We highlight the systematic differences in absolute surface area, pore shape, pore size, and phase transitions depending on a metal cation present in the analogous M-struvites. The amorphous structures of thermally decomposed Mg-, Ni- and NixCo1-x-struvites exhibit high surface areas and pore volumes (240 m²g-1 and 0.32 cm-3 g-1 for Mg and 90 m²g-1 and 0.13 cm-3 g-1 for Ni). We propose that the low-cost, environmentally friendly M-struvites could be obtained as recycling products from industrial and agricultural wastewaters. These waste products could be then upcycled into mesoporous TMPs through a simple thermal treatment for further applications, for instance, in (electro)catalysis. KW - Struvite KW - Pphosphates KW - Transition metal KW - In-situ SAXS/WAXS KW - Mesoporosity PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-569503 DO - https://doi.org/10.1039/D2NR05630E SN - 2040-3364 SP - 1 EP - 15 PB - Royal Society of Chemistry (RSC) AN - OPUS4-56950 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - RPRT A1 - Hodoroaba, Vasile-Dan A1 - Fontanges, R. A1 - Delvallée, A. A1 - Deumer, J. A1 - Salzmann, C. A1 - Crouzier, L. A1 - Gollwitzer, C. A1 - Klein, T. A1 - Koops, R. A1 - Sebaihi, N. A1 - Pauw, Brian Richard A1 - Smales, Glen Jacob A1 - Artous, S. A1 - Taché, O. A1 - Feltin, N. T1 - Report on full algorithm sequences for nanoparticle detection and size measurement as developed on both a physical basis and by machine learning N2 - he main objective of the nPSize project is to improve the measurement capabilities for nanoparticle size based on both measurement methods traceable to SI units and new reference materials. Two basic approaches have been used in order to develop measurement procedures resulting in traceable results of the nanoparticle size distribution: physical modelling for the methods used in the project (TSEM, SEM, AFM and SAXS) and machine learning. Physical modelling: In this part, the physical models associated with different shape measurements for the techniques TSEM, SEM, AFM and SAXS have been collected and further developed with the aim to simulate the resulting signal as measured by the individual methods. Uncertainties and traceability associated with each model were investigated and evaluated. In the following, the progress on these physical models is reported for each individual method. Machine Learning modelling: The aim of this part is to use machine learning to enable automatic measurement of nanoparticle shape from expert a-priori information only. No physical model will be used as a-priori information in this task. The accuracy and traceability of the size results obtained by each technique will be analyzed and compared with the physical modelling. A machine learning database will then be used to create automatic detection algorithms. KW - Nanoparticles KW - Particle size distribution KW - SEM KW - TSEM KW - TEM KW - SAXS KW - AFM PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-546531 DO - https://doi.org/10.5281/zenodo.5807864 SP - 1 EP - 20 PB - Zenodo CY - Geneva AN - OPUS4-54653 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -