TY - JOUR A1 - Kolmangadi, Mohamed A. A1 - Zhuoqing, L. A1 - Smales, Glen Jacob A1 - Pauw, Brian Richard A1 - Wuckert, E. A1 - Raab, A. A1 - Laschat, S. A1 - Huber, P. A1 - Schönhals, Andreas T1 - Confinement-suppressed phase transition and dynamic self-assembly of ionic superdiscs in ordered nanochannels: Implication for nanoscale applications N2 - Ionic Liquid Crystals are ionic liquids that exhibit liquid crystalline mesomorphism together with ionic conductivity. As known confined liquid crystal mesophases can show an anomalous dynamics and phase behavior. Investigations considering the factors controlling the macroscopic properties of ILCs in confinement are scare in the literature. This study reports the molecular mobility, and the phase transition behavior of a guanidinium based columnar ILC confined in the nanopores of self-ordered anodic aluminum oxide membranes of various pore diameters (25 – 180 nm) using Broadband Dielectric Spectroscopy (BDS), calorimetry and X-ray scattering. It is aimed to reveal in which way the pore size as well as the pore surface wettability (hydrophobic or hydrophilic) alters the molecular dynamics, and phase transition behavior for this system. These properties are crucial for applications. The DSC investigations reveal: (i) the phase transition temperature for the transition from the plastic crystalline to the crystalline-liquid state has non-monotonic dependence versus the inverse pore diameter and (ii) the transition from the liquid crystalline to the isotropic phase is suppressed for all nanoconfined samples. This transition suppressed in the thermal signal was evidenced by BDS and X-ray scattering. It is discussed as a continuous phase transition taking place in the pores instead of a discontinuous first order transition as observed for the bulk. BDS investigations show different relaxation processes for the bulk and the nanoconfined ILC. Molecular origins for various relaxation processes are discussed and suggested. It is further shown that the self-assembly of this ILC is dynamic in nature which might apply for other ILCs too. The obtained results will have implications for the nanoscale applications of ionic liquid crystals. KW - Ionic Liquid Crystals PY - 2023 DO - https://doi.org/10.1021/acsanm.3c02473 VL - 6 IS - 17 SP - 15673 EP - 15684 PB - ACS AN - OPUS4-58210 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mishmastnehi, M. A1 - Van Driessche, A. A1 - Smales, Glen Jacob A1 - Moya, A. A1 - Stawski, Tomasz T1 - Advanced materials engineering in historical gypsum plaster formulations N2 - We show how historical gypsum plaster preparation methods affect the microstructure and the wettability properties of the final stucco materials. We reproduced a traditional Persian recipe (Gach-e Koshteh, ~14th century AD), which involves a continuous mechanical treatment during plaster hydration. These samples were compared with a laboratory-replicated historical recipe from Renaissance Italy (Gesso Sottile, ~15th century AD) and contemporary low-strength plaster. The Koshteh recipe induces the formation of gypsum platelets, which exhibit preferential orientation in the plaster bulk. In contrast, the Italian and low-strength plasters comprise a typical needle-like morphology of gypsum crystals. The platelets in Koshteh expose the more hydrophilic {010} face of gypsum in a much more pronounced manner than needles. Consequently, the Iranian plaster displays enhanced wettability, enabling its direct use for water-based decoration purposes, or as a fine finishing thin layer, without the need of mixing it with a binder material. Contrary, in Sottile, gypsum crystals are left to equilibrate in large excess of water, which promotes the growth of long needles at the expense of smaller crystals. Typically, such needles are several times longer than those found in a control regular plaster. For this crystal habit, the total surface of hydrophilic faces is minimized. Consequently, such plaster layers tend to repel water, which can then be used, e.g., as a substrate for oilbased panel paintings. These findings highlight the development of advanced functional materials, by tuning their microtexture, already during the premodern era. KW - Gypsum KW - Calcium sulfate KW - Diffraction KW - Force microscopy PY - 2023 DO - https://doi.org/10.1073/pnas.2208836120  VL - 120 IS - 7 SP - 1 EP - 9 PB - National Academy of Sciences of the USA AN - OPUS4-57219 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 - 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 - Pallasch, Sebastian M. A1 - Bhosale, Manik A1 - Smales, Glen Jacob A1 - Schmidt, Caroline A1 - Riedel, Sibylle A1 - Zhao-Karger, Zhirong A1 - Esser, Birgit A1 - Dumele, Oliver T1 - Porous Azatruxene Covalent Organic Frameworks for Anion Insertion in Battery Cells N2 - Covalent organic frameworks (COFs) containing well-defined redox-active groups have become competitive materials for next-generation batteries. Although high potentials and rate performance can be expected, only a few examples of p-type COFs have been reported for charge storage to date with even fewer examples on the use of COFs in multivalent ion batteries. Herein, we report the synthesis of a p-type highly porous and crystalline azatruxene-based COF and its application as a positive electrode material in Li- and Mg-based batteries. When this material is used in Li-based half cells as a COF/carbon nanotube (CNT) electrode, a discharge potential of 3.9 V is obtained with discharge capacities of up to 70 mAh g−1 at a 2 C rate. In Mg batteries using a tetrakis(hexafluoroisopropyloxy)borate electrolyte, cycling proceeds with an averge discharge voltage of 2.9 V. Even at a fast current rate of 5 C, the capacity retention amounts to 84% over 1000 cycles. KW - COFs PY - 2024 DO - https://doi.org/10.1021/jacs.4c04044 VL - 146 IS - 25 SP - 17318 EP - 17324 PB - Journal of the American Chemical Society AN - OPUS4-60419 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kool, L. A1 - Dekker, F. A1 - Bunschoten, A. A1 - Smales, Glen Jacob A1 - Pauw, Brian Richard A1 - Velders, A. H. A1 - Saggiomo, V. T1 - Gold and silver dichroic nanocomposite in the quest for 3D printing the Lycurgus cup N2 - The Lycurgus cup is an ancient glass artefact that shows dichroism as it looks green when a white light is reflected on it and a red colouring appears when a white light is transmitted through it. This peculiar dichroic effect is due to silver and gold nanoparticles present in the glass. In this research we show the synthesis of dichroic silver nanoparticles and their embedding in a 3D printable nanocomposite. The addition of gold nanoparticles to the silver nanoparticle composite, gave a 3D printable nanocomposite with the same dichroism effect of the Lycurgus cup. KW - SAXS KW - Au KW - Ag KW - Nanocomposite KW - 3D printing PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-501831 DO - https://doi.org/10.3762/bjnano.11.2 SP - 16 EP - 23 AN - OPUS4-50183 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 - Wallau, Wilma A1 - Recknagel, Christoph A1 - Smales, Glen Jacob T1 - Structural silicone sealants after exposure to laboratory test for durability assessment N2 - During the service life of structural sealant glazing (SSG) facades, the loadbearing capacity of the silicone bonds needs to be guaranteed. Laboratory Tests can assess the durability of SSG-systems based on mechanical characteristics of the bond after simultaneous exposure to both climatic and mechanical loads. This article studies how the material characteristics of two common structural sealants are affected by laboratory and field exposure. Dynamic mechanical Analysis (DMA) confirms a reduction in the dynamic modulus of exposed Silicone samples. Results from thermogravimetric analysis, Fourier-transform infrared spectroscopy, differential scanning calorimetry, and small-angle X-ray scattering/wide-angle X-ray scattering show differences between the two sealants and indicate no/minor changes in the composition and morphology of the laboratory and field exposed sealants. Mechanical characterization methods, such as DMA, and tensile and shear testing of the structural bond, are shown to be sensitive toward the combined climatic and mechanical loadings, and are hence suitable for studying degradation mechanisms of structural sealants. KW - Aging KW - Analytical methods KW - Fatigue KW - Silicone elastomer KW - Structural sealant glazing PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-527217 DO - https://doi.org/10.1002/app.50881 VL - 138 IS - 35 SP - 50881 PB - Wiley AN - OPUS4-52721 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Smales, Glen Jacob T1 - Introduction to SAXS N2 - A simplified introductions to small-angle scattering (SAXS), to put across the main concepts and not get bogged down in equations. T2 - Better with Scattering workshop 2020 CY - BAM, Berlin, Germany DA - 16.03.2020 KW - SAXS KW - WAXS KW - MOFs KW - Data analysis KW - Nano PY - 2020 UR - https://www.youtube.com/watch?v=_YY9XtQfANk AN - OPUS4-51021 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Smales, Glen Jacob T1 - Following the formation of zeolites and MOFs in-situ N2 - Porous materials are of a great interest due to their ability to interact with ions and molecules not only on their surface but throughout their bulk. Porous materials are conventionally used in applications; such as ion exchange, adsorption/separation and in catalysis, exploiting the huge internal surface area of highly ordered porous materials. [1, 2] The ability for these materials to succeed, in a particular field, is dependent greatly upon the uniformity of the shape and size of the pores within the material. However, despite how well we are able to understand the stability of 3-D frameworks in crystalline or polycrystalline zeolites and ZIFs, there still remains major limitations in fully understanding the synthetic mechanisms occurring prior to their formation. [3, 4] Though the syntheses of a wide variety of porous solids are already well established, their formation mechanisms continue to be of great interest to both academic and industrial communities, with the thought that with greater understanding of the formation of these solids can lead to their rational design. By obtaining a better knowledge of the underlying nucleation mechanisms, it can allow for increased predictability of new structures and in addition can reveal valuable information regarding the particle dimensions aiding in controlling particle morphology and size. Small-angle and wide-angle X-ray scattering (SAXS/WAXS) are ideal techniques for determining morphological changes in-situ, where the shape, size and crystallinity can be followed at a high temporal resolution, and when these techniques are deployed alongside complimentary techniques, such as ex-situ microscopy, a great deal of information on the formation of materials can be obtained. The above-mentioned methodologies were utilised to study the formation of Silicalite-1 from multiple silica sources to obtain a detailed picture of the formation as a whole, including the formation of intermediate species (Image 1 show the in-situ SAXS data collected from the formation of Silicalite-1 from tetraethyl orthosilicate). In-situ SAXS/WAXS studies were also utilized to observe the formation of ZIF-8 alongside in-situ X-ray absorption spectroscopy (XAS) experiments to probe both the morphological changes, as well as any changes occurring to the local structure during synthesis (Image 2 show the in-situ SAXS data collected from the formation of ZIF-8). These timeresolved in-situ studies have been utilised to follow changes in crystallinity and crystallite size, whilst also providing valuable information on the formation of intermediate species, the nucleation of crystalline ZIFs, and their subsequent growth. References: [1] M E Davis. Nature, 417(6891):813–21, 2002 [2] S T Meek, J A Greathouse, M D Allendorf, Advanced Materials, 23 (2): 249-267, 2011 [3] J Grand, H Awala, CrystEngComm,18 (5): 650–664, 2016 [4] M J V Vleet, T Weng, X Li, J R Schmidt. Chem.Rev.,118 (7): 3681–3721, 2018 T2 - 8th Conference of the Federation of European Zeolite Associations (FEZA 2021) CY - Online meeting DA - 05.07.2021 KW - SAXS KW - Zeolites KW - MOFs KW - In situ PY - 2021 AN - OPUS4-53187 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Smales, Glen Jacob T1 - Structural characterization using small-angle X-ray scattering (SAXS) N2 - A short introduction to small-angle scattering, followed by a "choose your own adventure" style of talk on the characterisation of different materials using SAXS/WAXS. T2 - Operando workshop “SAXS and Ptychography” at the Paul Scherrer Institut CY - Villigen, Switzerland DA - 17.08.2021 KW - SAXS KW - Materials KW - Characterisation PY - 2021 AN - OPUS4-53188 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Pauw, Brian Richard A1 - Smales, Glen Jacob T1 - Complete set of raw and processed datasets, as well as associated Jupyter notebooks for analysis, associated with manuscript entitled: "The MOUSE project: a practical approach for obtaining traceable, wide-range X-ray scattering information" N2 - This dataset is a complete set of raw, processed and analyzed data, complete with Jupiter notebooks, associated with the manuscript mentioned in the title. In the manuscript, we provide a "systems architecture"-like overview and detailed discussions of the methodological and instrumental components that, together, comprise the "MOUSE" project (Methodology Optimization for Ultrafine Structure Exploration). Through this project, we aim to provide a comprehensive methodology for obtaining the highest quality X-ray scattering information (at small and wide angles) from measurements on materials science samples. KW - X-ray scattering KW - Measurement methodology KW - Traceability derivation KW - Multi-scale measurements KW - Systems architecture KW - Nanomaterials PY - 2020 DO - https://doi.org/10.5281/zenodo.4312953 PB - Zenodo CY - Geneva AN - OPUS4-51825 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Smales, Glen Jacob A1 - Pauw, Brian Richard T1 - The MOUSE project - A meticulous approach for obtaining traceable, wide-range X-ray scattering information N2 - Herein, we provide a "systems architecture"-like overview and detailed discussions of the methodological and instrumental components that, together, comprise the "MOUSE" project (Methodology Optimization for UltrafineStructure Exploration). The MOUSE project provides scattering information on a wide variety of samples, with traceable dimensions for both the scattering vector (q) and the absolute scattering cross-section (I). The measurable scattering vector-range of 0.012≤ q (nm-1) ≤ 92, allows information across a hierarchy of structures with dimensions ranging from ca. 0.1 to 400 nm. In addition to details that comprise the MOUSE project, such as the organisation and traceable aspects, several representative examples are provided to demonstrate its flexibility. These include measurements on alumina membranes, the tobacco mosaic virus, and dual-source information that overcomes fluorescence limitations on ZIF-8 and iron-oxide-containing carbon catalyst materials. KW - X-ray scattering KW - MOUSE KW - Instrumentation KW - SAXS KW - Methodology KW - Traceability KW - Wide-range KW - Data curation KW - FAIR KW - Uncertainties KW - Nanomaterials KW - Nanometrology PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-528669 DO - https://doi.org/10.1088/1748-0221/16/06/P06034 VL - 16 IS - 6 SP - 1 EP - 50 PB - IOP CY - Bristol, UK AN - OPUS4-52866 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Omar, Hassan A1 - Smales, Glen Jacob A1 - Henning, S. A1 - Li, Z. A1 - Wang, D.-Y. A1 - Schönhals, Andreas A1 - Szymoniak, Paulina T1 - Calorimetric and Dielectric Investigations of Epoxy-Based Nanocomposites with Halloysite Nanotubes as Nanofillers N2 - Epoxy nanocomposites are promising materials for industrial applications (i.e., aerospace, marine and automotive industry) due to their extraordinary mechanical and thermal properties. Here, the effect of hollow halloysite nanotubes (HNT) on an epoxy matrix (Ep) was the focus of the study. The structure and molecular mobility of the nanocomposites were investigated using a combination of X-ray scattering, calorimetry (differential (DSC) and fast scanning calorimetry (FSC)) and dielectric spectroscopy. Additionally, the effect of surface modification of HNT (polydopamine (PDA) and Fe(OH)3 nanodots) was considered. For Ep/HNT, the glass transition temperature (Tg) is was de-creased due to a nanoparticle-related decrease of the crosslinking density. For the modified system, Ep/m-HNT, the surface modification resulted in enhanced filler–matrix interactions leading to higher Tg values than the pure epoxy in some cases. For Ep/m-HNT, the amount of interface formed between the nanoparticles and the matrix ranged from 5% to 15%. Through BDS measurements, localized fluctuations were detected as a β- and γ-relaxation, related to rotational fluctuations of phenyl rings and local reorientations of unreacted components. A combination of calorimetry and BDS dielectric spectroscopy revealed a dynamic and structural heterogeneity of the matrix, as confirmed by two glassy dynamics in both systems, related to regions with different crosslinking densities. KW - Rigid amorphous fraction KW - Epoxy nanocomposites KW - Halloysite nanotubes KW - X-ray scattering KW - Differential scanning calorimetry KW - Broadband dielectric spectroscopy KW - Flash DSC PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-526668 DO - https://doi.org/10.3390/polym13101634 VL - 13 IS - 10 SP - 1634 PB - MDPI AN - OPUS4-52666 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kolmangadi, Mohamed Aejaz A1 - Szymoniak, Paulina A1 - Smales, Glen Jacob A1 - Alentiev, D. A1 - Bermeshev, M. A1 - Böhning, Martin A1 - Schönhals, Andreas T1 - Molecular Dynamics of Janus Polynorbornenes: Glass Transitions and Nanophase Separation N2 - For the first time, dielectric and calorimetric investigations of an homologous series of Janus polynorbornenes with rigid main backbones and flexible -Si(OR)3 side groups, of differing length alkyl chains (R = Propyl, Butyl, Hexyl, Octyl, Decyl) is reported. Generally, this class of polymers has some potential for applications in the field of gas separation membranes. Two dielectrically active processes are observed at low temperatures, denoted as β- and α- relaxation. The former can be assigned to localized fluctuations, whilst the latter is related to the glassy dynamics of the flexible -Si(OR)3 side groups, creating a nanophase separation in both the alkyl chain rich and backbone rich domains. This is confirmed through temperature modulated DSC measurements and X-ray scattering experiments. The glass transition temperatures of the backbone rich domains, which are beyond or near to their degradation temperatures in terms of conventional DSC, are determined for the first time using Fast Scanning Calorimetry employing both fast heating and cooling rates. This is complimented with scattering experiments that show how the size of the alkyl chain rich domains increases with chain length. Alongside these results, a significant conductivity contribution was observed for all poly(tricyclononenes) with -Si(OR)3 side groups, which is interpreted in terms of a percolation model. KW - Polynorbornenes KW - Broadband Dielectric Spectrscopy KW - Advanced calorimetry PY - 2020 DO - https://doi.org/10.1021/acs.macromol.0c01450 VL - 53 IS - 17 SP - 7410 EP - 7419 PB - ACS AN - OPUS4-51196 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kolmangadi, Mohamed Aejaz A1 - Szymoniak, Paulina A1 - Smales, Glen Jacob A1 - Bermeshev, M. A1 - Schönhals, Andreas A1 - Böhning, Martin T1 - Molecular mobility of polynorbornenes with trimethylsiloxysilyl side groups: Influence of the polymerization mechanism N2 - We report dielectric and calorimetric studies on metathesis and addition-type polytricyclononenes, both based on the same monomer bearing three pendant OSiMe3 groups. For the addition-type polymer, dielectric spectroscopy reveals a β*-process related to the microporosity, whereas for its metathesis counterpart, the segmental dynamics manifests as an α-process related to a glass transition. Besides active dielectric processes, a significant conductivity contribution is detected for both samples which for the microporous additiontype polymer is three orders of magnitude greater than for the metathesis polymer. The broadband dielectric spectroscopy is complemented by detailed calorimetric investigations, comprising DSC, FSC, and TMDSC. The calorimetric methods detected the glass transition for the metathesis polymer in agreement with the observed dielectric α-process. Furthermore, the already reported gas transport properties for both polymers are compared, setting them in correlation with the observed molecular mobility and conductivity behavior. The discussed results reflect significant differences in molecular mobility of the two polymers affecting the appearance of microporosity which strongly determines the gas transport properties. KW - Microporous polymers KW - Molecular mobility KW - Electrical conductivity KW - Membrane polymers KW - Gas separation PY - 2022 DO - https://doi.org/10.22079/JMSR.2021.538060.1495 SN - 2476-5406 VL - 8 IS - 3 SP - 1 EP - 9 PB - Membrane Processes Research Laboratory (MPRL) CY - Tehran AN - OPUS4-54303 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 - 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 - 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 - JOUR A1 - Hayward, E. C. A1 - Smales, Glen Jacob A1 - Pauw, Brian Richard A1 - Takeguchi, M. A1 - Kulak, A. A1 - Hunter, R. D. A1 - Schnepp, Z. T1 - The effect of catalyst precursors on the mechanism of iron-catalysed graphitization of cellulose N2 - Iron-catalysed graphitization of biomass is a simple and sustainable route to carbons with high graphitic content. It uses abundant precursors and moderate processing temperatures and generates carbons with high porosity. Recently, it has been demonstrated that the choice of biomass precursor can have a significant impact on the textural and compositional properties of the resulting carbon. In this paper, we demonstrate that the choice of catalyst is also critical to the carbon structure. Aqueous iron(III) nitrate and iron(III) chloride convert cellulose to carbons with very different textural properties. This is due to the choice of iron catalyst changing the mechanism of cellulose decomposition and also the nature of the active graphitization catalyst. KW - Catalyst KW - Carbon materials KW - Cellulose KW - Small-angle scattering KW - Green energy KW - Graphitic carbon KW - Green synthesis PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-614800 DO - https://doi.org/10.1039/D4SU00365A SP - 1 EP - 10 PB - Royal Society of Chemistry (RSC) AN - OPUS4-61480 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hallier, Dorothea C. A1 - Smales, Glen Jacob A1 - Seitz, H. A1 - Hahn, Marc Benjamin T1 - Bio-SAXS of single-stranded DNA-binding proteins: Radiation protection by the compatible solute ectoine N2 - Small-angle X-ray scattering (SAXS) can be used for structural determination of biological macromolecules and polymers in their native states (e.g. liquid phase). This means that the structural changes of (bio-)polymers, such as proteins and DNA, can be monitored in situ to understand their sensitivity to changes in chemical environments. In an attempt to improve the reliability of such experiments, the reduction of radiation damage occurring from exposure to X-rays is required. One such method, is to use scavenger molecules to protect macromolecules against radicals produced during radiation exposure, such as reactive oxygen species (ROS). In this study we investigate the feasibility of applying the compatible solute, osmolyte and radiation protector Ectoine (THP(B)), as a scavenger molecule during SAXS measurements of the single-stranded DNA-binding protein Gene-V Protein (G5P/GVP). In this case, we monitor the radiation induced changes of G5P during bio-SAXS measurments and the resulting microscopic energy-damage relation was determined from microdosimetric calculations by Monte-Carlo based particle scattering simulations with TOPAS/Geant4 and a custom target-model. This resulted in a median-lethal energy deposit of pure G5P at 4 mg mL−1 of E1/2 = 7 ± 5 eV, whereas a threefold increase of energy-deposit was needed under the presence of Ectoine to reach the same level of damage. This indicates that Ectoine increases the possible exposure time before radiation-damage to G5P is observed. Furthermore, the dominant type of damage shifted from aggregation in pure solutions towards a fragmentation for solutions containing Ectoine as a cosolute. These results are interpreted in terms of indirect radiation damage by reactive secondary species, as well as post-irradiation effects, related to preferential-exclusion of the cosolute from the protein surface. Hence, Ectoine is shown to provide a non-disturbing way to improve structure-determination of proteins via bio-SAXS in future studies. KW - BioSAXS KW - Bio-SAXS KW - Cosolute KW - Ectoine KW - G5P KW - GVP KW - Radiation damage KW - Radical Scavenger KW - Single-stranded DNA-binding proteins KW - X-ray scattering KW - DNA KW - ssDNA KW - Protein KW - SAXS KW - Small-angle xray scattering KW - McSAS3 KW - Dosimetry KW - Microdosimetry KW - Geant4 KW - Geant4-DNA KW - Topas KW - Topas-MC KW - Monte-Carlo simulations KW - Particle scattering simulations KW - Topas-nBio KW - OH Radical KW - OH radical scavenger KW - LEE KW - Ionizing radiation damage KW - Protein unfolding KW - Ectoin PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-568909 DO - https://doi.org/10.1039/d2cp05053f SN - 1463-9076 SN - 1463-9084 VL - 25 IS - 7 SP - 5372 EP - 5382 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-56890 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kolmangadi, Mohamed Aejaz A1 - Smales, Glen Jacob A1 - ZhuoQing, Li A1 - Yildirim, Arda A1 - Wuckert, E. A1 - Eutionnat, S. A1 - Demel, F. A1 - Huber, P A1 - Lasachat, S. A1 - Schönhals, Andreas T1 - Side Chain Length-Dependent Dynamics and Conductivity in Self-Assembled Ion N2 - We study the molecular mobility and electrical conductivity of a homologous series of linear shaped columnar ionic liquid crystals ILCn, (n = 8, 10, 12, 14, 16) using broadband dielectric spectroscopy (BDS), specific heat spectroscopy (SHS), and X-ray scattering. We aim to understand how the alkyl chain length influences the dynamics and electric conductivity in this system. Two dielectrically active relaxation modes are observed, the γ and the αcore process, that correspond to the localized fluctuations of the alkyl chains and cooperative motions of the aromatic core in the columns, respectively. Both the γ relaxation and the αcore process slow down with increasing alkyl chain length. SHS reveals one relaxation process, the αalkyl process that has a similar temperature dependence as that of the αcore process for ILC12, 14, and 16 but shifts to higher temperature for ILC8 and 10. For ILC12, 14, and 16, the absolute values of DC conductivity increase by 4 orders of magnitude at the transition from the plastic crystalline to hexagonal columnar phase. For ILC8 and 10, the DC conductivity behavior is similar to ionic liquids, where the conductivity is coupled with structural relaxation. Small-angle X-ray investigations reveal that both the intercolumnar distance and the disorder coherence length increase with alkyl chain length; conversely, the DC conductivity decreases monotonically. KW - Ionic Liquid Crystals PY - 2022 DO - https://doi.org/10.1021/acs.jpcc.2c03023 SN - 1932-7447 VL - 126 IS - 27 SP - 10995 EP - 11006 PB - ACS AN - OPUS4-55194 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hallier, Dorothea C. A1 - Smales, Glen Jacob A1 - Seitz, H. A1 - Hahn, Marc Benjamin T1 - Inside back cover for the article "Bio-SAXS of single-stranded DNA-binding proteins: Radiation protection by the compatible solute ectoine" N2 - Showcasing research from the Federal Institute for Material Research and Testing Berlin and Fraunhofer Institute for Celltherapy and Immunology Branch Bioanalytics and Bioprocesses Potsdam. Bio-SAXS of single-stranded DNA-binding proteins: Radiation protection by the compatible solute ectoine. We aimed to increase the possible undisturbed exposure time during bio-SAXS measurements of single-stranded DNA-binding proteins. Therefore small angle X-ray scattering was performed on Gene-V Protein (G5P/GVP), which is involved in DNA repair processes. To achieve this, irradiations were performed in presence and absence of the hydroxyl-radical scavenger and osmolyte Ectoine, which showed efficient radiation protection and prevented protein aggregation, thus allows for a non-disturbing way to improve structure-determination of biomolecules. KW - Bio-SAXS KW - BioSAXS KW - Cosolute KW - DNA KW - Dosimetry KW - Ectoin KW - Ectoine KW - G5P KW - GVP KW - Geant4 KW - Geant4-DNA KW - Ionizing radiation damage KW - LEE KW - McSAS3 KW - Microdosimetry KW - Monte-Carlo simulations KW - OH Radical KW - OH radical scavenger KW - Protein KW - Protein unfolding KW - Radiation damage KW - Radical Scavenger KW - SAXS KW - Single-stranded DNA-binding proteins KW - Small-angle xray scattering KW - Topas-MC KW - Topas-nBio KW - TopasMC KW - X-ray scattering KW - Particle scatterin simulations KW - ssDNA PY - 2023 DO - https://doi.org/10.1039/D3CP90056H SN - 1463-9076 SN - 1463-9084 VL - 25 IS - 7 SP - 5889 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-57006 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hunter, R. D. A1 - Hayward, E. C. A1 - Smales, Glen Jacob A1 - Pauw, Brian Richard A1 - Kulak, A. A1 - Guan, S. A1 - Schnepp, Z. T1 - The effect of nitrogen on the synthesis of porous carbons by iron-catalyzed graphitization N2 - This paper reports a systematic study into the effect of nitrogen on iron-catalyzed graphitization of biomass. Chitin, chitosan, N-acetylglucosamine, gelatin and glycine were selected to represent nitrogen-rich saccharides and amino-acid/polypeptide biomass precursors. The materials were pyrolyzed with an iron catalyst to produce carbons with a wide range of chemical and structural features such as mesoporosity and nitrogen-doping. Many authors have reported the synthesis of nitrogen-doped carbons by pyrolysis and these have diverse applications. However, this is the first systematic study of how nitrogen affects pyrolysis of biomass and importantly the catalytic graphitization step. Our data demonstrates that nitrogen inhibits graphitization but that some nitrogen survives the catalytic graphitization process to become incorporated into various chemical environments in the carbon product. KW - Graphitization KW - Nanoparticles KW - Nanocomposite KW - Porous carbon KW - Nitrogen KW - Scattering PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-575351 DO - https://doi.org/10.1039/d3ma00039g VL - 4 SP - 2070 EP - 2077 PB - Royal Society of Chemistry AN - OPUS4-57535 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Henning, L. M. A1 - Smales, Glen Jacob A1 - Colmenares, M. G. A1 - Bekheet, M. F. A1 - Simon, U. A1 - Gurlo, A. T1 - Synthesis and properties of COK-12 large-pore mesocellularsilica foam N2 - Large, ink-bottle-shaped pores in mesocellular foams (MCFs) are desired for various applications requiring enhanced mass transfer or the immobilization of larger compounds. Hence, the cylindrical pores of COK-12, an ordered mesoporous silica structurally comparable to SBA-15 but synthesized at room-temperature at quasi-neutral pH, are chemically swollen into ink-bottle pores. Therefore, p-xylene is used as a more sustainable swelling agent compared to popular alternatives. Its high boiling point allows for an additional thermal aging step to amplify the mesostructure enlargement without needing additional chemicals. For COK-12, the MCFs obtained at room temperature reach an unprecedented plateau for the modal mesopore cell and window diameter of 19.9 and 5.5 nm, respectively, with an underlying broad pore size distribution and distorted hexagonal lattice up to 14.5 nm, involving hexagonal and spherical structures. The combined chemical and thermal swelling resulted in the selective enlargement of the window diameter to more than 200% and a slightly increased cell diameter, pore size distribution, and hexagonal lattice distortion in comparison to the room temperature synthesis. Such materials are thought to be promising alternatives to SBA-15-based MCFs, often utilizing toxic catalysts during synthesis. The presented results pave the way for enhanced adsorptive, catalytic, and drug delivery performances for COK-12-based materials. KW - SAXS KW - MOUSE KW - Mesocellular foam KW - Mesoporous silica PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-569590 DO - https://doi.org/10.1002/nano.202200223 SP - 1 EP - 11 AN - OPUS4-56959 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Pauw, Brian Richard A1 - Smales, Glen Jacob T1 - Electric Safety Interlock N2 - This interlock is designed to prevent electrical shock from high voltage (>60V) equipment. While the general safety interlock can be generically applied, this particular example employs an external vacuum-activated switch. It is for safeguarding human operations inside a vacuum sample chamber while the chamber doors are open. The circuit is closed (output is active) when a sufficient level of vacuum is reached, i.e. when all accessible openings are necessarily closed. The initial application is to interrupt power to a 220V, 250W heating cartridge (itself mounted inside a small sample holder with potentially exposed contacts) when the sample chamber is open. The external circuit can be modified to use different interlock mechanisms as needed. Note that the external interlock circuit is only a single circuit (with two signal lines) and thus is not protected against external shorts. To accomodate a range of safety interlocks, the 4-pin M12 connector is wired as follows: Pin 1 (Brown): +24V for power supply, max current 0.6A Pin 2 (White): Safety interlock system signal 1 (0 or 24V) Pin 3 (Blue) : Safety interlock system signal 2 (0 or 24V) Pin 4 (Black): 0V for power supply The safety is interlocked (output active) when both signal pins are set high (24V), with sufficient current to activate the two relays. Pin 1 and 4 can be used to power safety hardware (such as light curtains or proximity detectors) with 24VDC up to a current of 0.6A. A larger power supply can be installed when higher currents are needed, while staying within the current limits imposed by the wiring cross-section. KW - Electric Safety Interlock KW - MOUSE KW - 60-230V PY - 2023 DO - https://doi.org/10.6084/m9.figshare.22265920.v1 PB - Digital Science CY - Cambridge, MA, USA AN - OPUS4-57138 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Smales, Glen Jacob A1 - Pauw, Brian Richard A1 - Kolmangadi, Mohamed Aejaz T1 - X-ray scattering datasets associated with the publication "Molecular Mobility of Polynorbornenes with Trimethylsiloxysilyl side groups: Influence of the Polymerization Mechanism" N2 - X-ray scattering datasets for samples described in the 2022 publication "Molecular Mobility of Polynorbornenes with Trimethylsiloxysilyl side groups: Influence of the Polymerization Mechanism". This dataset includes both raw and processed X-ray scattering data for samples APTCN and MPTCN, alongside background measurements files (BKG). KW - X-ray scattering KW - SAXS KW - MOUSE KW - Membrane polymers KW - Microporous polymers PY - 2023 DO - https://doi.org/10.5281/zenodo.7621204 PB - Zenodo CY - Geneva AN - OPUS4-56972 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Smales, Glen Jacob A1 - Pauw, Brian Richard A1 - Kolmangadi, Mohamed Aejaz T1 - X-ray scattering datasets associated with the publication "Side chain length dependent dynamics and conductivity in self assembled ion channels" N2 - X-ray scattering datasets for samples described in the 2022 publication "Side chain length dependent dynamics and conductivity in self assembled ion channels". This dataset includes both raw and processed X-ray scattering data for samples ILC8, ILC10, ILC12, ILC14 and ILC16 alongside background measurement files (BKG). KW - X-ray scattering KW - SAXS KW - MOUSE KW - Columnar ionic liquid crystals KW - Liquid crystals PY - 2023 DO - https://doi.org/10.5281/zenodo.7621358 PB - Zenodo CY - Geneva AN - OPUS4-56973 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Monroy, José del Refugio A1 - Deshpande, Tejas A1 - Schlecht, Joël A1 - Douglas, Clara A1 - Stirling, Robbie A1 - Grabicki, Niklas A1 - Smales, Glen Jacob A1 - Kochovski, Zdravko A1 - Fabozzi, Filippo Giovanni A1 - Hecht, Stefan A1 - Feldmann, Sascha A1 - Dumele, Oliver T1 - Homochiral versus racemic 2D covalent organic frameworks N2 - The synthesis of homochiral two-dimensional covalent organic frameworks (2D COFs) from chiral π-conjugated building blocks is challenging, as chiral units often lead to misaligned stacking interactions. In this work, we introduce helical chirality into 2D COFs using configurationally stable enantiopure and racemic [5]helicenes as linkers in the backbone of 2D [5]HeliCOFs as powders and films. Through condensation with 1,3,5-triformylbenzene (TFB) or 1,3,5-triformylphloroglucinol (TFP), our approach enables the efficient formation of a set of homochiral and racemic 2D [5]HeliCOFs. The resulting carbon-based crystalline and porous frameworks exhibit distinct structural features and different properties between homochiral and racemic counterparts. Propagation of helical chirality into the backbone of the crystalline frameworks leads to the observation of advanced chiroptical properties in the far-red visible spectrum, along with a less compact structure compared with the racemic frameworks. Homogeneous thin films of [5]HeliCOFs disclosed photoluminescent properties arising from the controlled growth of highly ordered π-conjugated lattices. The present study offers insight into general chiral framework formation and extends the Liebisch−Wallach rule to 2D COFs. KW - Chirality KW - Covalent organic frameworks KW - Diffraction KW - Lattices KW - Thin films PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-633755 DO - https://doi.org/10.1021/jacs.5c01004 SN - 0002-7863 VL - 147 IS - 21 SP - 17750 EP - 17763 PB - American Chemical Society (ACS) CY - Washington, DC AN - OPUS4-63375 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 - GEN A1 - Pauw, Brian Richard A1 - Smales, Glen Jacob T1 - Small-angle scattering data analysis round robin dataset - Original for participants N2 - These are four datasets that were made available to the participants of the Small-angle Scattering data analysis round robin. The intent was to find out how comparable results from different researchers are, who analyse exactly the same processed, corrected dataset. In this repository, there are: 1) a PDF document with more details for the study, 2) the datasets for people to try and fit, 3) an Excel spreadsheet to document the results. Datasets 1 and 2 were modified from: Deumer, Jerome, & Gollwitzer, Christian. (2022). npSize_SAXS_data_PTB (Version 5) [Data set]. Zenodo. https://doi.org/10.5281/zenodo.5886834 Datasets 3 and 4 were collected in-house on the MOUSE instrument. KW - Round robin KW - SAXS KW - Small angle scattering KW - SANS KW - X-ray KW - Neutron KW - Human factor KW - Data analysis KW - Data fitting KW - Human influence PY - 2023 DO - https://doi.org/10.5281/zenodo.7506365 PB - Zenodo CY - Geneva AN - OPUS4-56799 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Pauw, Brian Richard A1 - Smales, Glen Jacob T1 - X-ray scattering Datasets of gold and silver nanoparticle composites, relating to the publication "Gold and silver dichroic nanocomposite in the quest for 3D printing the Lycurgus cup" N2 - Wide-range X-ray scattering datasets and analyses for all samples described in the 2020 publication "Gold and silver dichroic nanocomposite in the quest for 3D printing the Lycurgus cup". These datasets are composed by combining multiple small-angle x-ray scattering and wide-angle x-ray scattering curves into a single dataset. They have been analyzed using McSAS to extract polydispersities and volume fractions. They have been collected using the MOUSE project (instrument and methodology). KW - X-ray scattering KW - MOUSE KW - Saxs KW - Waxs KW - Analyses KW - Datasets PY - 2022 DO - https://doi.org/10.5281/zenodo.7193859 PB - Zenodo CY - Geneva AN - OPUS4-55979 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Smales, Glen Jacob A1 - Pauw, Brian Richard T1 - Technical Drawings for The MOUSE Modular Sample Holder: Capillary Flow-through Cell N2 - OpenSCAD, STL and technical drawings for the capillary flow-through cell designed primarily for use with The MOUSE instruments. This flow-through cell can be used in conjunction with: - Modular sample holder (10.5281/zenodo.7499416) - Solid sample rack/plate (10.5281/zenodo.7499424) - Laser-cut sample holder (10.5281/zenodo.7499437) KW - X-ray scattering KW - SAXS KW - Sample holder KW - MOUSE PY - 2023 DO - https://doi.org/10.5281/zenodo.7499421 PB - Zenodo CY - Geneva AN - OPUS4-56776 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Smales, Glen Jacob A1 - Pauw, Brian Richard T1 - Technical Drawings for The MOUSE Modular Sample Holder: Solid Sample Rack/Plate N2 - OpenSCAD, STL and technical drawings for the solid sample rack designed primarily for use with The MOUSE instruments. This solid sample rack can be used in conjunction with: - Laser-cut sample holder (10.5281/zenodo.7499437) - Modular sample holder (10.5281/zenodo.7499416) - Capillary flow-cell for liquid samples (10.5281/zenodo.7499421) KW - X-ray scattering KW - SAXS KW - Sample holder KW - MOUSE PY - 2023 DO - https://doi.org/10.5281/zenodo.7499424 PB - Zenodo CY - Geneva AN - OPUS4-56778 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Smales, Glen Jacob A1 - Pauw, Brian Richard T1 - Technical Drawings for The MOUSE Modular Sample Holder: Laser-cut Sample Holder N2 - PDF file for the laser-cut sample holder designed primarily for use with The MOUSE instruments. This sample holder can be used in conjunction with: - Solid sample rack/plate (10.5281/zenodo.7499424) - Modular sample holder (10.5281/zenodo.7499416) - Capillary flow-cell for liquid samples (10.5281/zenodo.7499421) KW - X-ray scattering KW - SAXS KW - Sample holder KW - MOUSE PY - 2023 DO - https://doi.org/10.5281/zenodo.7499437 PB - Zenodo CY - Geneva AN - OPUS4-56779 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Smales, Glen Jacob A1 - Hahn, Marc Benjamin A1 - Hallier, Dorothea C. A1 - Seitz, H. T1 - X-ray scattering datasets and simulations associated with the publication "Bio-SAXS of single-stranded DNA-binding proteins: Radiation protection by the compatible solute ectoine" N2 - This dataset contains the processed and analysed small-angle X-ray scattering data associated with all samples from the publications "Bio-SAXS of Single-Stranded DNA-Binding Proteins: Radiation Protection by the Compatible Solute Ectoine" (https://doi.org/10.1039/D2CP05053F). Files associated with McSAS3 analyses are included, alongside the relevant SAXS data, with datasets labelled in accordance to the protein (G5P), its concentration (1, 2 or 4 mg/mL), and if Ectoine is present (Ect) or absent (Pure). PEPSIsaxs simulations of the GVP monomer (PDB structure: 1GV5 ) and dimer are also included. TOPAS-bioSAXS-dosimetry extension for TOPAS-nBio based particle scattering simulations can be obtained from https://github.com/MarcBHahn/TOPAS-bioSAXS-dosimetry which is further described in https://doi.org/10.26272/opus4-55751. This work was funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under grant number 442240902 (HA 8528/2-1 and SE 2999/2-1). We acknowledge Diamond Light Source for time on Beamline B21 under Proposal SM29806. This work has been supported by iNEXT-Discovery, grant number 871037, funded by the Horizon 2020 program of the European Commission. KW - SAXS KW - Radiation protection KW - Microdosimetry KW - G5P KW - Ectoine KW - DNA-Binding protein PY - 2023 DO - https://doi.org/10.5281/zenodo.7515394 PB - Zenodo CY - Geneva AN - OPUS4-56811 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Pauw, Brian Richard A1 - Röder, Bettina A1 - Smales, Glen Jacob T1 - High temperature in-vacuum flow-through sample holder (sandwich design version 1.1) N2 - Technical drawings and documents for building a compact, heated, vacuum compatible flow-through sample holder. This holder is in use at the BAM MOUSE instrument as well as at the I22 beamline at the Diamond Light Source (see references for instrument details). This holder has several features: - The holder can be used in vacuum environments as well as in atmosphere - It has two G 1/4" UNF fittings to attach HPLC tubing for (optionally) flowing a medium through the sample cell - There are two additional (unflowed) sample positions for backgrounds and calibrants, held at the same temperature - The low-mass design coupled with a 250W heating element can achieve heating rates of 1 degree C per second, when coupled (for example) with an Omron E5CC PID controller. - The sample holder insert can be made from various materials depending on the application. Sealing the sample from the vacuum can be achieved using kapton, teflon or Magic tape, depending on the temperature requirements. The inlet and outlet holes will need to be punctured with a needle to enable flow. - Large exit cones ensure a clear exit angle of at least 45 degrees two theta. - It has been tested with temperatures up to 400 degrees C. - Compression area has been raised and polished to ensure a good vacuum seal. KW - SAXS KW - X-ray scattering KW - Sample cell KW - Sample holder KW - Heated KW - Flow-through KW - Vacuum compatible KW - XRD KW - WAXS PY - 2023 DO - https://doi.org/10.5281/zenodo.7501030 PB - Zenodo CY - Geneva AN - OPUS4-56777 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Smales, Glen Jacob A1 - Pauw, Brian Richard A1 - Kolmangadi, Mohamed Aejaz T1 - X-ray scattering datasets associated with the publication "Molecular Dynamics of Janus Polynorbornenes: Glass Transitions and Nanophase Separation" N2 - X-ray scattering datasets for samples described in the 2020 publication "Molecular Dynamics of Janus Polynorbornenes: Glass Transitions and Nanophase Separation". This dataset includes both raw and processed X-ray scattering data for samples PTCHSiO-Pr, Bu, Hx, Oc and De, alongside background measurements files (BKG). This data was collected using the MOUSE project (instrument and methodology). KW - X-ray scattering KW - SAXS KW - MOUSE KW - Alkyls KW - Polymers PY - 2023 DO - https://doi.org/10.5281/zenodo.7614835 PB - Zenodo CY - Geneva AN - OPUS4-56971 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 - GEN A1 - Pauw, Brian Richard A1 - Smales, Glen Jacob A1 - Rosalie, Julian T1 - Small-angle scattering data analysis round robin - Anonymized results, figures and Jupyter notebook N2 - The intent of this round robin was to find out how comparable results from different researchers are, who analyse exactly the same processed, corrected dataset. This zip file contains the anonymized results and the jupyter notebook used to do the data processing, analysis and visualisation. Additionally, TEM images of the samples are included. KW - Round robin KW - Small-angle scattering KW - Data analysis PY - 2023 DO - https://doi.org/10.5281/zenodo.7509710 PB - Zenodo CY - Geneva AN - OPUS4-56803 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 - CONF A1 - Smales, Glen Jacob T1 - THE MAUS: A GI-/ULTRA-/W/SAXS Instrument of the future N2 - The Multi-scale Analyzer for Ultrafine Structures or the “MAUS” for short, is a SAXS instrument that combines a multitude of features that make it both unique, and one of the most adaptable instruments around. T2 - SAS2018 CY - Traverse City, MI, USA DA - 07.10.2018 KW - SAXS KW - MAUS KW - Small-angle scattering KW - DAWN KW - Grazing incidence PY - 2018 AN - OPUS4-46523 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hahn, Marc Benjamin A1 - Smales, Glen Jacob A1 - Seitz, H. A1 - Solomun, Tihomir A1 - Sturm, Heinz T1 - Ectoine interaction with DNA: Influence on ultraviolet radiation damage N2 - Ectoine is a small zwitterionic osmolyte and compatible solute, which does not interfere with cell metabolism even at molar concentrations. Plasmid DNA (pUC19) was irradiated with ultraviolet radiation (UV-C at 266 nm) under quasi physiological conditions (PBS) and in pure water in the presence and absence of ectoine (THP(B)) and hydroxyectoine (THP(A)). Different types of UV induced DNA damage were analysed: DNA single-strand breaks (SSBs), abasic sites and cyclobutane pyrimidine dimers (CPDs). A complex interplay between these factors was observed with respect to the nature and occurrence of DNA damage with 266 nm photons. In PBS, the cosolutes showed efficient protection against base damage, whilst in pure water, a dramatic shift from SSB damage to base damage was observed when cosolutes were added. To test whether these effects are caused by ectoine binding to DNA, further experiments were conducted: small-angle X-ray scattering (SAXS), surface-plasmon resonance (SPR) measurements and Raman spectroscopy. The results show, for the first time, a close interaction between ectoine and DNA. This is in stark contrast to the assumption made by preferential exclusion models, which are often used to interpret the behaviour of compatible solutes within cells and with biomolecules. It is tentatively proposed that the alterations of UV damage to DNA are attributed to ectoine influence on nucleobases through the direct interaction between ectoine and DNA. KW - Ectoine KW - DNA KW - Radiation damage KW - Radiation protection KW - SSB KW - DNA damage KW - DNA protection KW - Compatible solute KW - Zwitterion KW - Hydroxyectoine KW - Salt KW - PBS KW - UV absorption KW - DNA strand-break KW - DNA base damage KW - Ectoine UV absorption KW - Ectoine DNA protection KW - Excited states KW - UV irradiation KW - UV-A KW - UV-B KW - UV-C KW - 266nm KW - UV photons KW - Ectoine-DNA binding KW - Raman spectroscopy KW - UV-Vis KW - Radical scavenger KW - OH scavenger KW - Hydroxyl radicals KW - CPD KW - Abasic site KW - Agarose gel electrophorese KW - SYBR gold KW - DNA melting temperature KW - Counterions KW - Preferential exclusion KW - Cancer KW - Therapy KW - UV protection KW - Sunscreen PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-505772 DO - https://doi.org/10.1039/d0cp00092b SN - 1463-9076 SN - 1463-9084 VL - 22 IS - 13 SP - 6984 EP - 6992 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-50577 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Pauw, Brian Richard A1 - Smales, Glen Jacob T1 - Raw and processed X-ray scattering datasets for: "Entering a new dimension in powder processing for advanced ceramics shaping" N2 - This dataset is a complete set of raw, processed and analyzed data, associated with the manuscript mentioned in the title. All associated metadata and processing history has been added. Particle size distribution analyses using McSAS are included as well. The samples consisted of a 4.2 mass% dispersion of yttria-stabilized zirconia nanoparticles in a cross-linked matrix. The measurements show a good dispersion with minimal agglomeration. The wide-angle region shows diffraction information consistent with zirconia. KW - X-ray scattering KW - Nanocomposite KW - Ceramic microprinting KW - Yttria-stabilized zirconia KW - SAXS KW - Nanomaterials KW - Two-photon polymerization KW - Transparency KW - Mechanical testing PY - 2023 DO - https://doi.org/10.5281/zenodo.7498647 PB - Zenodo CY - Geneva AN - OPUS4-56766 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Cano Murillo, Natalia A1 - Szymoniak, Paulina A1 - Smales, Glen Jacob A1 - Sturm, Heinz A1 - Schönhals, Andreas T1 - Electrospun nanocomposites fibers of polycarbonate and taurine modified boehmite nanoparticles - What can be learned from structural and thermal investigations N2 - Though the reinforcing properties of inorganic particles in thermosetting nanocomposites, has been exploited, the integration of nanoparticles continues to be challenging in terms of their homogeneous distribution and their manipulation which can contribute to occupational hazards. Due to a second encapsulations of nanoparticles, electrospun nanocomposite fibers containing nanoparticles might be an alternative for overcoming these issues, as the fiber nonwovens contains the nanoparticles allowing for safer manipulation. Here, the morphology, and the thermal properties of electrospun polycarbonate fibers containing taurine modified boehmite nanoparticles (BNP) are investigated by means of small and wide-angle X-ray scattering as well as fast scanning and temperature modulated fast scanning calorimetry for the first time. The latter techniques allow the investigation of the thermal properties of single fibers at heating rates up to 10^4 K s^-1 keeping its structure intact. A quantitative analysis of the scattering data reveals a porous structure of the fibers. The porous structure is quantified regarding the pore volume and the pore size. A constant amount of aggregation is found even for the highly BNP loaded fibers. Thermal analysis on the fibers reveals a rigid amorphous fraction (RAF) where it is known that RAF determinates the properties of a nanocomposite to a large extent. For the fibers RAF amounts up to 40 wt%, which is essential higher compared to equally formulated PC/BNP composite cast films. The RAF in the case of the fibers, is not only due to the presence of particles in the polymer but also due to orientation effects induced by the electrospinning process. KW - Nanocomposite fibers KW - Electrospinning KW - X-ray scattering KW - Fast scanning calorimetry KW - Rigid amorphous fraction PY - 2021 DO - https://doi.org/10.1021/acsapm.1c01265 VL - 3 IS - 12 SP - 6572 EP - 6585 PB - ACS AN - OPUS4-53871 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Elert, Anna Maria A1 - Chen, Yong-Cin A1 - Smales, Glen Jacob A1 - Topolniak, Ievgeniia A1 - Sturm, Heinz A1 - Schönhals, Andreas A1 - Szymoniak, Paulina T1 - Effects of the charge density of nanopapers based on carboxymethylated cellulose nanofibrils investigated by complementary techniques N2 - Cellulose nanofibrils (CNFs) with different charge densities were prepared and investigated by a combination of different complementary techniques sensitive to the structure and molecular dynamics of the system. The morphology of the materials was investigated by scanning electron microscopy (SEM) and X-ray scattering (SAXS/WAXS). The latter measurements were quantitatively analyzed yielding to molecular parameters in dependence of the charge density like the diameter of the fibrils, the distance between the fibrils, and the dimension of bundles of nanofibrils, including pores. The influence of water on the properties and the charge density is studied by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and broadband dielectric spectroscopy. The TGA measurements reveal two mass loss processes. The one at lower temperatures was related to the loss of water, and the second process at higher temperatures was related to the chemical decomposition. The resulting char yield could be correlated to the distance between the microfibrils. The DSC investigation for hydrated CNFs revealed three glass transitions due to the cellulose segments surrounded by water molecules in different states. In the second heating scan, only one broad glass transition is observed. The dielectric spectra reveal two relaxation processes. At low temperatures or higher frequencies, the β-relaxation is observed, which is assigned to localized fluctuation of the glycosidic linkage. At higher temperatures and lower frequencies, the α-relaxation takes places. This relaxation is due to cooperative fluctuations in the cellulose segments. Both processes were quantitatively analyzed. The obtained parameters such as the relaxation rates were related to both the morphological data, the charge density, and the content of water for the first time. KW - Cellulose nanofibrils PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-600528 DO - https://doi.org/https://doi.org/10.1021/acsomega.4c00255 SN - 2470-1343 VL - 9 SP - 20152 EP - 20166 PB - ACS AN - OPUS4-60052 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Yildirim, Arda A1 - Sentker, K. A1 - Smales, Glen Jacob A1 - Pauw, Brian Richard A1 - Huber, P. A1 - Schönhals, Andreas T1 - Collective orientational order and phase behavior of a discotic liquid crystal under nanoscale confinement N2 - The phase behavior and molecular ordering of hexakishexyloxy triphenylene (HAT6) DLC under cylindrical nanoconfinement is studied utilizing differential scanning calorimetry (DSC) and dielectric spectroscopy (DS), where cylindrical nanoconfinement is established through embedding HAT6 into the nanopores of anodic aluminum oxide membranes (AAO), and a silica membrane with pore diameters ranging from 161 nm down to 12 nm. Both unmodified and modified pore walls were considered, and in the latter case the pore walls of AAO membranes were chemical treated with n octadecylphosphonic acid (ODPA) resulting in the formation of a 2.2 nm thick layer of grafted alkyl chains. Phase transition enthalpies decrease with decreasing pore size, indicating that a large proportion of the HAT6 molecules within the pores has a disordered structure, which increases with decreasing pore size for both pore walls. In the case of the ODPA modification the amount of ordered HAT6 is increased compared to the unmodified case. The pore size dependencies of the phase transition temperatures were approximated using the Gibbs Thomson equation, where the estimated surface tension is dependent on the molecular ordering of HAT6 molecules within the pores and upon their surface. DS was employed to investigate the molecular ordering of HAT6 within the nanopores. These investigations revealed that with a pore size of around 38 nm, for the samples with the unmodified pore walls, the molecular ordering changes from planar axial to homeotropic radial. However, the planar axial configuration, which is suitable for electronic applications, can be successfully preserved through ODPA modification for most of the pore sizes. KW - Discotic Liquid Crystals KW - Nanoconfinement PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-475222 DO - https://doi.org/10.1039/c8na00308d SN - 2516-0230 VL - 1 IS - 3 SP - 1104 EP - 1116 PB - RSC AN - OPUS4-47522 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 - 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 -