TY - JOUR A1 - Leng, Jing A1 - Purohit, Purv A1 - Kang, N. A1 - Wang, D.-Y. A1 - Falkenhagen, Jana A1 - Emmerling, Franziska A1 - Thünemann, Andreas A1 - Schönhals, Andreas T1 - Structure-property relationships of nanocomposites based on polylactide and MgAl layered double hydroxides N2 - Nanocomposites based on poly(ʟ-lactide) (PLA) and organically modified MgAl Layered Double Hydroxides (MgAl-LDH) were prepared by melt blending and investigated by a combination of Differential Scanning Calorimetry (DSC), Small- and Wide-Angle X-ray Scattering (SAXS, WAXS), and dielectric spectroscopy (BDS). Scanning microfocus SAXS investigations show that the MgAl-LDH is homogeneously distributed in the matrix as stacks of 6 layers and/or partly exfoliated layers. DSC and WAXS show that the degree of crystallinity decreases linearly with the content of LDH. The extrapolation of the dependencies (DSC and WAXS) to zero estimates a limiting concentration of LDH CCri of ca. 21 wt% where the crystallization of PLA is completely suppressed by the nanofiller. The dielectric behavior of neat PLA show two relaxation regions, a β-relaxation at low temperatures related to localized fluctuations and the α-relaxation at higher temperatures due to the dynamic glass transition. The dielectric spectra of the nanocomposites show several additional relaxation processes compared to neat PLA which are discussed in detail. For the nanocomposites around 260 K (ƒ = 1 kHz) an additional process is observed which intensity increases with increasing concentration of LDH. This process is mainly attributed to the exchanged dodecylbenzene sulfonate (SDBS) molecules which are adsorbed at the LDH layers and form a mixed phase with the polymer close to the layers and stacks. An analysis of this process provides information about the molecular dynamics in the interfacial region between the LDH layers and the PLA matrix which reveal glassy dynamics in this region. In the temperature range around 310 K (ƒ = 1 kHz) a further process is observed. Its relaxation rate has an unusual saddle-like temperature dependence. It was assigned to rotational fluctuations of water molecules in a nanoporous environment provided by the LDH filler. Above the glass transition temperature a further process is observed at temperatures above. It is related to Maxwell/Wagner/Sillars polarization due to the blocking of charges at the nanofiller. KW - Polymer based nanocomposites KW - Polylactide KW - Layered double hydroxides KW - Dielectric spectroscopy PY - 2015 DO - https://doi.org/10.1016/j.eurpolymj.2015.05.008 SN - 0014-3057 SN - 1873-1945 VL - 68 SP - 338 EP - 354 PB - Elsevier CY - Oxford AN - OPUS4-33257 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Linberg, Kevin A1 - Ali, Naveed Zafar A1 - Etter, M. A1 - Michalchuk, Adam A1 - Rademann, K. A1 - Emmerling, Franziska T1 - A Comparative Study of the Ionic Cocrystals NaX (α-d-Glucose)2 (X = Cl, Br, I) N2 - The mechanochemical formation of the ionic cocrystals of glucose (Glc) and sodium salts Glc2NaCl·H2O (1) and Glc2NaX (X = Br (2), I (3)) is presented. Products are formed by co-milling Glc with three sodium salts (NaCl, NaBr, NaI). The ionic cocrystals were obtained under both neat grinding and liquid-assisted grinding conditions, the later found to accelerate the reaction kinetics. The crystal structures of the ionic cocrystals (2) and (3) were solved from powder X-ray diffraction data. The structure solution contrasts with the structure of Glc2NaCl·H2O (1) where the electron density at three halide crystallographic sites is modeled as of being the intermediate between water molecule and a chloride ion. The reaction pathways of the three ionic cocrystals were investigated in real time using our tandem approach comprising a combination of in situ synchrotron powder X-ray diffraction and Raman spectroscopy. The results indicate the rapid formation of each cocrystal directly from their respective starting materials without any intermediate moiety formation. The products were further characterized by DTA-TG and elemental analysis. KW - In situ KW - Co-crystal KW - Mechanochemistry KW - Glucose PY - 2019 DO - https://doi.org/10.1021/acs.cgd.8b01929 VL - 19 IS - 8 SP - 4293 EP - 4299 PB - ACS Publications AN - OPUS4-48781 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Linberg, Kevin A1 - Emmerling, Franziska A1 - Michalchuk, Adam T1 - Unintended Rate Enhancement in Mechanochemical Kinetics by Using Poly(methyl methacrylate) Jars N2 - Time-resolved in situ (TRIS) X-ray diffraction has changed how mechanochemical transformations are studied but requires the use of X-ray transparent jars often made from poly(methyl methacrylate) (PMMA). However, using PMMA jars can alter the apparent kinetics of mechanochemical polymorphism by an order of magnitude, questioning the interpretability of established TRIS methods. Our results suggest that rate enhancement in PMMA jars may not be dominated by chemical effects of the polymer, but rather a result of different equilibrium temperatures within the jar. These features must be better understood before control over mechanochemical reactions can be achieved. KW - Mechanochemistry KW - Organic compounds KW - Polymers KW - Materials PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-565276 DO - https://doi.org/10.1021/acs.cgd.2c01227 SN - 1528-7483 SP - 1 EP - 5 PB - ACS Publications AN - OPUS4-56527 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Linberg, Kevin A1 - Röder, Bettina A1 - Al-Sabbagh, Dominik A1 - Emmerling, Franziska A1 - Michalchuk, Adam T1 - Controlling polymorphism in molecular cocrystals by variable temperature ball milling N2 - Mechanochemistry offers a unique opportunity to modify and manipulate crystal forms, often providing new products as compared with conventional solution methods. While promising, there is little known about how to control the solid form through mechanochemical means, demanding dedicated investigations. Using a model organic cocrystal system (isonicotinamide:glutaric acid), we here demonstrate that with mechanochemistry, polymorphism can be induced in molecular solids under conditions seemingly different to their conventional thermodynamic (thermal) transition point. Whereas Form II converts to Form I upon heating to 363 K, the same transition can be initiated under ball milling conditions at markedly lower temperatures (348 K). Our results indicate that mechanochemical techniques can help to reduce the energy barriers to solid form transitions, offering new insights into controlling polymorphic forms. Moreover, our results suggest that the nature of mechanochemical transformations could make it difficult to interpret mechanochemical solid form landscapes using conventional equilibrium-based tools. KW - Mechanochemistry KW - Kinetics KW - In situ PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-558878 DO - https://doi.org/10.1039/d2fd00115b SP - 1 EP - 16 PB - Royal Society of Chemistry AN - OPUS4-55887 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Linberg, Kevin A1 - Röder, Bettina A1 - Al-Sabbagh, Dominik A1 - Emmerling, Franziska A1 - Michalchuk, Adam T1 - Controlling polymorphism in molecular cocrystals by variable temperature ball milling N2 - Mechanochemistry offers a unique opportunity to modify and manipulate crystal forms, often providing new products as compared with conventional solution methods. While promising, there is little known about how to control the solid form through mechanochemical means, demanding dedicated investigations. Using a model organic cocrystal system (isonicotinamide:glutaric acid), we here demonstrate that with mechanochemistry, polymorphism can be induced in molecular solids under conditions seemingly different to their conventional thermodynamic (thermal) transition point. Whereas Form II converts to Form I upon heating to 363 K, the same transition can be initiated under ball milling conditions at markedly lower temperatures (348 K). Our results indicate that mechanochemical techniques can help to reduce the energy barriers to solid form transitions, offering new insights into controlling polymorphic forms. Moreover, our results suggest that the nature of mechanochemical transformations could make it difficult to interpret mechanochemical solid form landscapes using conventional equilibrium-based tools. KW - Mechanochemistry KW - Polymorphism KW - TRIS PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-564728 DO - https://doi.org/10.1039/d2fd00115b SP - 1 EP - 16 PB - Royal Society of Chemistry AN - OPUS4-56472 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Linberg, Kevin A1 - Szymoniak, Paulina A1 - Schönhals, Andreas A1 - Emmerling, Franziska A1 - Michalchuk, Adam T1 - The Origin of Delayed Polymorphism in Molecular Crystals Under Mechanochemical Conditions N2 - We show that mechanochemically driven polymorphic transformations can require extremely long induction periods, which can be tuned from hours to days by changing ball milling energy. The robust design and interpretation of ball milling experiments must account for this unexpected kinetics that arises from energetic phenomena unique to the solid state. Detailed thermal analysis, combined with DFT simulations, indicates that these marked induction periods are associated with processes of mechanical activation. Correspondingly, we show that the pre‐activation of reagents can also lead to marked changes in the length of induction periods. Our findings demonstrate a new dimension for exerting control over polymorphic transformations in organic crystals. We expect mechanical activation to have a much broader implication across organic solid‐state mechanochemistry. KW - General Chemistry KW - Catalysis KW - Organic Chemistry PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-589219 DO - https://doi.org/10.1002/chem.202302150 SN - 0947-6539 SP - e202302150 PB - Wiley AN - OPUS4-58921 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Liu, X. A1 - Michalchuk, Adam A1 - Bhattacharya, Biswajit A1 - Emmerling, Franziska A1 - Pulham, C. T1 - High-pressure reversibility in a plastically flexible coordination polymer crystal N2 - Single crystals which exhibit mechanical flexibility are promising materials for advanced technological applications. Before such materials can be used, a detailed understanding of the mechanisms of bending is needed. Using single crystal X-ray diffraction and microfocus Raman spectroscopy, we study in atomic detail the high-pressure response of the plastically flexible coordination polymer [Zn(μ-Cl)2(3,5-dichloropyridine)2]n (1). Contradictory to three-point bending, quasi-hydrostatic compression of (1) is completely reversible, even following compression to over 9 GPa. A structural phase transition is observed at ca. 5 GPa. DFT calculations show this transition to result from the pressure-induced softening of low-frequency vibrations. This phase transition is not observed during three-point-bending. Microfocus synchrotron X-ray diffraction revealed that bending yields significant mosaicity, as opposed to compression. Hence, our studies indicate of overall disparate mechanical responses of bulk flexibility and quasi-hydrostatic compression within the same crystal lattice. We suspect this to be a general feature of plastically bendable materials. KW - High pressure KW - Density functional theory KW - Mechanically flexible crystals PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-530360 DO - https://doi.org/10.1038/s41467-021-24165-x VL - 12 IS - 1 SP - 3871 AN - OPUS4-53036 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Liu, Yanchen A1 - de Oliveira Guilherme Buzanich, Ana A1 - Montoro, Luciano A. A1 - Liu, Hao A1 - Liu, Ye A1 - Emmerling, Franziska A1 - Russo, Patrícia A. A1 - Pinna, Nicola T1 - A partially disordered crystallographic shear block structure as fast-charging negative electrode material for lithium-ion batteries N2 - A well-ordered crystalline structure is crucial in battery electrodes, as the dimensionality and connectivity of the interstitial sites inherently influence Li+ ions diffusion kinetics. Niobium tungsten oxides block structures, composed of ReO3-type blocks of specific sizes with well-defined metal sites, are promising fast-charging negative electrode materials. Structural disorder is generally detrimental to conductivity or ion transport. However, here, we report an anomalous partially disordered Nb12WO33 structure that significantly enhances Li-ion storage performance compared to the known monoclinic Nb12WO33 phase. The partially disordered phase consists of corner-shared NbO6 octahedra blocks of varied sizes, including 5×4, 4×4, and 4×3, with a disordered arrangement of distorted WO4 tetrahedra at the corners of the blocks. This structural arrangement is robust during lithiation/delithiation, exhibiting minor local structure changes during cycling. It enables accelerated Li-ion migration, resulting in promising fast-charging performance, namely, 62.5 % and 44.7 % capacity retention at 20 C and 80 C, respectively. This study highlights the benefits of introducing disorder into niobium tungsten oxide shear structures, through the establishment of clear structure-performance correlations, offering guidelines for designing materials with targeted properties. KW - Lithium ion batteries KW - Oxides KW - XANES KW - XRD PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-637994 DO - https://doi.org/10.1038/s41467-025-61646-9 SN - 2041-1723 VL - 16 IS - 1 SP - 1 EP - 15 PB - Springer Science and Business Media LLC AN - OPUS4-63799 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Loges, A. A1 - Scholz, G. A1 - de Sousa Amadeu, Nader A1 - Jingjing, S. A1 - Emmerling, Franziska A1 - John, T. A1 - Paulus, B. A1 - Braun, T. T1 - Studies on the local structure of the F/OH site in topaz by magic angle spinning nuclear magnetic resonance and Raman spectroscopy N2 - he mutual influence of F and OH groups in neighboring sites in topaz (Al2SiO4(F,OH)2) was investigated using magic angle spinning nuclear magnetic resonance (MAS NMR) and Raman spectroscopy. The splitting of 19F and 1H NMR signals, as well as the OH Raman band, provides evidence for hydrogen bond formation within the crystal structure. Depending on whether a given OH group has another OH group or fluoride as its neighbor, two different hydrogen bond constellations may form: either OH···O···HO or F···H···O. The proton accepting oxygen was determined to be part of the SiO4 tetrahedron using 29Si MAS NMR. Comparison of the MAS NMR data between an OH-bearing and an OH-free topaz sample confirms that the 19F signal at −130 ppm stems from F− ions that take part in H···F bonds with a distance of ∼ 2.4 Å, whereas the main signal at −135 ppm belongs to fluoride ions with no immediate OH group neighbors. The Raman OH sub-band at 3644 cm−1 stems from OH groups neighboring other OH groups, whereas the sub-band at 3650 cm−1 stems from OH groups with fluoride neighbors, which are affected by H···F bridging. The integrated intensities of these two sub-bands do not conform to the expected ratios based on probabilistic calculations from the total OH concentration. This can be explained by a difference in the polarizability of the OH bond between the different hydrogen bond constellations or partial order or unmixing of F and OH, or a combination of both. This has implications for the quantitative interpretation of Raman data on OH bonds in general and their potential use as a probe for structural (dis-)order. No indication of tetrahedrally coordinated Al was found with 27Al MAS NMR, suggesting that the investigated samples likely have nearly ideal Al/Si ratios, making them potentially useful as high-density electron microprobe reference materials for Al and Si, as well as for F. KW - Topas KW - NMR KW - XRD PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-561863 DO - https://doi.org/10.5194/ejm-34-507-2022 SN - 1617-4011 VL - 34 IS - 5 SP - 507 EP - 521 PB - Copernicus Publications CY - Göttingen AN - OPUS4-56186 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lopes, Chrystal A1 - Casali, Lucia A1 - Emmerling, Franziska A1 - Leyssens, Tom A1 - Dupray, Valérie A1 - Brandel, Clement A1 - Cartigny, Yohann T1 - Efficient racemization of the pharmaceutical compound Levetiracetam using solvent-free mechanochemistry N2 - We present the racemization of an active pharmaceutical ingredient Levetiracetam using a novel approach. We demonstrate the design of a 100% solvent-free process that proceeds by high energy milling inside a regular mixer mill. The kinetics of the racemization process is drastically improved compared to the solution-based approach and illustrates the tremendous potential of mechanochemistry. In this study, we highlight the importance of mixing efficiency regarding data reproducibility, and we show, in particular, that water contamination has a negative impact on the reaction rate. Moreover, in situ X-ray diffraction gives us first insights into the mechanisms involved in the solid state during the mechanochemical racemization process. KW - Mechanochemistry PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-646108 DO - https://doi.org/10.1039/d4mr00103f SN - 2976-8683 VL - 2 IS - 1 SP - 83 EP - 90 PB - Royal Society of Chemistry (RSC) AN - OPUS4-64610 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lumpe, H. A1 - Menke, A. A1 - Haisch, C. A1 - Mayer, P. A1 - Kabelitz, Anke A1 - Yusenko, Kirill A1 - de Oliveira Guilherme Buzanich, Ana A1 - Block, T. A1 - Pöttgen, R. A1 - Emmerling, Franziska A1 - Daumann, L. J. T1 - The Earlier the Better: Structural Analysis and Separation of Lanthanides with Pyrroloquinoline Quinone N2 - Lanthanides (Ln) are critical raw materials, however, their mining and purification have a considerable negative environmental impact and sustainable recycling and separation strategies for these elements are needed. In this study, the precipitation and solubility behavior of Ln complexes with pyrroloquinoline quinone (PQQ), the cofactor of recently discovered lanthanide (Ln) dependent methanol Dehydrogenase (MDH) enzymes, is presented. In this context, the molecular structure of a biorelevant europium PQQ complex was for the first time elucidated outside a protein environment. The complex crystallizes as an inversion symmetric dimer, Eu2PQQ2, with binding of Eu in the biologically relevant pocket of PQQ. LnPQQ and Ln1Ln2PQQ complexes were characterized by using inductively coupled Plasma mass spectrometry (ICP-MS), infrared (IR) spectroscopy, 151Eu-Mössbauer spectroscopy, X-ray total scattering, and Extended X-ray absorption fine structure (EXAFS). It is shown that a natural enzymatic cofactor is capable to achieve Separation by precipitation of the notoriously similar, and thus difficult to separate, lanthanides to some extent. KW - Lanthanides KW - Structural Analysis KW - Separation PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-510821 DO - https://doi.org/10.1002/chem.202002653 SN - 0947-6539 VL - 26 SP - 1 EP - 8 PB - WILEY-VCH Verlag GmbH & co. KGaA AN - OPUS4-51082 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lumpe, H. A1 - Menke, Annika A1 - Haisch, C. A1 - Mayer, P. A1 - Kabelitz, Anke A1 - Yusenko, Kirill A1 - de Oliveira Guilherme Buzanich, Ana A1 - Block, T. A1 - Pöttgen, R. A1 - Emmerling, Franziska A1 - Daumann, L. T1 - The Earlier the Better: Structural Analysis and Separation of Lanthanides with Pyrroloquinoline Quinone N2 - Lanthanides (Ln) are critical raw materials, however, their mining and purification have a considerable negative environmental impact and sustainable recycling and separation strategies for these elements are needed. In this study, the precipitation and solubility behavior of Ln complexes with pyrroloquinoline quinone (PQQ), the cofactor of recently discovered lanthanide (Ln) dependent methanol dehydrogenase (MDH) enzymes, is presented. In this context, the molecular structure of a biorelevant europium PQQ complex was for the first time elucidated outside a protein environment. The complex crystallizes as an inversion symmetric dimer, Eu2PQQ2, with binding of Eu in the biologically relevant pocket of PQQ. LnPQQ and Ln1Ln2PQQ complexes were characterized by using inductively coupled plasma mass spectrometry (ICP‐MS), infrared (IR) spectroscopy, 151Eu‐Mössbauer spectroscopy, X‐ray total scattering, and extended X‐ray absorption fine structure (EXAFS). It is shown that a natural enzymatic cofactor is capable to achieve separation by precipitation of the notoriously similar, and thus difficult to separate, lanthanides to some extent. KW - PQQ KW - Lanthanoide KW - Coordination chemistry KW - Rare earth elements separations PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-512707 DO - https://doi.org/10.1002/chem.202002653 VL - 26 IS - 44 SP - 10133 EP - 10139 AN - OPUS4-51270 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Macchietti, Laura A1 - Casali, Lucia A1 - Emmerling, Franziska A1 - Braga, Dario A1 - Grepioni, Fabrizia T1 - Deriving kinetic insights from mechanochemically synthesized compounds using multivariate analysis (MCR-ALS) of powder X-ray diffraction data N2 - Kinetics information on the progress of the mechanochemical reactions is key to their understanding and subsequent scale-up. For crystalline materials, the most robust and tested method for obtaining kinetic data is the Quantitative Phase Analysis (QPA) via Rietveld refinement. In this work, we tested the feasibility of the Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) method on powder X-ray diffraction (PXRD) data of mechanochemical processes by studying the system theophylline (TP) and malonic acid (MA) in a 1 : 1 stoichiometric ratio at different milling conditions. We have highlighted the strengths and weaknesses of the MCR-ALS method, and we demonstrated why it may be an alternative route to obtain quantitative information on mechanochemical kinetics. KW - Mechanochemistry PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-646115 DO - https://doi.org/10.1039/d3mr00013c SN - 2976-8683 VL - 1 IS - 1 SP - 106 EP - 115 PB - Royal Society of Chemistry (RSC) AN - OPUS4-64611 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Manoharan, D. A1 - Ahmad, S. A1 - Emmerling, Franziska A1 - Bhattacharya, Biswajit A1 - Ghosh, S. T1 - Stress and light sensitive dual-mechanical property of acylhydrazone crystal N2 - Mechanically dual-responsive molecular crystals have gained ubstantial interest among researchers due to their significant applications in various fields. However, incorporation of disparate mechanical responses in the same crystalline material is still a challenging issue and is continuously being explored. Here, we report long acicular crystals derived from 4-bromobenzhydrazide and 9-anthraldehyde exhibit both stressinduced mechanical bending and blue-light induced photomechanical bending. Furthermore, the crystals show thermal back isomerization upon gradual heating. These two distinct mechanical responses in the crystalline phase have been studied and their structure–property correlation have been established. KW - Light sensitive crystal KW - Mechanical flexibility KW - Organic crystal PY - 2023 DO - https://doi.org/10.1039/d3ce00296a VL - 25 IS - 21 SP - 3237 EP - 3244 PB - Royal Society of Chemisty (RSC) CY - London/Cambridge AN - OPUS4-57593 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Manoharan, D. A1 - Megha, S. N. A1 - Kiran, M. S. R. N. A1 - Emmerling, Franziska A1 - Bhattacharya, Biswajit A1 - Ghosh, S. T1 - Designing the Mechanical Plasticity of Benzylidene Indanones Based Molecular Crystals by Crystal Engineering N2 - Mechanically flexible molecular crystals have important implications in flexible optoelectronics, optical waveguides, etc. We report a series of 2-benzylidene 1-indanone based plastic crystals. Moreover, we have shown how plasticity can be fine-tuned through controlling intermolecular interactions. KW - Mechanical flexibility KW - Organic crystal KW - Mechanical property PY - 2023 DO - https://doi.org/10.1021/acs.cgd.2c01137 SN - 1528-7483 VL - 23 SP - 657 EP - 661 PB - ACS Publications AN - OPUS4-57773 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Manoharan, Deepak A1 - Ahmad, Shamim A1 - Tothadi, Srinu A1 - Emmerling, Franziska A1 - Bhattacharya, Biswajit A1 - Ghosh, Soumyajit T1 - Linker size dependent mechanical properties of di-imine based molecular crystals N2 - We have demonstrated the ability to modify the mechanical flexibility of molecular crystals by modulating the length of intervening linker moieties while keeping the terminal shape synthons the same. KW - Mechanically flexible molecular crystals KW - Mechanical properties KW - Crystal Engineering PY - 2023 DO - https://doi.org/10.1039/D3CE00928A SN - 1466-8033 SP - 1 EP - 8 PB - RSC CY - London AN - OPUS4-58836 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Manoharan, Deepak A1 - Ranjan, Subham A1 - Emmerling, Franziska A1 - Bhattacharya, Biswajit A1 - Takamizawa, Satoshi A1 - Ghosh, Soumyajit T1 - Elasto-plastic behaviour with reversible thermosalient expansion in acrylonitrile-based organic crystals N2 - Crystalline materials that exhibit reversible mechanical responses upon exposure to external stimuli have garnered significant attention owing to their potential applications in various fields. Herein, we report a crystal of (2Z,2′Z)-2,2′-(1,4-phenylene)bis(3-(4-bromophenyl)acrylonitrile) (DSBr), which displays simultaneous elasto-plastic behaviour and reversible thermosalient effects. While elasto-plastic behaviour is attributed to underlying packing features, reversible thermosalient expansion is attributed to uniaxial expansion mediated by heat. Exceptional length increase and contraction upon cooling is due to the restorative nature of weak interactions through a cooperative effect. The cooperative movement of molecules is reflected in the unidirectional expansion of the habit plane. Thermosalient reversible expansion–contraction in elasto-plastic crystals have not been discussed in the literature so far. Detailed analysis reported herein provides a comprehensive understanding of the underlying mechanism of flexibility and thermosalient responses. This crystal's unique blend of reversible thermal expansion with flexibility holds substantial promise for applications in flexible thermal actuators. KW - Materials Chemistry KW - General Chemistry PY - 2024 DO - https://doi.org/10.1039/D3TC04272C SN - 2050-7526 SP - 1 EP - 11 PB - Royal Society of Chemistry (RSC) AN - OPUS4-59527 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Martins, I. A1 - Carta, M. A1 - Haferkamp, Sebastian A1 - Feiler, Torvid A1 - Delogu, F. A1 - Colacino, E. A1 - Emmerling, Franziska T1 - Mechanochemical N‑Chlorination Reaction of Hydantoin: In Situ Real-Time Kinetic Study by Powder X‑ray Diffraction and Raman Spectroscopy N2 - Mechanochemistry has become a valuable tool for the synthesis of new molecules, especially in the field of organic chemistry. In the present work, we investigate the kinetic profile of the chlorination reaction of N-3-ethyl-5,5-dimethylhydantoin (EDMH) activated and driven by ball milling. The reaction has been carried out using 2 mm, 4 mm, 5 mm, 6 mm, and 8 mm ball sizes in a new small custom-made Perspex milling jar. The Crystal structure of the starting material EDMH and the 1-chloro-3-ethyl5,5′-dimethyl hydantoin (CEDMH) chlorination product was solved by single-crystal X-ray diffraction. The reaction was monitored, in situ and in real time, by both powder X-ray diffraction (PXRD) and Raman spectroscopy. Our kinetic data show that the reaction progress to equilibrium is similar at all milling ball sizes. The induction period is very short (between 10 and 40 s) when using 4 mm, 5 mm, 6 mm, and 8 mm balls. For the reaction performed with a 2 mm ball, a significantly longer induction period of 9 min was observed. This could indicate that an initial energy accumulation and higher mixing efficiency are necessary before the reaction starts. Using different kinetic models, we found that the amount of powder affected by critical loading conditions during individual impacts is significantly dependent on the ball size used. An almost linear correlation between the rate of the chemical transformations and the ball volume is observed. KW - Mechanochemistry KW - In situ real-time monitoring KW - N-Chlorination KW - Kinetics KW - Hydantoin KW - Powder X-ray diffraction KW - Raman spectroscopy PY - 2021 DO - https://doi.org/10.1021/acssuschemeng.1c03812 VL - 9 IS - 37 SP - 12591 EP - 12601 AN - OPUS4-53541 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Martins, Ines A1 - Al-Sabbagh, Dominik A1 - Bentrup, U. A1 - Marquardt, Julien A1 - Schmid, Thomas A1 - Scoppola, E. A1 - Kraus, Werner A1 - Stawski, Tomasz A1 - de Oliveira Guilherme Buzanich, Ana A1 - Yusenko, Kirill A1 - Weidner, Steffen A1 - Emmerling, Franziska T1 - Formation Mechanism of a Nano-Ring of Bismuth Cations and Mono-Lacunary Keggin-Type Phosphomolybdate N2 - A new hetero-bimetallic polyoxometalate (POM) nano-ring was synthesized in a one-pot procedure. The structure consists of tetrameric units containing four bismuth-substituted monolacunary Keggin anions including distorted [BiO8] cubes. The nano-ring is formed via self-assembly from metal precursors in aqueous acidic medium. The compound (NH4)16[(BiPMo11O39)4] ⋅ 22 H2O; (P4Bi4Mo44) was characterized by single-crystal X-ray diffraction, extended X-ray absorption fine structure spectroscopy (EXAFS), Raman spectroscopy, matrix-assisted laser desorption/ionisation-time of flight mass spectrometry (MALDI-TOF), and thermogravimetry/differential scanning calorimetry mass spectrometry (TG-DSC-MS). The formation of the nano-ring in solution was studied by time-resolved in situ small- and wide-angle X-ray scattering (SAXS/WAXS) and in situ EXAFS measurements at the Mo−K and the Bi−L3 edge indicating a two-step process consisting of condensation of Mo-anions and formation of Bi−Mo-units followed by a rapid self-assembly to yield the final tetrameric ring structure. KW - Bismuth KW - In situ EXAFS KW - In situ SAXS/WAXS KW - Lacunary Keggin ion KW - Polyoxometalates KW - Self-assembly PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-546823 DO - https://doi.org/10.1002/chem.202200079 SN - 0947-6539 VL - 28 IS - 27 SP - 1 EP - 7 PB - Wiley-VCH CY - Weinheim AN - OPUS4-54682 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Martins, Inês C.B. A1 - Al-Sabbagh, Dominik A1 - Meyer, Klas A1 - Maiwald, Michael A1 - Scholz, G. A1 - Emmerling, Franziska T1 - Insight into the Structure and Properties of Novel Imidazole-Based Salts of Salicylic Acid N2 - The preparation of new active pharmaceutical ingredient (API) multicomponent Crystal forms, especially co-crystals and salts, is being considered as a reliable strategy to improve API solubility and bioavailability. In this study, three novel imidazole-based salts of the poorly water-soluble salicylic acid (SA) are reported exhibiting a remarkable improvement in solubility and dissolution rate properties. All structures were solved by powder X-ray diffraction. Multiple complementary techniques were used to solve co-crystal/salt ambiguities: density functional Theory calculations, Raman and 1H/13C solid-state NMR spectroscopies. In all molecular salts, the Crystal packing interactions are based on a common charged assisted +N-H SA)...O-(co-former) hydrogen bond interaction. The presence of an extra methyl group in different positions of the co-former, induced different supramolecular arrangements, yielding salts with different physicochemical properties. All salts present much higher solubility and dissolution rate than pure SA. The most promising results were obtained for the salts with imidazole and 1-methylimidazole co-formers. KW - Salicylic acid KW - Imidazole KW - Salts KW - Powder X-ray diffraction KW - SsNMR KW - DFT PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-502825 DO - https://doi.org/10.3390/molecules24224144 VL - 24 IS - 22 SP - 4144 PB - MDPI AN - OPUS4-50282 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Matoga, D. A1 - Roztocki, K. A1 - Wilke, Manuel A1 - Emmerling, Franziska A1 - Oszajca, M. A1 - Fitta, M. A1 - Bałanda, M. T1 - Crystalline bilayers unzipped and rezipped: solid-state reaction cycle of a metal–organic framework with triple rearrangement of intralayer bonds N2 - We present a series of remarkable structural transformations for a family of layered metal–organic frameworks (MOFs) in a three-step solid-state reaction cycle. The cycle represents new dynamic behavior of 2D coordination polymers and involves the sequence of reactions: {[Mn2(ina)4(H2O)2]·2EtOH}n (JUK-1) → {(NH4)2[Mn(ina)2(NCS)2]}n·xH2O (JUK-2) → {[Mn2(ina)2(Hina)2(NCS)2]}n (JUK-3) → JUK-1 (Hina = isonicotinic acid), each accompanied by rearrangement of intralayer coordination bonds and each induced by a different external stimulus. In situ investigation of the first step of the cycle by combined synchrotron X-ray diffraction and Raman spectroscopy reveals direct mechanochemical unzipping of JUK-1 bilayers to respective JUK-2 layers with reaction rates dependent on the milling conditions. In contrast, the reverse zipping of JUK-2 layers involves two steps and proceeds through a new MOF (JUK-3) whose structure was elucidated by powder X-ray diffraction. Magnetic measurements confirm conversions of manganese nodes in the reaction cycle. The findings indicate the possibility of developing coordination-based assemblies with large structural responses for use in smart stimuli-responsive systems and sensor technologies. KW - Mechanochemistry KW - In situ KW - XRD KW - MOF PY - 2017 UR - http://pubs.rsc.org/is/content/articlehtml/2017/ce/c7ce00655a DO - https://doi.org/10.1039/C7CE00655A VL - 19 SP - 2987 EP - 2995 AN - OPUS4-41517 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mazzeo, P A1 - Lampronti, G A1 - Michalchuk, Adam A1 - Belenguer, A A1 - Bacchi, A A1 - Emmerling, Franziska T1 - Accurate extrinsic and intrinsic peak broadening modelling for time-resolved in situ ball milling reactions via synchrotron powder X-ray diffraction N2 - The debate on the mechanisms which underpin mechanochemical reactions via ball mill grinding is still open. Our ability to accurately measure the microstructural (crystal size and microstrain) evolution of materials under milling conditions as well as their phase composition as a function of time is key to the in-depth understanding of the kinetics and driving forces of mechanochemical transformations. Furthermore, all ball milling reactions end with a steady state or milling equilibrium – represented by a specific phase composition and relative microstructure – that does not change as long as the milling conditions are maintained. The use of a standard sample is essential to determine the instrumental contribution to the X-ray powder diffraction (XRPD) peak broadening for time-resolved in situ (TRIS) monitoring of mechanochemical reactions under in operando conditions. Using TRIS-XRPD on a ball milling setup, coupled with low-energy synchrotron radiation, we investigated different data acquisition and analysis strategies on a silicon standard powder. The diffraction geometry and the microstructural evolution of the standard itself have been studied to model the instrumental contribution to XRPD peak broadening throughout the grinding activity. Previously proposed functions are here challenged and further developed. Importantly, we show that minor drifts of the jar position do not affect the instrumental resolution function significantly. We here report and discuss the results of such investigations and their application to TRIS-XRPD datasets of inorganic and organic ball mill grinding reactions. KW - Mechanochemistry KW - In situ diffraction KW - Synchrotron radiation KW - Sustainable chemisry PY - 2022 DO - https://doi.org/10.1039/d2fd00104g SP - 1 EP - 17 PB - Royal Society of Chemistry AN - OPUS4-55932 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mazzeo, P. P. A1 - Prencipe, M. A1 - Feiler, Torvid A1 - Emmerling, Franziska A1 - Bacchi, A. T1 - On the mechanism of cocrystal mechanochemical reaction via low melting eutectic: A time-resolved in situ monitoring investigation N2 - Mechanochemistry has become a sustainable and attractive cost-effective synthetic technique, largely used within the frame of crystal engineering. Cocrystals, namely, crystalline compounds made of different chemical entities within the same crystal structure, are typically synthesized in bulk via mechanochemistry; however, whereas the macroscopic aspects of grinding are becoming clear, the fundamental principles that underlie mechanochemical cocrystallization at the microscopic level remain poorly understood. Time-resolved in situ (TRIS) monitoring approaches have opened the door to exceptional detail regarding mechanochemical reactions. We here report a clear example of cocrystallization between two solid coformers that proceeds through the formation of a metastable low melting binary eutectic phase. The overall cocrystallization process has been monitored by time-resolved in situ (TRIS) synchrotron X-ray powder diffraction with a customized ball milling setup, currently available at μ Spot beamline at BESSY-II, Helmholtz-Zentrum Berlin. The binary system and the low melting eutectic phase were further characterized via DSC, HSM, and VT-XRPD. KW - Mechanochemistry KW - In situ KW - Cocrystal PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-552977 DO - https://doi.org/10.1021/acs.cgd.2c00262 SN - 1528-7505 VL - 22 IS - 7 SP - 4260 EP - 4267 PB - ACS Publ. CY - Washington, DC AN - OPUS4-55297 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Meißner, T. A1 - Bergmann, R. A1 - Oswald, J. A1 - Rode, K. A1 - Stephan, H. A1 - Richter, W. A1 - Zänker, H. A1 - Kraus, Werner A1 - Emmerling, Franziska A1 - Reck, Günter T1 - Chitosan-encapsulated Keggin anion [Ti2W10PO40]7-.Synthesis, characterization and cellular uptake studies N2 - The Keggin type polyoxotungstate [Ti2W10PO40]7- forms stable associates with the biopolymer chitosan in the nanometer size range. The cluster compound crystallizes from aqueous solution as K4H3[Ti2W10PO40] · 15H2O having a tetragonal structure. Both, the cluster compound and the chitosan/[Ti2W10PO40] associates show a high hydrolytic stability at pH 7.4. The associates formed between the cluster anion [Ti2W10PO40]7- with the polyaminosaccharide chitosan have been characterized by photon correlation spectroscopy, scanning electron microscopy, filtration, centrifugation and zeta potential measurements. The size of the associates formed is in the range of ca. 5×101 to 5×102 nm. These particles have a defined stoichiometry with 5–6 cluster anions bound per molecule chitosan. The isoelectric point determined by zeta potential measurements was found for a cluster anion to chitosan molar ratio of 5.5, indicating the charge neutralization between protonated chitosan and [Ti2W10PO40]7- anions. Cellular uptake studies with [Ti2W10PO40]7- using tumor cell lines FaDu (human squamous carcinoma) and HT-29 (human adenocarcinoma) showed that the tungsten amount inside the cells is remarkably enhanced in the presence of chitosan. KW - Cluster compound KW - Keggin structure KW - Bipolymer KW - Chitosan PY - 2006 DO - https://doi.org/10.1007/s11243-006-0035-z SN - 0340-4285 SN - 1572-901X VL - 31 IS - 5 SP - 603 EP - 610 PB - Springer CY - Dordrecht AN - OPUS4-12568 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Merkel, Stefan A1 - Köppen, Robert A1 - Koch, Matthias A1 - Emmerling, Franziska A1 - Nehls, Irene T1 - Ergometrinine N2 - The absolute configuration of ergometrinine, C19H23N3O2 {systematic name: (6aR,9S)-N-[(S)-1-hydroxypropan-2-yl]-7-methyl-4,6,6a,7,8,9-hexahydroindolo[4,3-fg]quinoline-9-carboxamide}, was established based on epimerization reaction of ergometrine, which was followed by preparative HPLC. The non-aromatic ring (ring C of the ergoline skeleton) directly fused to the aromatic rings is nearly planar [maximum deviation = 0.271 (3) Å] and shows an envelope conformation, whereas ring D, involved in an intramolecular N-HN hydrogen bond, exibits a slightly distorted chair conformation. The structure displays undulating layers in the ac plane formed by O-H...O and N-H...O hydrogen bonds. KW - Ergometrinine KW - Ergometrine KW - Ergot alkaloids KW - Indole alkaloids KW - Crystal structure KW - Epimerization PY - 2010 DO - https://doi.org/10.1107/S1600536810030825 SN - 1600-5368 VL - 66 IS - 9 SP - o2275, sup-1 - sup-9 PB - Munksgaard CY - Copenhagen AN - OPUS4-21806 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Merkel, Stefan A1 - Köppen, Robert A1 - Koch, Matthias A1 - Emmerling, Franziska A1 - Nehls, Irene T1 - Ergotaminine N2 - The title compound {systematic name: (6aR,9S)-N-[(2R,5S,10aS,10bS)-5-benzyl-10b-hydroxy-2-methyl-3,6-dioxooctahydro-8H-oxazolo[3,2-a]pyrrolo[2,1-c]pyrazin-2-yl]-7-methyl-4,6,6a,7,8,9-hexahydroindolo[4,3-fg]quinoline-9-carboxamide}, C33H35N5O5, was formed by an epimerization reaction of ergotamine. The non-aromatic ring (ring C of the ergoline skeleton) directly fused to the aromatic rings is nearly planar [maximum deviation = 0.317 (4) Å] and shows an envelope conformation, whereas ring D, involved in an intramolecular N–H···N hydrogen bond exhibits a slightly distorted chair conformation. The structure displays chains running approximately parallel to the diagonal of bc plane that are formed through N–H···O hydrogen bonds. PY - 2012 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-254528 DO - https://doi.org/10.1107/S1600536812003674 SN - 1600-5368 VL - 68 IS - 3 SP - o610-o611, sup1-sup11 PB - Munksgaard CY - Copenhagen AN - OPUS4-25452 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Merkel, Stefan A1 - Köppen, Robert A1 - Koch, Matthias A1 - Emmerling, Franziska A1 - Nehls, Irene T1 - Lysergol monohydrate N2 - In the title compound [systematic name: (7-methyl-4,6,6a,7,8,9-hexahydroindolo[4,3,2-fg]quinoline-9-yl)methanol monohydrate], C16H18N2O·H2O, the non-aromatic ring (ring C of the ergoline skeleton) directly fused to the aromatic rings is nearly planar, with a maximum deviation of 0.659 (3) Å, and shows an envelope conformation. In the crystal, hydrogen bonds between the lysergol and water molecules contribute to the formation of layers parallel to (10-2). PY - 2012 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-254015 DO - https://doi.org/10.1107/S1600536812002632 SN - 1600-5368 VL - 68 IS - 2 SP - o523, sup1 EP - sup8 PB - Munksgaard CY - Copenhagen AN - OPUS4-25401 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Merkel, Stefan A1 - Köppen, Robert A1 - Koch, Matthias A1 - Emmerling, Franziska A1 - Nehls, Irene T1 - Lumi-ergometrine - structural identification and occurrence in sclerotia N2 - The fungus Claviceps purpurea grows on grasses and cereal grains and produces six predominant ergot alkaloids. These toxic substances undergo different Transformation reactions during storage and cereal processing. One of these reactions is the addition of water to a double bond in the ergoline skeleton. Since light is required for this process, the substances formed were named lumi-ergot alkaloids. From these, a new asymmetric carbon and consequently two epimers with different polarities are formed. For investigations of lumi-ergot alkaloids, ergometrine was used exemplarily as it represents one of the six ergot Alkaloids predominantly formed by Claviceps purpurea. The main reaction product, the less polar compound of the two lumiergometrine epimers, was separated by HPLC and unambiguously identified as 10-(S)-lumi-ergometrine using X-ray structural analysis. A HPLC-MS/MS method was developed for the detection of this substance in sclerotia extracts. Using this method, the existence of both epimeric forms of lumiergometrinecould be proved in the sclerotia. This is the first time that the existence of a lumi-transformation product of ergot alkaloids was proved in naturally grown samples. KW - Lumi-ergot alkaloids KW - Sclerotia KW - Claviceps purpurea KW - HPLC-MS/MS PY - 2012 DO - https://doi.org/10.1007/s12550-011-0116-5 SN - 0178-7888 VL - 28 IS - 1 SP - 59 EP - 66 PB - Springer CY - Berlin; Heidelberg AN - OPUS4-25442 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Michalchuk, Adam A1 - Boldyreva, E. A1 - Belenguer, A. M. A1 - Emmerling, Franziska A1 - Boldyrev, V. V. T1 - Tribochemistry, mechanical alloying, mechanochemistry: what is in a name? N2 - Over the decades, the application of mechanical force to influence chemical reactions has been called by various names: mechanochemistry, tribochemistry, mechanical alloying, to name but a few. The evolution of these terms has largely mirrored the understanding of the field. But what is meant by these terms, why have they evolved, and does it really matter how a process is called? Which parameters should be defined to describe unambiguously the experimental conditions such that others can reproduce the results, or to allow a meaningful comparison between processes explored under different conditions? Can the information on the process be encoded in a clear, concise, and self-explanatory way? We address these questions in this Opinion contribution, which we hope will spark timely and constructive discussion across the international mechanochemistry community. KW - Mechanochemistry KW - Tribochemistry KW - Mechanical alloying KW - Tribology KW - Mechanical activation KW - Nomenclature KW - Mechanochemical pictographs PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-523291 DO - https://doi.org/10.3389/fchem.2021.685789 SN - 2296-2646 VL - 9 SP - 1 EP - 29 PB - Frontiers Media CY - Lausanne AN - OPUS4-52329 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Michalchuk, Adam A1 - Emmerling, Franziska T1 - Time-Resolved InSitu Monitoring of Mechanochemical Reactions N2 - Mechanochemical transformations offer environmentally benign synthesis routes, whilst enhancing both the speed and selec-tivity of reactions. In this light, mechanochemistry promises to trans-form the way in which chemistry is done in both academia and indus-try but is greatly hindered by a current lack in mechanistic understand-ing. The continued development and use of time-resolved in situ(TRIS) approaches to monitor mechanochemical reactions provides a new dimension to elucidatethese fascinating transformations. We here discuss recent trends in method development that have pushed the boundaries of mechanochemical research. New features of mech-anochemical reactions obtained by TRIS techniques are subse-quently discussed, shedding light on how different TRISapproaches have beenused. Emphasis is placed on the strength of combining complementary techniques. Finally, we outline our views for the po-tential of TRIS methods in mechanochemical research, towards es-tablishing a new, environmentally benign paradigm in the chemical sciences KW - Mechanochemistry KW - Material synthesis KW - Green chemistry PY - 2022 DO - https://doi.org/10.1002/anie.202117270 SN - 1433-7851 SP - 1 EP - 15 PB - Wiley-VCH CY - Weinheim AN - OPUS4-54321 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Miliūtė, Aistė A1 - Bustamante, Joana A1 - Karafiludis, Stephanos A1 - Zöllner, Moritz A1 - Eddah, Mustapha A1 - Emmerling, Franziska A1 - Mieller, Björn A1 - George, Janine A1 - Stawski, Tomasz M. T1 - Synthesis and phase purity of the negative thermal expansion material ZrV2O7 N2 - Synthesis of pure, homogeneous, and reproducible materials is key for the comprehensive understanding, design, and tailoring of material properties. In this study, we focus on the synthesis of ZrV2O7, a material known for its negative thermal expansion properties. We investigate the influence of solid-state and wet chemistry synthesis methods on the purity and homogeneity of ZrV2O7 samples. Our findings indicate that different synthesis methods significantly impact the material's characteristics. The solid-state reaction provided high-purity material through extended milling time and repeated calcination cycles, while the sol-gel reaction enabled a “near-atomic” level of mixing and, therefore, homogenous phase-pure ZrV2O7. We confirmed purity via X-ray diffraction and Raman spectroscopy, highlighting differences between phase-pure and multiphase ceramics. These analytical techniques allowed us to distinguish subtle differences in the structure of the material. Based on ab initio simulated phonon data, we were able to interpret the Raman spectra and visualise Raman active atom vibrations. We show that phase purity enables the unbiased characterisation of material properties such as negative thermal expansion. KW - NTE KW - Sol-gel KW - Solid-state KW - Ab-initio KW - XRD KW - Raman PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-624013 DO - https://doi.org/10.1039/d4tc04095c SN - 2050-7534 SP - 1 EP - 13 PB - Royal Society of Chemistry (RSC) AN - OPUS4-62401 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mishra, Rajesh K. A1 - Minussi, F.B. A1 - Kumari, Priyanka A1 - Shahi, Rohit R. A1 - Yadav, R.P. A1 - Emmerling, Franziska A1 - Araújo, E.B. T1 - Effect of sintering temperature on structural, microstructural, and dielectric properties of (Co0.2Fe0.2Ni0.2Al0.2Ti0.2)3O4 multi-cations high entropy oxides N2 - The study reports the effect of sintering temperature on structural, microstructural, and dielectric properties of (Co0.2Fe0.2Ni0.2Al0.2Ti0.2)3O4 spinel high-entropy oxides (HEOs) synthesized through the solid-state mechanochemistry method. The sintering of the ceramic powders was accomplished at three different temperatures (1000 ◦C, 1100 ◦C, and 1250 ◦C), followed by air quenching. XRD analysis along with Le-Bail refinement confirms that 1100 ◦C and 1250 ◦C sintered oxides comprised of a single cubic spinel phase (Fd3m), while 1000 ◦C sintered oxide contains constituent oxides and a spinel phase. The phase formation of oxides sintered at 1100 ◦C and 1250 ◦C has also been confirmed by Raman spectroscopic analysis. Microstructural analysis revealed that the aggregated particle size increases with the rise in sintering temperature. With the change in sintering temperature, the dielectric behavior of the ceramic changed extensively. The 1100 ◦C sintered ceramic exhibits high frequency-dependent behavior, whereas the 1250 ◦C sintered ceramic yields low frequency-dependent behavior. The 1250 ◦C sintered HEO exhibits low-loss tangent (tan δ = 0.01) with higher dielectric permittivity (εʹ = 44) at high frequency (1 MHz) compared to the 1100 ◦C sintered ceramic and many other conventional dielectrics. Fractal concept and impedance analysis have been employed to correlate the microstructure-dielectric property relation of (Co0.2Fe0.2Ni0.2Al0.2Ti0.2)3O4 spinel HEOs. The found Hurst exponent values for both different temperature-sintered HEOs are less than 0.5, indicating the anti-persistent behavior. This signifies that the height variations at neighboring pixels are negatively correlated. The present work is of fundamental importance in employing fractal analysis for the first time on spinel HEOs and correlating their properties. It also shows that processing conditions can effectively tailor the dielectric properties of the materials. KW - Multi-cations high entropy oxide KW - Mechanochemistry KW - Spinel structure KW - Fractal and impedance spectroscopic analysis PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-647584 DO - https://doi.org/10.1016/j.ceramint.2025.09.256 SN - 0272-8842 VL - 51 IS - 27 SP - 55341 EP - 55354 PB - Elsevier Ltd. AN - OPUS4-64758 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mönch, Bettina A1 - Emmerling, Franziska A1 - Kraus, Werner A1 - Becker, Roland A1 - Nehls, Irene T1 - n-Propyl 2,3,4,6-tetra-O-acetyl-beta-D-glucopyranoside N2 - The title compound [systematic name: (2R,3R,4S,5R,6R) 2-(acetoxymethyl)-6-propoxytetrahydro-2H-pyran-3,4,5-triyl triacetate], C17H26O10, was formed by a Koenigs-Knorr reaction of 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide and n-propanol. The central ring adopts a chair conformation. The crystal does not contain any significant interactions such as hydrogen bonds. PY - 2013 DO - https://doi.org/10.1107/S1600536812051495 SN - 1600-5368 VL - 69 IS - Part 2 SP - o158, sup-1 - sup-7 PB - Munksgaard CY - Copenhagen AN - OPUS4-27439 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mönch, Bettina A1 - Emmerling, Franziska A1 - Kraus, Werner A1 - Becker, Roland A1 - Nehls, Irene T1 - Isopropyl 2,3,4,6-tetra-O-acetyl-beta-D-glucopyranoside N2 - The title compound, C17H26O10, was formed by a Koenigs-Knorr reaction of 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide and propan-2-ol. The central ring adopts a chair conformation. The crystal does not contain any significant intermolecular interactions. PY - 2013 DO - https://doi.org/10.1107/S1600536812051483 SN - 1600-5368 VL - 69 IS - Part 2 SP - o157, sup-1 - sup-7 PB - Munksgaard CY - Copenhagen AN - OPUS4-27572 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mönch, Bettina A1 - Gebert, Antje A1 - Emmerling, Franziska A1 - Becker, Roland A1 - Nehls, Irene T1 - Koenigs-Knorr reaction of fusel alcohols with methyl (1-bromo-2,3,4-tri-O-acetyl-alpha-D-glucopyranosid)uronate leading to the protected alkyl glucuronides-crystal structures and high resolution 1H and 13C NMR data N2 - Crystal structures and high resolution 1H and 13C NMR spectral data for methyl (alkyl 2,3,4-tri-O-acetyl-β-D-glucopyranosid)uronates (alkyl = methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i-butyl, n-pentyl, 2-methyl-1-butyl and 3-methyl-1-butyl) are presented. KW - D-Glucuronic acid derivates KW - X-ray analysis KW - High resolution NMR KW - Anomeric configuration KW - Synthesis PY - 2012 DO - https://doi.org/10.1016/j.carres.2012.01.002 SN - 0008-6215 SN - 1873-426X VL - 352 SP - 186 EP - 190 PB - Elsevier CY - Amsterdam AN - OPUS4-25759 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mönch, Bettina A1 - Kraus, Werner A1 - Köppen, Robert A1 - Emmerling, Franziska T1 - The different conformations and crystal structures of dihydroergocristine N2 - The identification of different forms of dihydroergocristine (DHEC) was carried out by crystallization from different organic solvents. DHEC was identified as potential template for molecularly imprinted polymers (MIPs) for the epimeric specific analysis of ergot alkaloids (EAs) in food. DHEC was crystallized from different solvents in order to mimic the typical MIP synthesis conditions. Four new solvatomorphs of DHEC were obtained. All solvatomorphs contain a water molecule in the crystal structure, whereas three compounds contain an additional solvent molecule. Based on the conformation of DHEC a comparison with typical EA molecules was possible. The analysis showed that DHEC is a suitable template for MIPs for EAs. PY - 2016 DO - https://doi.org/10.1016/j.molstruc.2015.10.008 SN - 0022-2860 SN - 1872-8014 SN - 0377-046X VL - 1105 SP - 389 EP - 395 PB - Elsevier B.V. CY - Amsterdam AN - OPUS4-35009 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Nag, Sayak A1 - Emmerling, Franziska A1 - Tothadi, Srinu A1 - Bhattacharya, Biswajit A1 - Ghosh, Soumyajit T1 - Distinct photomechanical responses of two new 1,3-dimethylbarbituric acid derivative crystals N2 - We demonstrate two distinct photomechanical responses (i.e. photomechanical bending and photosalient bursting) of two new 1,3-dimethylbarbituric acid derivative crystals based on tailoring their substituents and the modulation of their spacers. KW - Crystal engineering KW - Fexible crystals PY - 2024 DO - https://doi.org/10.1039/D4CE00233D SP - 1 EP - 12 PB - Royal Society of Chemistry (RSC) AN - OPUS4-60141 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Nehls, Irene A1 - Hanebeck, Olaf A1 - Becker, Roland A1 - Emmerling, Franziska T1 - N-(beta-carboxyethyl)-alpha-isoleucine N2 - The title compound, {2-[(2-carbamoylethyl)amino]-3-methylpentanoic acid}, C9H18N2O3, is of interest with respect to its biological activity. It was formed during an addition reaction between acrylamide and the amino acid isoleucine. The crystal structure is a three-dimensional network built up by intermolecular N–H···O and O–H···N hydrogen bonds. KW - Acrylamid KW - Isoleucin KW - Derivatisierung PY - 2013 DO - https://doi.org/10.1107/S160053681205146X SN - 1600-5368 VL - 69 IS - Part 2 SP - o172-o173, sup-1 - sup-7 PB - Munksgaard CY - Copenhagen AN - OPUS4-27573 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Nguyen, Thi Yen A1 - Rademann, K. A1 - Emmerling, Franziska T1 - Direct evidence of polyamorphism in paracetamol N2 - While polymorphism is a common phenomenon in the crystallization processes of organic compounds, polyamorphism has gained importance only recently. Using sophisticated sample environments and applying in situ scattering methods and vibrational spectroscopy, the complete crystallization process of organic compounds from solution can be traced and characterized. Diffuse scattering from amorphous intermediates can be investigated by analyzing the atomic pair distribution function (PDF) to gain further insights into molecular pre-orientation. The crystallization behavior of paracetamol was studied exemplarily under defined, surface-free conditions. Based on the choice of the solvent, the formation of different polymorphs is promoted. The thermodynamically stable form I and the metastable orthorhombic form II could be isolated in pure form directly from solution. For both polymorphs, the crystallization from solution proceeds via a distinct amorphous precursor phase. PDF analyses of these different amorphous states indicate a specific pre-orientation of the analyte molecules introduced by the solvent. The resulting crystalline polymorph is already imprinted in these proto-crystalline precursors. Direct experimental evidence for the polyamorphism of paracetamol is provided. PY - 2015 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-351366 DO - https://doi.org/10.1039/C5CE01583A SN - 1466-8033 VL - 17 IS - 47 SP - 9029 EP - 9036 PB - Royal Society of Chemistry CY - London, UK AN - OPUS4-35136 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Nguyen, Thi Yen A1 - Roessler, Ernst A1 - Rademann, Klaus A1 - Emmerling, Franziska T1 - Control of organic polymorph formation: crystallization pathways in acoustically levitated droplets N2 - Theoretical and experimental studies indicate that crystal nucleation can take more complex pathways than expected on the ground of the classical nucleation theory. Among these pathways are the formation of pre-nucleation clusters and amorphous precursor phases. A direct in situ observation of the different pathways of nucleation from solution is challenging since the paths can be influenced by heterogeneous nucleation sites, such as container walls. Here, we provide insights into the crystallization process using the in situ combination of an acoustic levitator, Raman spectroscopy, and X-ray scattering. The contactless sample holder enables the observation of homogeneous crystallization processes and the detection of intermediates and final crystalline forms. We provide evidence for the existence of multiple pathways of nucleation based on the investigation of the crystallization of organic molecules from different solvents. Starting from a diluted solution, a supersaturation is reached during the experiment due to the evaporation of the solvent. The highly supersaturated solution reveals different pathways of crystallization. Depending on the degree of supersaturation either the thermodynamically stable or the metastable crystal form is observed. KW - Crystallization KW - In situ XRD KW - Polymorphism KW - Polyamorphism KW - Raman spectroscopy PY - 2017 DO - https://doi.org/10.1515/zkri-2016-1964 SN - 2194-4946 SN - 2196-7105 VL - 232 IS - 1-3 SP - 15 EP - 24 PB - De Gruyter CY - Berlin AN - OPUS4-39708 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Noack, J. A1 - Emmerling, Franziska A1 - Kirmse, H. A1 - Kemnitz, E. T1 - Sols of nanosized magnesium fluoride: formation and stabilisation of nanoparticles N2 - The formation of magnesium fluoride sols and xerogels according to the fluorolytic sol–gel synthesis based on the reaction of Mg(OMe)2 with non-aqueous HF has been thoroughly investigated by X-ray scattering (WAXS/XRD), TEM, SAXS, DLS and 19F MAS NMR spectroscopy. Mechanistic insights were gained by following the reaction progress and formation of intermediate phases of the fluorination of magnesium alkoxides. For F:Mg ratios of 0.3 and 0.4 the formation of two crystalline phases was observed containing the recently obtained compound [Mg6F2(OCH3)10(CH3OH)14] hexanuclear dicubane units. The stoichiometric reaction yields magnesium fluoride nanoparticles with crystallite sizes below 5 nm, which show broad reflections in the X-ray diffraction pattern. Metal fluoride sols prepared by this way undergo tremendous changes over the first several weeks after synthesis. Immediately after the fluorination, particles of about 120 nm—probably agglomerates—are formed, which break apart in the course of about one month of ageing and low-viscous, transparent sols with particles of about 12 nm are obtained. At the same time structural re-organisation processes within the magnesium fluoride particles are observed by an increase of the (110) reflection in WAXS. KW - Surface modification KW - Colloidal particles KW - Gold nanoparticles KW - Gel synthesis KW - Small-angle scattering KW - Oxide KW - Polyelectrolytes KW - Aggregation KW - Dispersion PY - 2011 DO - https://doi.org/10.1039/c1jm11943e SN - 0959-9428 SN - 1364-5501 VL - 21 IS - 38 SP - 15015 EP - 15021 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-26183 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Opitz, P. A1 - Asta, M. A1 - Fernandez-Martinez, A. A1 - Panthöfer, M. A1 - Kabelitz, Anke A1 - Emmerling, Franziska A1 - Mondeshki, M. A1 - Tremel, W. T1 - Monitoring a Mechanochemical Syntheses of Isostructural Luminescent Cocrystals of 9-Anthracenecarboxylic Acid with two Dipyridines Coformers N2 - Amorphous calcium carbonate (ACC) is an important precursor in the biomineralization of crystalline CaCO3. In nature, it serves as a storage material or as a permanent structural element, whose lifetime is regulated by an organic matrix. The relevance of ACC in materials science is primarily related to our understanding of CaCO3 crystallization pathways and CaCO3/(bio)polymer nanocomposites. ACC can be synthesized by liquid–liquid phase separation, and it is typically stabilized with macromolecules. We have prepared ACC by milling calcite in a planetary ball mill. Phosphate “impurities” were added in the form of monetite (CaHPO4) to substitute the carbonate anions, thereby stabilizing ACC by substitutional disorder. The phosphate anions do not simply replace the carbonate anions. They undergo shear-driven acid/base and condensation reactions, where stoichiometric (10%) phosphate contents are required for the amorphization to be complete. The phosphate anions generate a strained network that hinders ACC recrystallization kinetically. The amorphization reaction and the structure of BM-ACC were studied by quantitative Fourier transform infrared spectroscopy and solid state 31P, 13C, and 1H magic angle spinning nuclear magnetic resonance spectroscopy, which are highly sensitive to symmetry changes of the local environment. In the first—and fast—reaction step, the CO32– anions are protonated by the HPO42– groups. The formation of unprecedented hydrogen carbonate (HCO3–) and orthophosphate anions appears to be the driving force of the reaction, because the phosphate group has a higher Coulomb energy and the tetrahedral PO43– unit can fill space more efficiently. In a competing second—and slow—reaction step, pyrophosphate anions are formed in a condensation reaction. No pyrophosphates are formed at higher carbonate contents. High strain leads to such a large energy barrier that any reaction is suppressed. Our findings aid in the understanding of the mechanochemical amorphization of calcium carbonate and emphasize the effect of impurities for the stabilization of the amorphous phases in general. Our approach allowed the synthesis of new amorphous alkaline earth defect variants containing the unique HCO3– anion. Our approach outlines a general strategy to obtain new amorphous solids for a variety of carbonate/phosphate systems that offer promise as biomaterials for bone regeneration. KW - Crystallization KW - Mechanochemistry KW - PDF PY - 2020 DO - https://doi.org/10.1021/acs.cgd.0c00912 VL - 20 IS - 10 SP - 6831 EP - 6846 PB - American Chemical Society AN - OPUS4-51819 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Opitz, P. A1 - Besch, L. A1 - Panthöfer, M. A1 - Kabelitz, Anke A1 - Unger, R. A1 - Emmerling, Franziska A1 - Mondeshki, M. A1 - Tremel, W. T1 - Insights into the In Vitro Formation of Apatite from Mg‐Stabilized Amorphous Calcium Carbonate N2 - A protein‐free formation of bone‐like apatite from amorphous precursors through ball‐milling is reported. Mg2+ ions are crucial to achieve full amorphization of CaCO3. Mg2+ incorporation generates defects which strongly retard a recrystallization of ball‐milled Mg‐doped amorphous calcium carbonate (BM‐aMCC), which promotes the growth of osteoblastic and endothelial cells in simulated body fluid and has no effect on endothelial cell gene expression. Ex situ snapshots of the processes revealed the reaction mechanisms. For low Mg contents (<30%) a two phase system consisting of Mg‐doped amorphous calcium carbonate (ACC) and calcite “impurities” was formed. For high (>40%) Mg2+ contents, BM‐aMCC follows a different crystallization path via magnesian calcite and monohydrocalcite to aragonite. While pure ACC crystallizes rapidly to calcite in aqueous media, Mg‐doped ACC forms in the presence of phosphate ions bone‐like hydroxycarbonate apatite (dahllite), a carbonate apatite with carbonate substitution in both type A (OH−) and type B (PO43−) sites, which grows on calcite “impurities” via heterogeneous nucleation. This process produces an endotoxin‐free material and makes BM‐aMCC an excellent “ion storage buffer” that promotes cell growth by stimulating cell viability and metabolism with promising applications in the treatment of bone defects and bone degenerative diseases. KW - Total Scattering KW - XRD KW - Mechanochemistry PY - 2020 DO - https://doi.org/10.1002/adfm.202007830 VL - 31 IS - 3 SP - 7830 PB - Wiley VHC-Verlag AN - OPUS4-51761 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Orgzall, I. A1 - Emmerling, Franziska A1 - Schulz, B. A1 - Franco, O. T1 - High-pressure studies on molecular crystals - relations between structure and high-pressure behavior N2 - This paper summarizes attempts to understand structure–property relationships for a large class of aromatic diphenyl-1,3,4-oxadiazole molecules. Starting from the investigation of the crystal structure several common packing motifs as well as characteristic differences are derived. Many different molecules show a rather planar conformation in the solid state. A stronger intermolecular twist is only observed for compounds with substituents occupying the ortho-positions of the phenyl rings. Most crystal structures are characterized by the formation of stacks leading to intense π–π acceptor–donor interactions between oxadiazole and phenyl rings. High-pressure investigations result in a soft compression behavior typical for organic molecular crystals. The bulk behavior may be described by the Murnaghan equation of state with similar coefficients (bulk modulus and its pressure derivative) for nearly all investigated compounds but also for related substances. The compression shows a strong anisotropy resulting from the specific features and packing motifs of the crystal structure. This is clearly indicated by a corresponding strain analysis. Additionally to the crystal structure the Raman spectrum was also investigated under increasing pressure. The different pressure behavior of external and internal modes reflects the difference between intra- and intermolecular interactions. KW - Diphenyl-1,3,4-oxadiazole KW - Crystal structure KW - High pressure investigations KW - Equation of state KW - Strain analysis KW - Raman investigations PY - 2008 DO - https://doi.org/10.1088/0953-8984/20/29/295206 SN - 0953-8984 SN - 1361-648X VL - 20 SP - 295206-1 - 295206-15 PB - IOP Publ. Ltd. CY - Bristol AN - OPUS4-17784 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ortel, Erik A1 - Fischer, A. A1 - Chuenchom, L. A1 - Polte, Jörg A1 - Emmerling, Franziska A1 - Smarsly, B.M. A1 - Kraehnert, R. T1 - New triblock copolymer templates, PEO-PB-PEO, for the synthesis of titania films with controlles mesopore size, wall thickness, and bimodal porosity N2 - The synthesis and properties of a series of new structure-directing triblock copolymers with PEO-PB-PEO structure (PEO = poly(ethylene oxide) and PB = polybutadiene) and their application as superior pore-templates for the preparation of mesoporous titania coatings are reported. Starting from either TiCl4 or from preformed TiO2 nanocrystalline building blocks, mesoporous crystalline titanium oxide films with a significant degree of mesoscopic ordered pores are derived, and the pore size can be controlled by the molecular mass of the template polymer. Moreover, the triblock copolymers form stable micelles already at very low concentration, i.e., prior to solvent evaporation during the evaporation-induced self-assembly process (EISA). Consequently, the thickness of pore walls can be controlled independently of pore size by changing the polymer-to-precursor ratio. Thus, unprecedented control of wall thickness in the structure of mesoporous oxide coatings is achieved. In addition, the micelle formation of the new template polymers is sufficiently distinct from that of typical commercial PPO-PEO-PPO polymers (Pluronics; PPO = poly(propylene oxide)), so that a combination of both polymers facilitates bimodal porosity via dual micelle templating. KW - Mesoporous materials KW - Titanium oxide films KW - Anatase nanoparticles KW - PEO-PB-PEO KW - Dual templating PY - 2012 DO - https://doi.org/10.1002/smll.201101520 SN - 1613-6810 SN - 1613-6829 VL - 8 IS - 2 SP - 298 EP - 309 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-26277 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ortel, Erik A1 - Polte, J. A1 - Bernsmeier, D. A1 - Eckhardt, B. A1 - Paul, B. A1 - Bergmann, A. A1 - Strasser, P. A1 - Emmerling, Franziska A1 - Kraehnert, R. T1 - Pd/TiO2 coatings with template-controlled mesopore structure as highly active hydrogenation catalyst N2 - Micro-structured reactors offer excellent mass and heat transport capabilities and can therefore sustain very high reaction rates and space–time-yields also for highly exothermic catalytic reactions. However, such high rates cannot be reached when the reactors are coated or filled with conventional catalysts powders. We present a strategy for the direct synthesis of highly active wall-coated supported catalysts via co-deposition of a pore template (here micelles formed from PEO-b-PPO-b-PEO) and a precursors for the metal oxide (TiCl4) along with a compatible precursor for the active metal (PdCl2). The obtained catalytic coatings possess a template-controlled open pore structure and excellent mechanical stability. Moreover, the active metal is highly dispersed and well-distributed across the coating also at high Pd loadings. The corresponding high activity along with rapid mass transfer enabled by the open pore system results in the best space–time-yields in the gas-phase hydrogenation of butadiene reported so far in literature for a supported catalyst. KW - Titanium oxide films KW - Palladium nanoparticle KW - Wall-coated supported catalysts KW - Template-controlled mesoporous materials KW - Hydrogenation of 1,3-butadiene PY - 2015 DO - https://doi.org/10.1016/j.apcata.2014.12.044 SN - 0926-860X SN - 1873-3875 VL - 493 SP - 25 EP - 32 PB - Elsevier CY - Amsterdam AN - OPUS4-32465 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Pakrashy, S. A1 - Mandal, P. K. A1 - Goswami, J. N. A1 - Dey, S. K. A1 - Choudhury, S. M. A1 - Bhattacharya, Biswajit A1 - Emmerling, Franziska A1 - Alasmary, F. A. A1 - Dolai, M. T1 - Bioinformatics and Network Pharmacology of the First Crystal Structured Clerodin: Anticancer and Antioxidant Potential against Human Breast Carcinoma Cell N2 - Clerodin was isolated from the medicinal plant Clerodendrum infortunatum, and CSD search showed the first crystal structure of clerodin by a single-crystal X-ray diffraction study. We checked its binding potential with target proteins by docking and conducted network pharmacology analysis, ADMET analysis, in silico pathway analysis, normal mode analysis (NMA), and cytotoxic activity studies to evaluate clerodin as a potential anticancer agent. The cell viability studies of clerodin on the human breast carcinoma cell line (MCF-7) showed toxicity on MCF-7 cells but no toxicity toward normal human lymphocyte cells (HLCs). The anticancer mechanism of clerodin was validated by its enhanced capacity to produce intracellular reactive oxygen species (ROS) and to lower the reduced glutathione content in MCF-7 cells. KW - Anticancer KW - Clerodin PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-567600 DO - https://doi.org/10.1021/acsomega.2c07173 SN - 2470-1343 VL - 7 IS - 51 SP - 48572 EP - 48582 PB - ACS Publ. CY - Washington, DC AN - OPUS4-56760 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Pakrashy, Sourav A1 - Chakraborty, Souvik A1 - Manna, Sounik A1 - Nanda Goswami, Juli A1 - Bhattacharya, Biswajit A1 - Emmerling, Franziska A1 - Mandal, Jishu A1 - Misra, Sourav A1 - Maiti Choudhury, Sujata A1 - Okla, Mohammad K. A1 - Bose, Adity A1 - Maurya, Pawan Kumar A1 - Majhi, Anjoy A1 - Dolai, Malay T1 - Inhibition of Human Colorectal Cancer by a Natural Product 7-Acetylhorminone and Interactions with BSA/HSA: Multispectral Analysis and In Silico and In Vitro Studies N2 - We have semi-synthesized a natural product 7-acetylhorminone from crude extract of Premna obtusifolia (Indian headache tree), which is active against colorectal cancer after probation through computational screening methods as it passed through the set parameters of pharmacokinetics (most important nonblood–brain barrier permeant) and drug likeliness (e.g., Lipinski’s, Ghose’s, Veber’s rule) which most other phytoconstituents failed to pass combined with docking with EGFR protein which is highly upregulated in the colorectal carcinoma cell. The structure of 7-acetylhorminone was confirmed by single crystal X-ray diffraction studies and 1H NMR, 13C NMR, and COSY studies. To validate the theoretical studies, first, in vitro experiments were carried out against human colorectal carcinoma cell lines (HCT116) which revealed the potent cytotoxic efficacy of 7-acetylhorminone and verified preliminary investigation. Second, the drugability of 7-acetylhorminone interaction with serum albumin proteins (HSA and BSA) is evaluated both theoretically and experimentally via steady-state fluorescence spectroscopic studies, circular dichroism, isothermal titration calorimetry, and molecular docking. In summary, this study reveals the applicability of 7-acetylhorminone as a potent drug candidate or as a combinatorial drug against colorectal cancer. KW - Molecular docking KW - In situ synthesis KW - ADMET PY - 2024 DO - https://doi.org/10.1021/acsabm.4c00335 VL - 7 IS - 5 SP - 3414 EP - 3430 PB - American Chemical Society (ACS) AN - OPUS4-61114 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Paris, O. A1 - Li, C. A1 - Siegel, S. A1 - Weseloh, G. A1 - Emmerling, Franziska A1 - Riesemeier, Heinrich A1 - Erko, A. A1 - Fratzl, P. T1 - A new experimental station for simultaneous X-ray microbeam scanning for small- and wide-angle scattering and fluorescence at BESSY II N2 - A new instrument for simultaneous microbeam small- and wide-angle X-ray scattering and X-ray fluorescence (SAXS/WAXS/XRF) is presented. The instrument is installed at the microfocus beamline at BESSY II and provides a beam of 10 µm size with a flux of about 109 photons s-1. A SAXS resolution up to 500 Å d-spacing and a range of scattering vectors of almost three orders of magnitude are reached by using a large-area high-resolution CCD-based detector for simultaneous SAXS/WAXS. The instrument is particularly suited for scanning SAXS/WAXS/XRF experiments on hierarchically structured biological tissues. The necessary infrastructure, such as a cryo-stream facility and an on-site preparation laboratory for biological specimens, are available. KW - Scanning SAXS KW - Scanning WAXS KW - Microbeam KW - Synchrotron radiation PY - 2007 SN - 0021-8898 SN - 1600-5767 VL - 40 IS - Supplement SP - s466 EP - s470 PB - Blackwell CY - Oxford AN - OPUS4-15049 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Parthasarathy, Thiyagaraj A1 - Bhattacharya, Biswajit A1 - Emmerling, Franziska A1 - Ghosh, Soumyajit T1 - Design of mechanically flexible photoresponsive cyanostilbene molecular crystals N2 - Photoresponsive molecular crystals have sparked interest owing to their potential application prospects. In this study, we achieved dual mechanical responses of a cyanostilbene-based crystal BN. The crystal exhibited both stress-induced mechanical flexibility and light-induced photomechanical bending. Two distinct mechanical responses are related to different underlying phenomena and were not interlinked. While elasticity is attributed to criss-cross packing arrangement in the isotropic structure, photomechanical bending is attributed to the formation of heterogeneous phase distribution due to monomer to dimer cycloaddition product formation. The crystal did not demonstrate photoswitching activity. However, it exhibited thermal reversibility, highlighting reversible dimer to monomer conversion. KW - Flexible KW - Molecular crystals PY - 2024 DO - https://doi.org/10.1039/D4CE00571F VL - 26 SP - 4634 EP - 4642 PB - Royal Society of Chemistry (RSC) AN - OPUS4-60888 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -