TY - JOUR A1 - Beyer, Sebastian A1 - Prinz, Carsten A1 - Schürmann, Robin A1 - Feldmann, Ines A1 - Zimathies, Annett A1 - Blocki, Anna A1 - Bald, Ilko A1 - Schneider, Rudolf A1 - Emmerling, Franziska T1 - Ultra-sonication of ZIF-67 crystals results in ZIF-67 nano-flakes N2 - Zeolitic Imidazolate Frameworks (ZIFs) are crystalline materials that comprise of metal nodes and Imidazole derivatives as linkers. ZIF-67 is often used in polymer composite materials e. g. for gas separation membranes. Post-synthesis treatment of ZIF-67 crystals with ultrasound leads to unforeseen plasticity that resulted in sintered ZIF-67 and ZIF-67 nano-flakes. Consequently, ultrasound increases the external surface area of ZIF-67 which might improve e.g. blending with polymers in composite materials. These new morphologies of ZIF-67 were characterized by transmission electron, scanning electron, and atomic force microscopy. The ultrasound treatment of ZIF-67 did not result in the formation of an amorphous framework or a meta-stable crystal structure as indicated by powder x-ray diffraction. In addition, ultra-sonicated ZIF-67 retained the high gas adsorption capacity and pore size compared to synthesized ZIF-67. The morphological changes are hard to detect with standard analytical methods that are usually utilized for MOF characterization. These findings also suggest that sonochemical treatment of ZIFs leads to structural effects beyond increasing the amount of nucleation clusters during sono-chemical synthesis, which is currently not addressed in the field. KW - ZIF PY - 2016 DO - https://doi.org/10.1002/slct.201601513 SN - 2365-6549 VL - 1 IS - 18 SP - 5905 EP - 5908 AN - OPUS4-38496 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fischer, Franziska A1 - Greiser, Sebastian A1 - Peifer, Dietmar A1 - Jäger, Christian A1 - Rademann, K. A1 - Emmerling, Franziska T1 - Mechanochemically Induced Conversion of Crystalline Benzamide Polymorphs by Seeding N2 - Benzamide has been known for its polymorphism for almost 200 years.Three polymorphic forms are described. To date,itwas only possible to crystallizeametastable form in amixture together with the thermodynamically most stable form I. Acomplete transformation of form Iinto the metastable form III by mechanochemical treatment has been achieved. Catalytic amounts of nicotinamide seeds were used to activate the conversion by mechanochemical seeding. NMR experiments indicated that the nicotinamide molecules were incorporated statistically in the crystal lattice of benzamide form III during the conversion. The transformation pathway was evaluated using in situ powder X-ray diffraction. KW - Nicotinamide KW - Benzamide KW - In situ reactions KW - Mechanochemistry KW - Polymorphs PY - 2016 DO - https://doi.org/10.1002/anie.201607358 VL - 128 IS - 46 SP - 14493 EP - 14497 PB - WILEY-VCH CY - Weinheim AN - OPUS4-38472 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wilke, Manuel A1 - Kabelitz, Anke A1 - Gorelik, T. E. A1 - de Oliveira Guilherme Buzanich, Ana A1 - Reinholz, Uwe A1 - Kolb, U. A1 - Rademann, K. A1 - Emmerling, Franziska T1 - The crystallisation of copper(II) phenylphosphonates N2 - The crystal structures and syntheses of four different copper(II) phenylphosphonates, the monophenylphosphonates α-, β-, and γ-Cu(O3PC6H5)·H2O (α-CuPhPmH (1) β-CuPhPmH (2) and γ-CuPhPmH (3)), and the diphosphonate Cu(HO3PC6H5)2·H2O (CuPhP2mH (4)), are presented. The compounds were synthesized from solution at room temperature, at elevated temperature, under hydrothermal conditions, and mechanochemical conditions. The structures of α-CuPhPmH (1) and CuPhP2mH (4) were solved from powder X-ray diffraction data. The structure of β-CuPhPmH (2) was solved by single crystal X-ray analysis. The structures were validated by extended X-ray absorption fine structure (EXAFS) and DTA analyses. Disorder of the crystal structure was elucidated by electron diffraction. The relationship between the compounds and their reaction pathways were investigated by in situ synchrotron measurements. KW - Mechanochemistry KW - Metal phosphonate KW - In situ PY - 2016 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-384217 DO - https://doi.org/10.1039/C6DT02904C SN - 1477-9226 SN - 1477-9234 VL - 45 IS - 43 SP - 17453 EP - 17463 PB - The Royal Society of Chemistry AN - OPUS4-38421 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sobina, E. A1 - Zimathis, Anett A1 - Prinz, Carsten A1 - Emmerling, Franziska A1 - de Santis Neves, R. A1 - Galhardo, C. E. A1 - De Robertis, E. A1 - WANG, H. A1 - Mizuno, K. A1 - Kurokawa, A. A1 - Unger, Wolfgang T1 - Final report of CCQM-K136 measurement of porosity properties (specific adsorption, BET specific surface area, specific pore volume and pore diameter) of nanoporous Al2O3 N2 - The CCQM-K136 key comparison for determination of the porosity properties of aluminum oxide has been organized jointly by the surface and micro/nano analysis working groups of CCQM to test the abilities of the metrology institutes to measure the porosity properties (specific adsorption, BET specific surface area, specific pore volume and pore diameter) of nanoporous Al2O3. Ural Scientific Research Institute for Metrology (UNIIM) acted as the coordinating laboratory for this comparison with BAM Federal Institute for Materials Research and Testing (BAM) as co-coordinating laboratory. Five NMIs and one DI participated in this key comparison. All participants used a gas adsorption method, here nitrogen adsorption at 77.3 K, for analysis according to the international standards ISO 15901-2 and 9277. KW - BET specific surface area KW - Specific adsorption KW - Pore diameter KW - Specific pore volume KW - Nanoporous Al2O3 PY - 2016 UR - http://iopscience.iop.org/article/10.1088/0026-1394/53/1A/08014 DO - https://doi.org/10.1088/0026-1394/53/1A/08014 SN - 0026-1394 SN - 1681-7575 VL - 2016 IS - 53 Technical Supplement SP - Article 08014, 1 EP - 39 PB - IOPscience AN - OPUS4-38282 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fischer, Franziska A1 - Lubjuhn, Dominik A1 - Greiser, Sebastian A1 - Rademann, K. A1 - Emmerling, Franziska T1 - Supply and demand in the ball mill: competitive cocrystal reactions N2 - The stability of different theophylline cocrystals under milling conditions was investigated by competitive cocrystal reactions. To determine the most stable cocrystal form under milling conditions, the active pharmaceutical ingredient theophylline was either ground with two similar coformers (benzoic acid, benzamide, or isonicotinamide), or the existing theophylline cocrystals were ground together with a competitive coformer. All competitive reactions were investigated by in situ powder X-ray diffraction disclosing the formation pathway of the milling processes. On the basis of these milling reactions, a stability order (least to most stable) was derived: tp/bs < tp/ba < tp/ina < bs/ina. KW - Mechanochemistry KW - Cocrystal KW - Milling PY - 2016 DO - https://doi.org/10.1021/acs.cgd.6b00928 SN - 1528-7483 SN - 1528-7505 VL - 16 IS - 10 SP - 5843 EP - 5851 AN - OPUS4-38097 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fischer, Franziska A1 - Wenzel, Klaus-Jürgen A1 - Rademann, K. A1 - Emmerling, Franziska T1 - Quantitative determination of activation energies in mechanochemical reactions N2 - Mechanochemical reactions often result in 100% yields of single products, making purifying procedures obsolete. Mechanochemistry is also a sustainable and eco-friendly method. The ever increasing interest in this method is contrasted by a lack in mechanistic understanding of the mechanochemical reactivity and selectivity. Recent in situ investigations provided direct insight into formation pathways. However, the currently available theories do not predict temperature T as an influential factor. Here, we report the first determination of an apparent activation energy for a mechanochemical reaction. In a temperaturedependent in situ study the cocrystallisation of ibuprofen and nicotinamide was investigated as a model system. These experiments provide a pivotal step towards a comprehensive understanding of milling reaction mechanisms. KW - Mechanochemistry KW - Cocrystal KW - Activation energy KW - Milling PY - 2016 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-377444 DO - https://doi.org/10.1039/c6cp04280e SN - 1463-9076 SN - 1463-9084 VL - 18 IS - 33 SP - 23320 EP - 23325 AN - OPUS4-37744 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bach, S. A1 - Panthöfer, M. A1 - Bienert, Ralf A1 - de Oliveira Guilherme Buzanich, Ana A1 - Emmerling, Franziska A1 - Tremel, W. T1 - Role of water during crystallization of amorphous cobalt phosphate nanoparticles N2 - The transformation of amorphous precursors into crystalline solids and the associated mechanisms are still poorly understood. We illuminate the formation and reactivity of an amorphous cobalt phosphate hydrate precursor and the role of water for its crystallization process. Amorphous cobalt phosphate hydrate nanoparticles (ACP) with diameters of ∼20 nm were prepared in the absence of additives from aqueous solutions at low concentrations and with short reaction times. To avoid the kinetically controlled transformation of metastable ACP into crystalline Co₃(PO₄)₂ × 8H₂O (CPO) its separation must be fast. The crystallinity of ACP could be controlled through the temperature during precipitation. A second amorphous phase (HT-ACP) containing less water and anhydrous Co₃(PO₄)₂ was formed at higher temperature by the release of coordinating water. ACP contains approximately five molecules of structural water per formula unit as determined by thermal analysis (TGA) and quantitative IR spectroscopy. The Co²+ coordination in ACP is tetrahedral, as shown by XANES/EXAFS spectroscopy, but octahedral in crystalline CPO. ACP is stable in the absence of water even at 500 °C. In the wet state, the transformation of ACP to CPO is triggered by the diffusion and incorporation of water into the structure. Quantitative in situ IR analysis allowed monitoring the crystallization kinetics of ACP in the presence of water. KW - Fluorapatite-gelatin nanocomposites KW - Calcium-carbonate KW - Zinc phosphate KW - Crystal-growth KW - Nucleation KW - Polymorphism PY - 2016 DO - https://doi.org/10.1021/acs.cgd.6b00208 SN - 1528-7483 SN - 1528-7505 VL - 16 IS - 8 SP - 4232 EP - 4239 PB - ACS Publications AN - OPUS4-37616 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kulla, Hannes A1 - Greiser, Sebastian A1 - Benemann, Sigrid A1 - Rademann, K. A1 - Emmerling, Franziska T1 - In Situ Investigation of a Self-Accelerated Cocrystal Formation by Grinding Pyrazinamide with Oxalic Acid N2 - A new cocrystal of pyrazinamide with oxalic acid was prepared mechanochemically and characterized by PXRD, Raman spectroscopy, solid-state NMR spectroscopy, DTA-TG, and SEM. Based on powder X-ray diffraction data the structure was solved. The formation pathway of the reaction was studied in situ using combined synchrotron PXRD and Raman spectroscopy. Using oxalic acid dihydrate the initially neat grinding turned into a rapid self-accelerated liquid-assisted grinding process by the release of crystallization water. Under these conditions, the cocrystal was formed directly within two minutes. KW - in situ KW - cocrystal KW - mechanochemistry KW - pyrazinamide KW - hydrate PY - 2016 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-372357 DO - https://doi.org/10.3390/molecules21070917 SN - 1420-3049 VL - 21 IS - 7 SP - Article 917, 1 EP - 9 AN - OPUS4-37235 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hoffmann, Holger A1 - Baldofski, Stefanie A1 - Hoffmann, Kristin A1 - Flemig, Sabine A1 - Silva, C. P. A1 - Esteves, V. I. A1 - Emmerling, Franziska A1 - Panne, Ulrich A1 - Schneider, Rudolf T1 - Structural considerations on the selectivity of an immunoassay for sulfamethoxazole N2 - Sulfamethoxazol (SMX),a sulfonamide, is a widely used bacteriostatic antibiotic and therefore a promising marker for the entry of anthropogenic Pollution in the environment. SMX is frequently found in wastewater and surface water. This study presents the production of high affinity and selective polyclonal antibodies for SMX and the development and Evaluation of a direct competitive enzyme-linked immunosorbent assay(ELISA)for the quantification of SMX in environmental watersamples. The crystal structures of the cross-reacting compounds sulfamethizole, N4-acetyl-SMX andsuccinimidyl-SMX were determined by x-ray diffraction aiming to explain their high cross-reactivity. These crystal structures are described for the first time. The quantification range of the ELISA is 0.82–63 µg/L. To verify our results, the SMX concentration in 20 environmental samples,including wastewater and surfacewater,was determined by ELISA and tandem mass spectrometry(MS/MS).A good Agreement of the measured SMX concentrations was found with average recoveries of 97–113%for the results of ELISA compared to LC-MS/MS. KW - X-Ray diffraction KW - Sulfamethoxazole KW - ELISA KW - LC-MS/MS PY - 2016 DO - https://doi.org/10.1016/j.talanta.2016.05.049 SN - 0039-9140 SN - 1873-3573 IS - 158 SP - 198 EP - 207 PB - Elsevier B.V. CY - Amsterdam, Netherlands AN - OPUS4-36676 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bach, S. A1 - Visnow, E. A1 - Panthöfer, M. A1 - Gorelik, T. A1 - de Oliveira Guilherme Buzanich, Ana A1 - Gulo, A. A1 - Kolb, U. A1 - Emmerling, Franziska A1 - Lind, C. A1 - Tremel, W. T1 - Hydrate networks under mechanical stress – A case study for Co3(PO4)2·8H2O N2 - The nature of the bound water in solids with hydrogen-bonded networks depends not only on temperature and pressure but also on the nature of the constituents. The collapse and reorientation of these network structures determines the stability of hydrated solids and transitions to other crystalline or amorphous phases. Here, we study the mechanochemically induced loss of bound water in Co₃(PO₄)₂·8H₂O and compare this process to the behavior under hydrostatic pressure. The associated phase transition and its kinetics were monitored by X-ray powder diffraction with Synchrotron radiation and quantitative IR spectroscopy. High shearing forces are responsible for the degradation of the hydrogen-bonded network and the concomitant crystalline–amorphous transformation. UV/Vis spectroscopy, extended X-ray absorption spectroscopy (EXAFS), and X-ray absorption near-edge spectroscopy (XANES) provided information about the short-range order in the amorphous solid, and thermal analysis revealed its composition and showed that the moderate charge densities of the Co²⁺ and PO₄³⁻ ions, which make the hydration enthalpy comparable to the binding energy of the counteranions, and the Formation of hydrogen-bonded networks favor multistage crystallization processes associated with the release and uptake of coordinated water. The changes of the Co²⁺ coordination induce a color change from pink to blue; therefore, Co₃(PO₄)₂·8H₂O can be used as an overheat temperature indicator. KW - Mechanochemistry KW - Amorphous materials KW - Hydrates KW - Cobalt KW - Phosphates PY - 2016 DO - https://doi.org/10.1002/ejic.201501481 SN - 1434-1948 SN - 1099-0682 VL - 2016 IS - 13-14 SP - 2072 EP - 2081 PB - Wiley-VCH Verlag GmbH & Co. KGaA CY - Weinheim, Germany AN - OPUS4-36434 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -