TY - JOUR A1 - Abbott, A. P. A1 - Abolibda, T. Z. A1 - Davis, S.J. A1 - Emmerling, Franziska A1 - Lourdin, D. A1 - Leroy, E. A1 - Wise, W. R. T1 - Glycol based plasticisers for salt modified starch N2 - Starch is one of the most common and easily obtained natural polymers, making it attractive as a potential bio-based alternative to synthetic polymers. This study shows that a simple quaternary ammonium salt combined with urea or glycols forms effective modifiers that produce flexible plastics with good mechanical properties that are comparable to some polyolefin plastics. The processing conditions are shown to significantly affect the structure of the polymer which has a concomitant effect upon the mechanical and physical properties of the resulting plastic. Using a glycerol based modifier results in a totally sustainable and biodegradable material which can be injection moulded. KW - biodegradable material KW - flexible plastics KW - injection moulded PY - 2014 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-351426 DO - https://doi.org/10.1039/C4RA06220E SN - 2046-2069 VL - 4 IS - 76 SP - 40421 EP - 40427 PB - RSC Publishing CY - London AN - OPUS4-35142 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Accorsi, M. A1 - Tiemann, M. A1 - Wehrhan, L. A1 - Finn, Lauren M. A1 - Cruz, R. A1 - Rautenberg, Max A1 - Emmerling, Franziska A1 - Heberle, J. A1 - Keller, B. G. A1 - Rademann, J. T1 - Pentafluorophosphato-Phenylalanines: Amphiphilic Phosphotyrosine Mimetics Displaying Fluorine-Specific Protein Interactions N2 - Phosphotyrosine residues are essential functional switches in health and disease. Thus, phosphotyrosine biomimetics are crucial for the development of chemical tools and drug molecules. We report here the discovery and investigation of pentafluorophosphato amino acids as novel phosphotyrosine biomimetics. A mild acidic pentafluorination protocol was developed and two PF5-amino acids were prepared and employed in peptide synthesis. Their structures, reactivities, and fluorine-specific interactions were studied by NMR and IR spectroscopy, X-ray diffraction, and in bioactivity assays. The mono-anionic PF5 motif displayed an amphiphilic character binding to hydrophobic surfaces, to water molecules, and to protein-binding sites, exploiting charge and H−F-bonding interactions. The novel motifs bind 25- to 30-fold stronger to the phosphotyrosine binding site of the protein tyrosine phosphatase PTP1B than the best current biomimetics, as rationalized by computational methods, including molecular dynamics simulations. KW - Chemical Biology KW - Drug Development KW - Pentafluorophosphates KW - Phosphotyrosine Biomimetics KW - Protein Tyrosine Phosphatases PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-549984 DO - https://doi.org/10.1002/anie.202203579 SN - 1433-7851 VL - 134 IS - 25 SP - 1 EP - 6 PB - Wiley-VCH GmbH AN - OPUS4-54998 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Adhami, Forogh A1 - Safavi, Maliheh A1 - Ehsani, Maryam A1 - Ardestani, Sussan K. A1 - Emmerling, Franziska A1 - Simyari, Farzaneh T1 - Synthesis, crystal structure, and cytotoxic activity of novel cyclic systems in [1,2,4]thiadiazolo[2,3-a]pyridine benzamide derivatives and their copper(ii) complexes N2 - Three N-(pyridine-2-ylcarbamothioyl)benzamide derivatives were synthesized by the reaction of potassium thiocyanate, benzoyl chloride, and 2-amino pyridine derivatives in one pot. The obtained derivatives were oxidized using copper(II) chloride. During the oxidation, two hydrogen atoms were removed, cyclization of the derivatives occurred, and finally, three new N-(2H-[1,2,4]thiadiazolo[2,3-a]pyridine-2-ylidene)benzamide derivatives were produced. Coordination of these three new derivative ligands to the copper(II) ion resulted in the formation of three new complexes: dichlorobis(N-(2H-[1,2,4]thiadiazolo[2,3-a]pyridine-2-ylidene)benzamide)copper(II), dichlorobis(N-(7-methyl-2H-[1,2,4]thiadiazolo[2,3-a]pyridine-2ylidene)benzamide)copper(II), and dichlorobis(N-(5-methyl-2H-[1,2,4]thiadiazolo[2,3-a]pyridine-2-ylidene)benzamide)copper(II). All the synthesized products were characterized by IR, 1H NMR, and 13C NMR spectroscopies. Crystal structures of the obtained N-(pyridine-2-ylcarbamothioyl)benzamide derivatives, N-(2H-[1,2,4]thiadiazolo[2,3-a]pyridine-2-ylidene)benzamide derivatives, and complexes were determined using X-ray single-crystal diffraction; the positions of atoms, bond lengths, bond angles, and dihedral angles were also determined. In all complexes, the coordination of two large monodentate ligands and two chloride anions to the copper(II) ion resulted in the formation of a stable planar geometry around the central ion. Three N-(pyridine-2-ylcarbamothioyl)benzamide derivatives, three N-(2H-[1,2,4]thiadiazolo[2,3-a]pyridine-2-ylidene)benzamide derivatives, and three complexes were evaluated for their cytotoxicity against five human cancer cell lines (breast cancer cell line MDA-MB-231, neuroblastoma cell line SK-N-MC, prostate adenocarcinoma cell line LNCap, nasopharyngeal epidermoid carcinoma cell line KB, and liver cancer cell line HEPG-2) using an in vitro analysis. The N-(pyridine-2-ylcarbamothioyl)benzamide derivatives showed no cytotoxic activity, whereas the N-(2H-[1,2,4]thiadiazolo[2,3-a]pyridine-2-ylidene)benzamide derivatives and their complexes showed significant cytotoxicity, especially against MDA-MB-231 and LNCap cell lines. The complexes demonstrated smaller IC50 values than N-(2H-[1,2,4]thiadiazolo[2,3-a]pyridine-2-ylidene)benzamide derivatives. KW - Copper complexes PY - 2014 DO - https://doi.org/10.1039/c3dt52905c SN - 1477-9226 VL - 43 IS - 21 SP - 7945 EP - 7957 PB - Royal Society of Chemistry (RSC) AN - OPUS4-65449 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Aichmayer, B. A1 - Wiedemann-Bidlack, F. B. A1 - Gilow, C. A1 - Simmer, J.P. A1 - Yamakoshi, Y. A1 - Emmerling, Franziska A1 - Margolis, H.C. A1 - Fratzl, P. T1 - Amelogenin nanoparticles in suspension: Deviations from spherical shape and pH-dependent aggregation N2 - It is well-known that amelogenin self-assembles to form nanoparticles, usually referred to as amelogenin nanospheres, despite the fact that not much is known about their actual shape in solution. In the current paper, we combine SAXS and DLS to study the three-dimensional shape of the recombinant amelogenins rP172 and rM179. Our results show for the first time that amelogenins build oblate nanoparticles in suspension using experimental approaches that do not require the proteins to be in contact with a support material surface. The SAXS studies give evidence for the existence of isolated amelogenin nano-oblates with aspect ratios in the range of 0.45-0.5 at pH values higher than pH 7.2 and show an aggregation of these nano-oblates at lower pH values. The role of the observed oblate shape in the formation of chain-like structures at physiological conditions is discussed as a key factor in the biomineralization of dental enamel. KW - Enamel KW - Recombinant amelogenin KW - rP172 KW - rM179 KW - Self-assembly KW - SAXS KW - DLS KW - Shape KW - Nanospheres KW - Oblates KW - pH dependency PY - 2010 DO - https://doi.org/10.1021/bm900983b SN - 1525-7797 VL - 11 IS - 2 SP - 369 EP - 376 PB - ACS Publ. CY - Washington, DC, USA AN - OPUS4-20939 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Akhmetova, Irina A1 - Beyer, Sebastian A1 - Schutjajew, K. A1 - Tichter, T. A1 - Wilke, Manuel A1 - Prinz, Carsten A1 - B. Martins, Inês C. A1 - Al-Sabbagh, Dominik A1 - Roth, C. A1 - Emmerling, Franziska T1 - Cadmium benzylphosphonates - the close relationship between structure and properties N2 - Cadmium benzylphosphonate Cd(O3PBn)·H2O and its fluorinated derivates Cd(O3PBn-3F)·H2O, Cd(O3PBn-4F)·H2O, and Cd(O3PBn-F5)·H2O were synthesized mechanochemically. The Crystal structures of the compounds were determined based on powder X-ray diffraction (PXRD) data. The influence of the ligand substitution on the crystal structure of the metal phosphonate was determined. The hydrophobicity as a function of degree of fluorination was investigated using dynamic vapor sorption. KW - Mechanochemistry KW - Metal phosphonates KW - PXRD KW - DVS PY - 2019 DO - https://doi.org/10.1039/c9ce00776h VL - 21 SP - 5958 EP - 5964 PB - RSC Royal Society of Chemistry AN - OPUS4-49930 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Akhmetova, Irina A1 - Schuzjajew, K. A1 - Wilke, M. A1 - de Oliveira Guilherme Buzanich, Ana A1 - Rademann, K. A1 - Roth, C. A1 - Emmerling, Franziska T1 - Synthesis, characterization and in situ monitoring of the mechanochemical reaction process of two manganese(II)-phosphonates with N-containing ligands N2 - Two divalent manganese aminophosphonates, manganese mono (nitrilotrimethylphosphonate) (MnNP3) and manganese bis N-(carboxymethyl)iminodi(methylphosphonate)) (Mn(NP2AH)2), have been prepared by mechanochemical synthesis and characterized by powder X-ray diffraction (PXRD). The structure of the novel compound Mn(NP2AH)2 was determined from PXRD data. MnNP3 as well as Mn(NP2AH)2 exhibits a chain-like structure. In both cases, the manganese atom is coordinated by six oxygen atoms in a distorted octahedron. The local coordination around Mn was further characterized by extended X-ray absorption fine structure. The synthesis process was followed in situ by synchrotron X-ray diffraction revealing a three-step reaction mechanism. The asprepared manganese(II) phosphonates were calcined on air. All samples were successfully tested for their suitability as catalyst material in the oxygen evolution reaction. KW - Mechanochemistry KW - In situ KW - XRD PY - 2018 DO - https://doi.org/10.1007/s10853-018-2608-6 SN - 0022-2461 SN - 1573-4803 VL - 53 IS - 19 SP - 13390 EP - 13399 PB - Springer Science + Business Media B.V. AN - OPUS4-45673 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Al-Terkawi, Abdal-Azim A1 - Prinz, Carsten A1 - Scholz, Gudrun A1 - Kemnitz, Erhard A1 - Emmerling, Franziska T1 - Ca-, Sr-, and Ba-Coordination polymers based on anthranilic acid via mechanochemistry N2 - Ca-, Sr-, and Ba-Based coordination polymers (CPs) were prepared mechanochemically by milling metal-hydroxide samples with anthranilic acid (oABAH). {[Ca(oABA)2(H2O)3]}n consists of one-dimensional polymeric chains that are further connected by a hydrogen-bonding network. {[Sr(oABA)2(H2O)2]·H2O}n is a one-dimensional CP in which water molecules bridge Sr2+ ions and increase the dimensionality by building an extended network. {[Ba(oABA)2(H2O)]}n crystallizes as a two-dimensional CP comprising one bridging water molecule. The cation radii influence the inorganic connectivity and dimensionality of the resulting crystal structures. The crystal structures were refined from powder X-ray diffraction data using the Rietveld method. The local coordination environments were studied via extended X-ray absorption fine structure (EXAFS) measurements. The compounds were further characterized using comprehensive analytical methods such as elemental analysis, thermal analysis, MAS NMR, imaging, and dynamic vapor sorption (DVS) measurements. Compounds 1, 2, and 3 exhibit small surface areas which decrease further after thermal annealing experiments. All compounds exhibit a phase transformation upon heating, which is only reversible in 3. KW - Mechanochemistry KW - XRD PY - 2019 DO - https://doi.org/10.1039/c9dt00991d SN - 1477-9226 SN - 1477-9234 VL - 48 IS - 19 SP - 6513 EP - 6521 PB - Royal Society of Chemistry AN - OPUS4-48014 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Al-Terkawi, Abdal-Azim A1 - Scholz, G. A1 - de Oliveira Guilherme Buzanich, Ana A1 - Reinsch, Stefan A1 - Kemnitz, E. A1 - Emmerling, Franziska T1 - Ca- and Sr- tetrafluoroisophthalates: mechanochemical synthesis, characterization, and ab initio structure determination N2 - New fluorinated coordination polymers were prepared mechanochemically by milling the alkaline earth metal hydroxides MII(OH)2·xH2O (MII: Ca, Sr) with tetrafluoroisophthalic acid (H2mBDC-F4). The structures of [{Ca(mBDC-F4)(H2O)2}·H2O] and [{Sr(mBDC-F4)(H2O)2}·H2O] were determined based on ab initio calculations and their powder X-ray diffraction (PXRD) data. The compounds are isomorphous and crystallize in the orthorhombic space group P212121. The determined structures were validated by using extended X-ray absorption (EXAFS) data. The new materials were thoroughly characterized using elemental analysis, thermal analysis, magic angle spinning NMR, and attenuated total reflection-infrared spectroscopy. Further characterization methods such as BET, dynamic vapor sorption, and scanning electron microscopy imaging were also used. Our investigations indicate that mechanochemistry is an efficient method for preparing such materials. KW - Mechanochemistry KW - In situ KW - XRD KW - Coordination polymers PY - 2017 UR - http://pubs.rsc.org/-/content/articlehtml/2017/dt/c7dt00734e DO - https://doi.org/10.1039/c7dt00734e VL - 46 IS - 18 SP - 6003 EP - 6012 AN - OPUS4-41516 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Al-Terkawi, Abdal-Azim A1 - Scholz, G. A1 - Emmerling, Franziska A1 - Kemnitz, E. T1 - Mechanochemical synthesis, characterization, and structure determination of new alkaline earth metal-tetrafluoroterephthalate frameworks: Ca(pBDC‑F4 )·4H2O, Sr(pBDC‑F4 )·4H2O, and Ba(pBDC‑F4 ) N2 - New fluorinated alkaline earth metal−organic frameworks were successfully synthesized by milling of metal hydroxides M(OH)2 with tetrafluoroterephthalic acid H2 pBDC-F4. Both calcium- and strontium-tetrafluoroterephthalates are tetrahydrated, while the barium tetrafluoroterephthalate is free of coordinating water molecules. The two isomorphic structures Ca(pBDC-F4)·4H2O and Sr(pBDC-F4)·4H2O were solved from the powder diffraction data by ab initio structure determination and subsequent Rietveld refinement. The products were thoroughly characterized by elemental analysis, thermal analysis, magicangle spinning NMR, Fourier transform infrared spectroscopy, scanning electron microscopy imaging, and Brunauer−Emmett−Teller measurements. Our findings suggest that the mechanochemical synthesis route is a promising approach for the preparation of new fluorinated alkaline earth metal−organic frameworks. KW - Mechanochemistry KW - MOFs KW - XRD PY - 2016 UR - http://pubs.acs.org/doi/abs/10.1021/acs.cgd.5b01457 DO - https://doi.org/10.1021/acs.cgd.5b01457 SN - 1528-7483 VL - 16/4 SP - 1923 EP - 1933 PB - American Chemical Society CY - Washington, DC, USA AN - OPUS4-35940 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Al-Terkawi, Abdal-Azim A1 - Scholz, G. A1 - Emmerling, Franziska A1 - Kemnitz, E. T1 - Strontium-coordination polymers based on tetrafluorophthalic and phthalic acids: mechanochemical synthesis, ab initio structures determination, and spectroscopic characterization N2 - Two strontium-based dicarboxylate systems [Sr(oBDC-F4)(H2O)2] (1) and [{Sr(oBDC)(H2O)2)·H2O] (2) were synthesized mechanochemically via milling of Sr(OH)2·8H2O with tetrafluorophthalic acid (H2oBDC-F4) or phthalic acid (H2oBDC), respectively. The new structures were determined ab initio from the powder X-ray diffraction (PXRD) data. Both compounds 1 and 2 crystallize in the monoclinic space group P21 /c as two-dimensional coordination polymers (2D-CPs). The determined structures were validated by extended X-ray absorption (EXAFS) data. Compounds 1 and 2 show different thermal stabilities. The fluorinated CP 1 is decomposed at 300 °C while the nonfluorinated CP 2 transforms into a new phase after thermal treatment at 400 °C. The two hydrated CPs exhibit small surface areas which increase after the thermal posttreatment for 1 but remains unchanged for the dehydrated sample of 2. Dynamic vapor sorption (DVS) experiments indicate that both the dehydrated and hydrated samples of 2 depict no significant differences in their adsorption isotherms. The DVS of water indicates that the phase transition after thermal posttreatment of 2 is irreversible. KW - Mechanochemistry KW - XRD KW - NMR PY - 2017 DO - https://doi.org/10.1039/c7dt02564e SN - 1477-9226 SN - 1477-9234 VL - 46 IS - 37 SP - 12574 EP - 12587 PB - The Royal Society of Chemistry CY - Cambridge AN - OPUS4-42261 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Al-Terkawi, Abdal-Azim A1 - Scholz, G. A1 - Prinz, Carsten A1 - Zimathies, Annett A1 - Emmerling, Franziska A1 - Kemnitz, E. T1 - Hydrated and dehydrated Ca-coordination polymers based on benzene-dicarboxylates: mechanochemical synthesis, structure refinement, and spectroscopic characterization N2 - A series of Ca-based coordination polymers were prepared mechanochemically by milling Ca(OH)2 with phthalic acid (H2oBDC), isophthalic acid (H2mBDC), and terephthalic acid (H2pBDC). The hydrated compounds [Ca(oBDC)(H2O)], [Ca(mBDC)(H2O)3.4], and [Ca(pBDC)(H2O)3] were prepared for the first time via mechanochemical routes. The refined structures were validated by extended X-ray absorption data. The new dehydrated compound [Ca(oBDC)] (1-H2O), obtained after the thermal post-treatment of 1 in a reversible phase transition process, was determined ab initio based on the powder X-ray diffraction (PXRD) data. The materials were thoroughly characterized using elemental analysis, thermal analysis, and spectroscopic methods: magic-angle spinning NMR and attenuated total reflection-infrared spectroscopy. The specific surface areas and sorption properties of the hydrated and dehydrated samples were determined using the isotherms of gas sorption and dynamic vapor sorption measurements. KW - Mechanochemistry KW - XRD PY - 2018 UR - http://pubs.rsc.org/en/content/articlehtml/2017/ce/c7ce01906h DO - https://doi.org/10.1039/C7CE01906H VL - 20 SP - 946 EP - 961 PB - Royal Society of Chemistry AN - OPUS4-44440 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Al-Terkawi, Abdal-Azim A1 - Scholz, Gudrun A1 - Emmerling, Franziska A1 - Kemnitz, Erhard T1 - Barium coordination polymers based on fluorinated and fluorine-free benzene-dicarboxylates: Mechanochemical synthesis and spectroscopic characterization N2 - A series of new Ba-based coordination polymers (CPs) were mechanochemically synthesized by milling Ba-hydroxide samples with perfluorinated and fluorine-free benzene-dicarboxylic acids, including tetrafluoroisophthalic acid (H2mBDC-F4), tetrafluorophthalic acid (H2oBDC-F4), isophthalic acid (H2mBDC) and phthalic acid (H2oBDC). The new fluorinated CPs: [Ba(mBDC-F4)$0.5H2O] (1) and [Ba(oBDC-F4)·1.5H2O] (2) are compared to their nonfluorinated counterparts: [Ba(mBDC)·2.5H2O] (3), and [Ba(oBDC)·1H2O] (4). These materials are thoroughly characterized using powder X-ray diffraction. The products obtained by milling are all hydrated but vary in their water contents. Compositions and local structures are investigated by elemental analysis, thermal analysis, MAS NMR and attenuated total reflectioninfrared spectroscopy. These materials exhibit high thermal stabilities but small surface areas that remain unchanged even after thermal treatments. KW - Mechanochemical synthesis KW - Barium KW - Fluorine KW - Coordination polymers KW - PXRD KW - MAS NMR spectroscopy PY - 2018 UR - https://www.sciencedirect.com/science/article/pii/S1293255817310798 DO - https://doi.org/10.1016/j.solidstatesciences.2018.03.013 SN - 1293-2558 SN - 1873-3085 VL - 79 SP - 99 EP - 108 PB - Elsevier AN - OPUS4-44880 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Al-Terkawi, Abdal-Azim A1 - Scholz, Gudrun A1 - Emmerling, Franziska A1 - Kemnitz, Erhard T1 - Ca-Tetrafluorophthalate and Sr-isophthalate: mechanochemical synthesis and characterization in comparison with other Ca-and Sr-coordination polymers N2 - New Ca- and Sr-based coordination polymers (CPs) were mechanochemically synthesized by milling metal hydroxide samples (M = Ca, Sr) with tetrafluorophthalic acid (H2oBDC-F4) and isophthalic acid (H2mBDC). [Ca(oBDC-F4)(H2O)2] (1) exhibits a small surface area which is slightly increased after removing the crystal water. On the other hand, the hydrated sample of the nonfluorinated [Sr(mBDC)(H2O)3.4] (2) reveals a small BET surface area which remains unchanged even after the release of crystal water via thermal treatment. The new compounds 1 and 2 are similar to their Sr- and Ca-analogs, respectively. These findings are confirmed by thermal analysis, MAS NMR, and ATR-IR measurements, in addition to the Le Bail refinements for the measured powder X-ray data of 1 and 2. Ca- and Sr-CPs based on perfluorinated dicarboxylic systems and their nonfluorinated analogs diverse in structural and chemical properties depending on the geometries of the organic linkers and the presence of fluorine atoms. The fluorinations of organic ligands lead to the formation of fluorinated CPs with higher dimensionalities compared to their nonfluorinated counterparts. Conversely, the thermal stabilities of the latter are higher than those of the fluorinated CPs. KW - Mechanochemistry PY - 2018 DO - https://doi.org/10.1039/c8dt00695d SN - 1477-9226 SN - 1477-9234 VL - 47 IS - 16 SP - 5743 EP - 5754 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-44696 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Alić, Jasna A1 - Schlegel, Moritz-Caspar A1 - Emmerling, Franziska A1 - Stolar, Tomislav T1 - Meeting the UN Sustainable Development Goals with Mechanochemistry N2 - Chemistry traditionally relies on reactions in solution, but this method is increasingly problematic due to the scale of chemical processes and their economic and environmental impact. Handling residual chemical waste, including solvents, incurs significant costs and environmental pressure. Conversely, novel chemical approaches are needed to address pressing societal issues such as climate change, energy scarcity, food insecurity, and waste pollution. Mechanochemistry, a sustainable chemistry discipline that uses mechanical action to induce chemical reactivity without bulk solvents, is a hot topic in academic research on sustainable and green chemistry. Given its fundamentally different working principles from solution chemistry, mechanochemistry offers more efficient chemical processes and the opportunity to design new chemical reactions. Mechanochemistry has a profound impact on many urgent issues facing our society and it is now necessary to use mechanochemistry to address them. This Minireview aims to provide a guide for using mechanochemistry to meet the United Nations (UN) Sustainable Development Goals (SDGs), thereby contributing to a prosperous society. Detailed analysis shows that mechanochemistry connects with most UN SDGs and offers more cost‐efficiency than other approaches together with a superior environmental performance. KW - Mechanochemistry KW - SDGs PY - 2024 DO - https://doi.org/10.1002/anie.202414745 SP - 1 EP - 3 PB - Wiley AN - OPUS4-61108 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 - 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 - TY - JOUR A1 - Balski, Matthias A1 - Emmerling, Franziska A1 - Kipphardt, Heinrich A1 - Panne, Ulrich T1 - Determination of boron in silicon without use of additional complexing agents N2 - Methods for the determination of boron in various matrices described in the literature usually employ complexing agents like mannitol to retain the volatile boron species during matrix evaporation steps. However, also relatively high boron recoveries from silicon containing samples have been reported when no complexing agents were added to the digestion acids. The mechanism behind this matrix-dependant recovery has been investigated by studying the boron recovery in the analysis of solar grade silicon. It was found that the NH4+ ion formed by the reduction of nitric acid during sample digestion is responsible for the higher recovery of boron, which leads to a possible analysis method without the use of complexing agents if the sample preparation procedure is carefully optimized. KW - Boron KW - Complexing agents KW - Matrix evaporation KW - Sample enrichment PY - 2014 DO - https://doi.org/10.1039/c4ay00410h SN - 1759-9660 SN - 1759-9679 VL - 6 IS - 12 SP - 4003 EP - 4008 PB - RSC Publ. CY - Cambridge AN - OPUS4-30956 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Baláž, Matej A1 - Birinci, Mustafa A1 - Şentürk, Kader A1 - Achimovičová, Marcela A1 - Baláž, Peter A1 - Tampubolon, Imelda Octa A1 - Stolar, Tomislav A1 - Bienert, Ralf A1 - Emmerling, Franziska A1 - Erdemoğlu, Sema A1 - Sis, Hikmet A1 - Erdemoğlu, Murat T1 - Utilizing Taguchi method and in situ X-ray powder diffraction monitoring to determine the influence of mechanical activation conditions on the physico-chemical properties and Al leachability of K-feldspar N2 - K-feldspar represents an important natural resource of potassium and aluminum. Within the framework of this study, the K-feldspar was mechanically activated in a planetary ball mill under different conditions planned according to 43 Taguchi orthogonal array experimental design. As outputs, specific surface area (SBET), median particle size (d50), amorphization degree of mineral phases , and Al recovery were used. It was found that the initial d50 value of 293 μm could be reduced to 6.7 μm and the SBET value of 4.7 m2/g could be increased up to 32.5 m2/g upon milling. Both microcline KAl3SiO8, and albite NaAl3SiO8 could be almost completely amorphized, whereas quartz SiO2 still maintained some crystallinity even under the most intensive conditions. Increasing SBET and decreasing the d50 values did not lead to a significant improvement in Al leach recovery, whereas a clear relationship between the amorphization of microcline and the recovered aluminum was found. Analysis of Variance (ANOVA) showed that increasing ball-to-powder ratio is the most beneficial for the improvement in Al recovery. In situ powder X-ray diffraction monitoring performed in an oscillation ball mill under synchrotron irradiation has shown very rapid amorphization of microcline phase at the beginning. However, amorphization of microcline was only partial after two hours of the treatment in this mill, apart from almost complete process in the planetary ball mill. In the end, regressions for the calculation of Al recovery by knowing the values of input parameters were calculated. In general, by just using mechanical activation without the subsequent roasting process that is commonly used to boost metal recoveries, it was possible to quantitatively recover aluminum from K-feldspar. KW - Mechanochemistry KW - Mechanical activation KW - Design of experiments PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-611059 DO - https://doi.org/10.1016/j.jmrt.2024.08.156 SN - 2238-7854 VL - 32 SP - 3886 EP - 3895 PB - Elsevier B.V. AN - OPUS4-61105 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Batteas, James A1 - Blank, Kerstin G. A1 - Colacino, Evelina A1 - Emmerling, Franziska A1 - Friščić, Tomislav A1 - Mack, James A1 - Moore, Jeffrey A1 - Rivas, Maria Elena A1 - Tysoe, Wilfred T1 - Moving mechanochemistry forward N2 - Arguably mechanochemistry is one of the oldest, and at the same time one of the newest, areas of chemistry. One of the oldest, because it has been theorized that early hominids were able to develop rapidly due to their ability to heat and mechanically process their food to make it easier to digest. Old, because the ancient Greeks knew that mechanically activating stones (consisting of cinnabar) with vinegar in a copper pestle and mortar caused them to convert into mercury. We might be forgiven for thinking that this could have led our alchemical forbears to wonder if there were other stones that might also be persuaded to convert into gold. Early chemical luminaries such as Michael Faraday and Wilhelm Röntgen dabbled in mechanochemistry. However, in the late 19th and early 20th centuries, the field developed separately in many areas. Perhaps most significantly, synthetic chemists realized that reactions could be carried out with surprisingly high yields and selectivities by shaking them in a ball mill, and that they could even make novel compounds that their colleagues just using heat were not able to. Physicists were mechanically rearranging atoms into new configurations (i.e., doing chemistry) using exotic means such as atomic force microscope tips and optical tweezers. Scientists and engineers studying the formation of lubricious and anti-wear films realized that they were mechanochemically formed. Biochemists found molecular motor proteins, such as myosin and kinesin, that were able to convert chemical energy into motion or, vice versa, mechanical energy into the biochemical energy storage molecule adenosine triphosphate. In 2023, this confluence of advances convinced the Royal Society of Chemistry that the time was ripe to establish a new journal dedicated to the field of mechanochemistry. It is rare that a journal has the privilege of helping to create a new sub-branch of chemistry but, having done so, it has the obligation of helping to define the field and, optimistically, suggesting how the field might develop. This editorial has two major goals. The first is to bring to the attention of the scientific community the challenges faced by the field to set people thinking about how they might contribute and, second, to form the basis for more thorough discussions in the future. The sub-topics below outline current thoughts brought forward from members of our editorial board. We lay out areas and topics here with the intent of establishing a new editorial series, which we invite the community to contribute to, and outline topics and hopefully lay out challenges, which will enable us as a community to come together to move mechanochemistry forward. KW - Mechanochemistry PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-646086 DO - https://doi.org/10.1039/d4mr90021a SN - 2976-8683 VL - 2 IS - 1 SP - 10 EP - 19 PB - Royal Society of Chemistry (RSC) AN - OPUS4-64608 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Batzdorf, Lisa A1 - Emmerling, Franziska T1 - Mechanochemical synthesis and characterisation of cocrystals and metal-organic compounds N2 - The mechanochemical synthesis of two model compounds, a metal organic framework ([Bi(1,4-bdc)2]*(Im) (bdc = benzene dicarboxylate, Im = imidazole cation)) and a cocrystal (Carbamazepine:Indometacin 1:1) were followed ex situ by combined analytical methods. Powder X-ray diffraction (XRD) and Raman spectroscopy data were evaluated for the synthesis of the metal organic framework. XRD measurements and REM images were analysed for the synthesis of the cocrystal. The measurements revealed that both model compounds were synthesised within minutes. The metal organic framework [Bi(1,4-bdc)2]*(Im) is synthesised via an intermediate structure. The cocrystal Carbamazepine:Indometacin 1:1 is formed within few seconds and afterwards the crystallite size decreases extremely. KW - Powder X-ray diffraction (XRD) KW - Raman spectroscopy KW - mechanochemical synthesis PY - 2014 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-306305 UR - http://pubs.rsc.org/en/content/articlepdf/2014/fd/c3fd00163f DO - https://doi.org/10.1039/C3FD00163F SN - 1359-6640 SN - 1364-5498 N1 - Geburtsname von Batzdorf, Lisa: Tröbs, L. - Birth name of Batzdorf, Lisa: Tröbs, L. SP - 109 EP - 119 PB - RSC CY - Cambridge [u.a.] AN - OPUS4-30630 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Batzdorf, Lisa A1 - Fischer, Franziska A1 - Wilke, Manuel A1 - Wenzel, Klaus-Jürgen A1 - Emmerling, Franziska T1 - Direct in situ investigation of milling reactions using combined x-ray diffraction and raman spectroscopy N2 - The combination of two analytical methods including time-resolved in situ X-ray diffraction (XRD) and Raman spectroscopy provides a new opportunity for a detailed analysis of the key mechanisms of milling reactions. To prove the general applicability of our setup, we investigated the mechanochemical synthesis of four archetypical model compounds, ranging from 3D frameworks through layered structures to organic molecular compounds. The reaction mechanism for each model compound could be elucidated. The results clearly show the unique advantage of the combination of XRD and Raman spectroscopy because of the different information content and dynamic range of both individual methods. The specific combination allows to study milling processes comprehensively on the level of the molecular and crystalline structures and thus obtaining reliable data for mechanistic studies. PY - 2015 DO - https://doi.org/10.1002/anie.201409834 SN - 1433-7851 SN - 1521-3773 SN - 0570-0833 VL - 54 IS - 6 SP - 1799 EP - 1802 PB - Wiley-VCH CY - Weinheim AN - OPUS4-34630 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Batzdorf, Lisa A1 - Nguyen, Thi Yen A1 - Rump, Doreen A1 - Emmerling, Franziska T1 - Crystallization behavior of carbamazepine N2 - Carbamazepine (CBZ) is known for its variety of anhydrous and hydrous polymorphs. Herein, a thorough analysis of the crystallization behavior of CBZ is presented. The influence of the solvent and the concentration on the crystallization behavior under different environmental conditions is investigated by combined in situ XRD and Raman spectroscopy measurements. Crystallization studies conducted via conventional crystallization in glass tubes and in levitated droplets using an acoustic levitator indicate a dependence of the crystallization process from solvent and surface. KW - Carbamazepine KW - Polymorphism KW - Acoustic levitation KW - XRD KW - Raman spectroscopy PY - 2014 DO - https://doi.org/10.1515/zpch-2013-0452 SN - 0942-9352 SN - 2196-7156 SN - 0044-3336 SN - 0044-3328 N1 - Geburtsname von Batzdorf, Lisa: Tröbs, L. - Birth name of Batzdorf, Lisa: Tröbs, L. VL - 228 IS - 4-5 SP - 493 EP - 501 PB - Oldenbourg CY - München AN - OPUS4-30627 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Batzdorf, Lisa A1 - Wilke, Manuel A1 - Szczerba, Wojciech A1 - Reinholz, Uwe A1 - Emmerling, Franziska T1 - Mechanochemical synthesis and characterisation of two new bismuth metal organic frameworks N2 - Two metal organic structures composed of the ligands benzene-1,4-dicarboxylate and pyridine-2,5-dicarboxylate and bismuth cations are presented: (H2Im)[Bi(1,4-bdc)2] (1) and [Bi(pydc)(NO3)2(H2O)2]*H2O (2) (bdc = benzenedicarboxylate, H2Im = imidazole cation, pydc = pyridinedicarboxylate). Both compounds were synthesised via grinding and the crystal structure of compound (2) was solved based on its powder diffraction pattern. Compound 1 crystallises isostructurally to the dimethyl ammonium containing compound (dma)[(Bi(1,4-bdc)2]. Raman spectroscopy and Extended X-ray absorption fine structure (EXAFS) measurements provided additional information about the two mechanochemically synthesised metal organic compounds. KW - Crystal structure KW - Mechanochemically synthesis KW - Powder diffraction measurements PY - 2014 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-306296 DO - https://doi.org/10.1039/C3CE42633E SN - 1466-8033 N1 - Geburtsname von Batzdorf, Lisa: Tröbs, L. - Birth name of Batzdorf, Lisa: Tröbs, L. VL - 16 IS - 25 SP - 5560 EP - 5565 CY - London, UK AN - OPUS4-30629 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Batzdorf, Lisa A1 - Zientek, Nicolai A1 - Rump, Doreen A1 - Fischer, Franziska A1 - Maiwald, Michael A1 - Emmerling, Franziska T1 - Make and break - Facile synthesis of cocrystals and comprehensive dissolution studies N2 - Mechanochemistry is increasingly used as a ‘green alternative’ for synthesizing various materials including pharmaceutical cocrystals. Herein, we present the mechanochemical synthesis of three new cocrystals containing the API carbamazepine (cocrystals CBZ:Indometacin 1:1, CBZ:Benzamide 1:1, and CBZ:Nifedipine 1:1). The mechanochemical reaction was investigated in situ documenting a fast and complete reaction within one minute. Online NMR spectroscopy proved the direct influence of the dissolution behaviour of the coformers to the dissolution behaviour of the API carbamazepine. The dissolution behaviour of the organic cocrystals is compared to the behaviour of the pure drug indicating a general applicability of this approach for detailed cocrystal dissolution studies. KW - Cocrystals KW - Carbamazepine KW - Mechanochemistry KW - Powder diffraction KW - Online NMR spectroscopy PY - 2017 DO - https://doi.org/10.1016/j.molstruc.2016.11.063 SN - 0022-2860 SN - 1872-8014 VL - 1133 SP - 18 EP - 23 AN - OPUS4-38664 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Batzdorf, Lisa A1 - Zimathies, Annett A1 - Panne, Ulrich A1 - Emmerling, Franziska T1 - Mechanochemical synthesis of [Zn3(C2O4)3(4,4'-bipy)4] and its reorganization at high temperatures N2 - The metal organic layered structure catena-(bis(µ2-4,4'-bipyridine)-tris(µ2-oxalato)-bis(4,4'-bipyridine)-tri-zinc(ii)) ([Zn3(C2O4)3(4,4'-bipy)4]) was synthesized mechanochemically applying three different routes. The synthesis succeeded by i) simultaneously neat grinding the three starting materials zinc acetate dihydrate, oxalic acid dihydrate and 4,4'bipyridine, ii) grinding two compounds and adding the third afterwards, independent of the sequence. The products were characterized using powder X-ray diffraction, Raman spectroscopy, gas adsorption measurements, and scanning electron microscopy. Temperature-dependent synchrotron XRD measurements revealed that the monoclinic structure of [Zn3(C2O4)3(4,4'-bipy)4] rearranges reversibly to a higher ordered orthorhombic structure [Zn(C2O4)(4,4'-bipy)] at high temperatures. KW - Mechanochemistry KW - Metal organic compounds KW - Synchrotron radiation KW - Reorganization PY - 2014 DO - https://doi.org/10.1515/zpch-2014-0445 SN - 0942-9352 SN - 2196-7156 SN - 0044-3336 SN - 0044-3328 N1 - Geburtsname von Batzdorf, Lisa: Tröbs, L. - Birth name of Batzdorf, Lisa: Tröbs, L. VL - 228 IS - 4-5 SP - 575 EP - 585 PB - Oldenbourg CY - München AN - OPUS4-30628 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Belenguer, A. A1 - Lampronti, G. A1 - Michalchuk, Adam A1 - Emmerling, Franziska A1 - Sanders, J. T1 - Quantitative reversible one pot interconversion of three crystalline polymorphs by ball mill grinding N2 - We demonstrate here using a disulfide system the first example of reversible, selective, and quantitative transformation between three crystalline polymorphs by ball mill grinding. This includes the discovery of a previously unknown polymorph. Each polymorph is reproducibly obtained under well-defined neat or liquid-assisted grinding conditions, revealing subtle control over the apparent thermodynamic stability. We discovered that the presence of a contaminant as low as 1.5% mol mol−1 acting as a template is required to enable all these three polymorph transformations. The relative stabilities of the polymorphs are determined by the sizes of the nanocrystals produced under different conditions and by surface interactions with small amounts of added solvent. For the first time, we show evidence that each of the three polymorphs is obtained with a unique and reproducible crystalline size. This mechanochemical approach gives access to bulk quantities of metastable polymorphs that are inaccessible through recrystallisation. KW - Mechanochemistry KW - Polymorph KW - XRD PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-549934 DO - https://doi.org/10.1039/D2CE00393G SP - 1 EP - 7 PB - Royal Society of Chemistry AN - OPUS4-54993 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Belombe, M.M. A1 - Nenwa, J. A1 - Emmerling, Franziska T1 - Stacking structure of quinolinium hydrogensquarate N2 - A new proton-transfer organic salt, quinolinium hydrogensquarate (C13H9NO4), has been synthesized and fully characterized by single crystal x-ray diffraction. The salt crystallizes in the monoclinic space group P21/n with the parameters: a = 3.8290(12) Å, b = 20.960(6) Å, c = 13.802(4) Å, β = 95.452(5)°, V = 1102.7(6) Å3, Z = 4 formula units. The structure consists of uncommon supramolecular neutral dimers which pile up parallel to [100] forming infinite sheets. These centrosymmetric dimers are held together by lateral hydrogen-bonds whereby two neighboring coplanar hydrogensquarate anions act as a bridge between two terminal quinolinium cations and C-H...O bridgings interlink next neighboring sheets. The bulk structure of this salt is consolidated by weak π–π interactions within the sheets which are neatly ordered side-by-side relative to one another. KW - Quinolinium squarate KW - Supramolecular dimer KW - Crystal structure KW - Proton-transfer salt PY - 2011 SN - 0973-4945 VL - 8 IS - 2 SP - 603 EP - 608 CY - Tamil Nadu AN - OPUS4-24627 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bentrup, U. A1 - Radnik, J. A1 - Armbruster, U. A1 - Martin, A. A1 - Leiterer, Jork A1 - Emmerling, Franziska A1 - Brückner, A. T1 - Linking simultaneous in situ WAXS/SAXS/Raman with Raman/ATR/UV-vis spectroscopy: comprehensive insight into the synthesis of molybdate catalyst precursors N2 - A new setup is presented which enables simultaneous wide- and small-angle X-ray scattering (WAXS/SAXS) and Raman spectroscopic experiments during the synthesis of Mo-based mixed oxide catalyst precursors at the µ-spot beamline at the Berliner Elektronenspeicherring-Gesellschaft für Synchrotronstrahlung (BESSY). Furthermore, we report about the separate monitoring of the same reactions under comparable conditions by simultaneous combined ATR/UV–vis/Raman spectroscopic measurements. For testing the performance of both experimental setups two syntheses were described comprising the precipitation of metal molybdates by mixing solutions of metal nitrates and ammonium heptamolybdate. Additionally, the effect of H3PO4 admixture on precipitation was investigated. The combined evaluation of spectroscopic and WAXS/SAXS data allows the discrimination between different molybdate species appearing in solution and precipitate. Furthermore, these molybdate species could be assigned to separate phases of different crystallinity. KW - In situ KW - WAXS/SAXS KW - Raman KW - ATR KW - UV-vis KW - Mixed oxide catalyst KW - Synthesis PY - 2009 DO - https://doi.org/10.1007/s11244-009-9309-y SN - 1022-5528 VL - 52 IS - 10 SP - 1350 EP - 1359 PB - Springer Science + Business Media CY - Dordrecht AN - OPUS4-19794 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bernardes, C. E. S. A1 - Feliciano, I.O. A1 - Naese, Christoph A1 - Emmerling, Franziska A1 - Minas da Piedade, M. T1 - Energetics of dehydroepiandrosterone polymorphs I and II from solution and drop-sublimation Calvet microcalorimetry measurements N2 - The lattice enthalpies and monotropic relationship of two dehydroepiandrosterone (DEHA) polymorphs (forms I and II) were evaluated through a combination of differential scanning calorimetry (DSC), isothermal solution microcalorimetry, and drop-sublimation Calvet microcalorimetry experiments. The standard molar enthalpy of transition between both forms was determined as ΔtrsHom (II→I, 298.15 K) = - 0.90 ± 0.07 kJ mol-1 and ΔtrsHom (II→I, 417.8 K) = - 1.7 ± 1.0 kJ mol- 1, from measurements of standard molar enthalpies of solution in dimethyl sulfoxide and enthalpies of fusion, respectively. Drop-sublimation Calvet microcalorimetry experiments on form I led to ΔsubHom (cr I, 298.15 K) = 132.0±3.3 kJ mol - 1. This result, when combined with the more precise ΔtrsHom (II→I) value obtained by solution calorimetry, afforded ΔsubHom (cr II, 298.15 K) = 131.1±3.3 kJ mol - 1. The overall data indicate that on enthalpic grounds form I is more stable than form II from 298.15 K up to fusion. This conclusion, and the fact that DSC experiments indicated that form I has also a considerably higher temperature fusion, namely, Tfus(cr I)= 422.5±0.2 K and Tfus(cr II) = 413.1±0.2 K, suggest that the two polymorphs are monotropically related. KW - Calorimetry KW - Polymorphism KW - Enthalpy of solution KW - Enthalpy of sublimation KW - Thermochemistry KW - Lattice enthalpy PY - 2023 DO - https://doi.org/10.1016/j.jct.2023.107137 SN - 0021-9614 SN - 1096-3626 VL - 186 SP - 1 EP - 7 PB - Elsevier AN - OPUS4-58418 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - 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 - Beyer, Sebastian A1 - Schürmann, Robin A1 - Feldmann, Ines A1 - Blocki, A. A1 - Bald, Ilko A1 - Schneider, Rudolf A1 - Emmerling, Franziska T1 - Maintaining Stable Zeolitic Imidazolate Framework (ZIF) Templates during Polyelectrolyte Multilayer Coating N2 - Equipping ZIF particles with a polyelectrolyte membrane provides functional groups at their interface, enabling further conjugations necessary for applications such as targeted drug delivery. Previous approaches to coat ZIF particles with polyelectrolytes led to surface corrosion of the template material. This work overcomes previous limitations by performing a Layer-by-Layer (LbL) polyelectrolyte coating onto ZIF-8 and ZIF-67 particles in nonaqueous environment. Using the 2-methylimidazolium salt of polystyrensulfonic acid instead of the acid itself and polyethyleneimine in methanol led to intact ZIF particles after polyelectrolyte coating. This was verified by electron microscopy. Further, zetapotential and atomic force microscopy measurements confirmed a continuous polyelectrolyte multilayer built up. The here reported adaption to the well-studied (LbL) polyelectrolyte selfassembly process provides a facile method to equip ZIF particles with a nanometer thin polyelectrolyte multilayer membrane. KW - Zeolithe KW - Molecular Organic Frameworks KW - MOF KW - ZIF KW - Layer-by-Layer KW - Beschichtung KW - Polyelektrolyt PY - 2018 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-447729 DO - https://doi.org/10.1016/j.colcom.2017.11.004 SN - 2215-0382 VL - 22 SP - 14 EP - 17 PB - Elsevier B.V. CY - Amsterdam, NL AN - OPUS4-44772 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bhattacharya, Biswajit A1 - Michalchuk, Adam A1 - Silbernagl, Dorothee A1 - Rautenberg, Max A1 - Schmid, Thomas A1 - Feiler, Torvid A1 - Reimann, K. A1 - Ghalgaoui, A. A1 - Sturm, Heinz A1 - Paulus, B. A1 - Emmerling, Franziska T1 - A Mechanistic Perspective on Plastically Flexible Coordination Polymers N2 - Mechanical flexibility in single crystals of covalently bound materials is a fascinating and poorly understood phenomenon. We present here the first example of a plastically flexible one-dimensional (1D) coordination polymer. The compound [Zn(m-Cl)2(3,5-dichloropyridine)2]n is flexible over two crystallographic faces. Remarkably, the single crystal remains intact when bent to 1808. A combination of microscopy, diffraction, and spectroscopic studies have been used to probe the structural response of the crystal lattice to mechanical bending. Deformation of the covalent polymer chains does not appear to be responsible for the observed macroscopic bending. Instead, our results suggest that mechanical bending occurs by displacement of the coordination polymer chains. Based on experimental and theoretical evidence, we propose a new model for mechanical flexibility in 1D coordination polymers. Moreover, our calculations propose a cause of the different mechanical properties of this compound and a structurally similar elastic material KW - Coordination polymer KW - Flexible crystals KW - Mechanical properties KW - Plastic deformation PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-504755 DO - https://doi.org/10.1002/anie.201914798 VL - 59 IS - 14 SP - 5557 EP - 5561 PB - Wiley-VCH AN - OPUS4-50475 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bhattacharya, Biswajit A1 - Michalchuk, Adam A1 - Silbernagl, Dorothee A1 - Yasuda, N. A1 - Feiler, Torvid A1 - Sturm, Heinz A1 - Emmerling, Franziska T1 - An atomistic mechanism for elasto-plastic bending in molecular crystals N2 - Mechanically flexible single crystals of molecular materials offer potential for a multitude of new directions in advanced materials design. Before the full potential of such materials can be exploited, insight into their mechanisms of action must be better understood. Such insight can be only obtained through synergistic use of advanced experimentation and simulation. We herein report the first detailed mechanistic study of elasto-plastic flexibility in a molecular solid. An atomistic origin for this mechanical behaviour is proposed through a combination of atomic force microscopy, μ-focus synchrotron X-ray diffraction, Raman spectroscopy, ab initio simulation, and computed elastic tensors. Our findings suggest that elastic and plastic bending are intimately linked and result from extensions of the same molecular deformations. The proposed mechanism bridges the gap between contested mechanisms, suggesting its applicability as a general mechanism for elastic and plastic bending in organic molecular crystals. KW - Mechanical property KW - Mechanical flexibility KW - Organic crystal PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-577722 DO - https://doi.org/10.1039/D2SC06470G SN - 2041-6520 VL - 14 IS - 13 SP - 3441 EP - 3450 PB - Royal Society of Chemisty (RSC) CY - London/Cambridge AN - OPUS4-57772 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bienert, Ralf A1 - Emmerling, Franziska A1 - Thünemann, Andreas T1 - The size distribution of 'gold standard' nanoparticles N2 - The spherical gold nanoparticle reference materials RM 8011, RM 8012, and RM 8013, with a nominal radius of 5, 15, and 30 nm, respectively, have been available since 2008 from NIST. These materials are recommended as standards for nanoparticle size measurements and for the study of the biological effects of nanoparticles, e.g., in pre-clinical biomedical research. We report on determination of the size distributions of these gold nanoparticles using different small-angle X-ray scattering (SAXS) instruments. Measurements with a classical Kratky type SAXS instrument are compared with a synchrotron SAXS technique. Samples were investigated in situ, positioned in capillaries and in levitated droplets. The number-weighted size distributions were determined applying model scattering functions based on (a) Gaussian, (b) log-normal, and (c) Schulz distributions. The mean radii are 4.36 ± 0.04 nm (RM 8011), 12.20 ± 0.03 nm (RM 8012), and 25.74 ± 0.27 nm (RM 8013). Low polydispersities, defined as relative width of the distributions, were detected with values of 0.067 ± 0.006 (RM 8011), 0.103 ± 0.003, (RM 8012), and 0.10 ± 0.01 (RM 8013). The results are in agreement with integral values determined from classical evaluation procedures, such as the radius of gyration (Guinier) and particle volume (Kratky). No indications of particle aggregation and particle interactions-repulsive or attractive-were found. We recommend SAXS as a standard method for a fast and precise determination of size distributions of nanoparticles. KW - Small-angle scattering KW - Reference materials KW - Metrology KW - Nanoparticles PY - 2009 DO - https://doi.org/10.1007/s00216-009-3049-5 SN - 1618-2642 SN - 1618-2650 VL - 395 IS - 6 SP - 1651 EP - 1660 PB - Springer CY - Berlin AN - OPUS4-20473 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bornemann-Pfeiffer, Martin A1 - Wolf, Jakob A1 - Meyer, Klas A1 - Kern, S. A1 - Angelone, D. A1 - Leonov, A. A1 - Cronin, L. A1 - Emmerling, Franziska T1 - Standardization and control of Grignard reactions in a universal chemical synthesis machine using online NMR T1 - Standardisierung und Kontrolle von Grignard-Reaktionen mittels Online-NMR in einer universellen chemischen Syntheseplattform N2 - A big problem with the chemistry literature is that it is not standardized with respect to precise operational parameters, and real time corrections are hard to make without expert knowledge. This lack of context means difficult reproducibility because many steps are ambiguous, and hence depend on tacit knowledge. Here we present the integration of online NMR into an automated chemical synthesis machine (CSM aka. “Chemputer” which is capable of small-molecule synthesis using a universal programming language) to allow automated analysis and adjustment of reactions on the fly. The system was validated and benchmarked by using Grignard reactions which were chosen due to their importance in synthesis. The system was monitored in real time using online-NMR, and spectra were measured continuously during the reactions. This shows that the synthesis being done in the Chemputer can be dynamically controlled in response to feedback optimizing the reaction conditions according to the user requirements. N2 - Ein Problem der chemischen Literatur ist die fehlende Standardisierung bezüglich genauer Bedingungen, auch Echtzeit-Korrekturen sind ohne Expertenwissen nur schwer möglich. Dieser Mangel an Details erschwert experimentelle Reproduzierbarkeit, da Schritte oft mehrdeutig sind und daher von implizitem Wissen abhängen. Hier präsentieren wir die Integration von Online-NMR Spektroskopie in eine automatisierte chemische Syntheseplattform (CSM aka. “Chemputer”, unter Verwendung einer universellen Programmiersprache zur Synthese kleiner Moleküle fähig), um eine automatisierte Analyse und Anpassung von Reaktionen im laufenden Betrieb zu ermöglichen. Das System wurde anhand von Grignard-Reaktionen, die aufgrund ihrer Bedeutung für die Synthese ausgewählt wurden, validiert und einem Härtetest unterzogen. Synthesen wurden in Echtzeit mit Online-NMR überwacht, und die Spektren wurden während der Reaktionen kontinuierlich aufgenommen und analysiert. Dies zeigt, dass der Chemputer dynamisch mittels einer Regelung kontrolliert werden kann, um die Reaktionsbedingungen entsprechend den Anforderungen des Benutzers zu optimieren. KW - Grignard reaction KW - NMR spectroscopy KW - Process analytical technology KW - Process control KW - Grignard-Reaktion KW - NMR-Spektroskopie KW - Prozessanalytik KW - Prozesskontrolle PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-531260 DO - https://doi.org/10.1002/anie.202106323 SN - 1521-3773 SN - 1433-7851 N1 - Bibliografische Angaben für die deutsche Version: Angewandte Chemie 2021, Jg. 133, S. 1–7, ISSN 0044-8249, ISSN 1521-3757, https://doi.org/10.1002/ange.202106323 - Bibliographic information for the German version: Angewandte Chemie 2021, vol. 133, p. 1–7, ISSN 0044-8249, ISSN 1521-3757, https://doi.org/10.1002/ange.202106323 VL - 60 IS - 43 SP - 1 EP - 6 PB - Wiley-VCH CY - Weinheim AN - OPUS4-53126 LA - mul AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bothe, Martin A1 - Emmerling, Franziska A1 - Pretsch, Thorsten T1 - Poly(ester urethane) with varying polyester chain length: Polymorphism and shape-memory behavior N2 - The swelling, viscoelastic, and mechanical behavior of phase-segregated poly(ester urethane) (PEU) block copolymers, composed of 4,4'-methylenediphenyl diisocyanate, 1,4-butanediol as a chain extender, and crystallizable poly(1,4-butylene adipate) (PBA) with molecular weights between 1330 and 4120 g mol-1, are investigated. Wide-angle X-ray scattering (WAXS) is employed to study the overall PEU crystallinity, which increases from 8.6 to 13.6% at higher PBA contents. The existence of two crystalline, polymorphic PBA phases, a thermodynamically stable α phase and a metastable β phase, is confirmed by further WAXS measurements. Calorimetric and thermomechanical investigations give evidence for controllable PBA polymorphic behavior. The crystallization conditions, like the cooling rate, affect the emerging polymorphic mixture, whereas the storage conditions either promote or inhibit the polymorphic (β to α) transition. The introduced concepts represent a new approach for gaining control over programmable thermo­responsiveness, which may be transferable to other shape-memory polymers with polymorphic switching segments. KW - Shape-memory polymers KW - Stimuli-sensitive polymers KW - Poly(ester urethane) KW - Polymorphism PY - 2013 DO - https://doi.org/10.1002/macp.201300464 SN - 1022-1352 SN - 1521-3935 VL - 214 IS - 23 SP - 2683 EP - 2693 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-29892 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Brandenburg, E. A1 - von Berlepsch, H. A1 - Leiterer, Jork A1 - Emmerling, Franziska A1 - Koksch, B. T1 - Formation of alpha-helical nanofibers by mixing beta-structured and alpha-helical coiled coil peptides N2 - The helical coiled coil is a well-studied folding motif that can be used for the design of nanometer-sized bioinspired fibrous structures with potential applications as functional materials. A two-component system of coiled coil based model peptides is investigated, which forms, under acidic conditions, uniform, hundreds of nanometers long, and ~2.6 nm thick trimeric α-helical fibers. In the absence of the other component and under the same solvent conditions, one model peptide forms β-sheet-rich amyloid fibrils and the other forms stable trimeric α-helical coiled coils, respectively. These observations reveal that the complementary interactions driving helical folding are much stronger here than those promoting the intermolecular β-sheet formation. The results of this study are important in the context of amyloid inhibition but also open up new avenues for the design of novel fibrous peptidic materials. PY - 2012 DO - https://doi.org/10.1021/bm300882d SN - 1525-7797 VL - 13 IS - 11 SP - 3542 EP - 3551 PB - ACS Publ. CY - Washington, DC, USA AN - OPUS4-27126 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Breitfeld, Steffen A1 - Scholz, G. A1 - Emmerling, Franziska A1 - Kemnitz, E. T1 - BaF-benzenedicarboxylate: the first mechanochemical N2 - Anewbariumcoordination polymer, BaF-benzenedicarboxylate (BaF(p-BDC)0.5), with fluorine directly coordinated to the metal cation, was prepared by mechanochemical synthesis routes. Phase-pure BaF-benzenedicarboxylate was synthesized by milling starting either from barium hydroxide or from Barium acetate as sources for barium cations. In both cases, the second reactant was 1,4-benzenedicarboxylic acid (H2(p-BDC)). Ammonium fluoride was used as fluorinating agent directly at milling. This is the first mechanochemical synthesis of coordination polymers where fluorine is directly coordinated to the metal cation. Following the second possibility, barium acetate fluoride (Ba(OAc)F) is formed as ntermediate product after milling, and the new coordination polymer is accessible only after washing with water and dimethyl sulfoxide. The new compound BaF(p-BDC)0.5 was characterized by X-ray powder diffraction, FTIR-, and 19F, 1H-13C CP MAS NMR spectroscopies, DTA-TG, and elemental Analysis. KW - Milling KW - MOF PY - 2018 DO - https://doi.org/10.1007/s10853-018-2331-3 SN - 0022-2461 VL - 53 IS - 19 SP - 13682 EP - 13689 PB - Springer AN - OPUS4-45677 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bui, M. A1 - Hoffmann, K. F. A1 - Braun, T. A1 - Riedel, S. A1 - Heinekamp, Christian A1 - Scheurell, K. A1 - Scholz, G. A1 - Stawski, Tomasz A1 - Emmerling, Franziska T1 - An Amorphous Teflate Doped Aluminium Chlorofluoride: A Solid Lewis-Superacid for the Dehydrofluorination of Fluoroalkanes N2 - Ananion-dopedaluminiumchlorofluoride AlCl0.1F2.8(OTeF5)0.1(ACF-teflate) was synthesized.The material contains pentafluor-oorthotellurate(teflate)groups, which mimic fluoride ions electronically, but are sterically more demanding. They are embedded into the amorphous structure. The latter was studied by PDF analysis, EXAFS data and MAS NMR spectroscopy. The mesoporous powder is a Lewis superacid, and ATR-IR spectra of adsorbed CD3CN reveal a blue-shift of the adsorption band by73 cm-1, which is larger than the shift for SbF5. Remarkably,ACF-teflate catalyzes dehydrofluorination reactions of mono-fluoroalkanes to yield olefins in C6D6. In these cases,no Friedel-Crafts products were formed. KW - Aluminium fluorides KW - Aluminium teflates KW - C-F bond activation KW - Lewis superacids KW - Silanes PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-572290 DO - https://doi.org/10.1002/cctc.202300350 SN - 1867-3880 SP - 1 EP - 7 PB - Wiley VHC-Verlag AN - OPUS4-57229 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bui, Minh A1 - Heinekamp, Christian A1 - Fuhry, Emil A1 - Weidner, Steffen A1 - Radnik, Jörg A1 - Ahrens, Mike A1 - Scheurell, Kerstin A1 - Balasubramanian, Kannan A1 - Emmerling, Franziska A1 - Braun, Thomas T1 - Lewis-acid induced mechanochemical degradation of polyvinylidene fluoride: transformation into valuable products N2 - Polyvinylidene fluoride (–[CH2CF2]n–, PVDF) waste poses significant environmental challenges due to its recalcitrant nature and widespread use. This study addresses the end-of-life management of PVDF by introducing a novel, sustainable mechanochemical approach for its valorisation. We investigated the degradation of PVDF into value-added materials using ball milling with anhydrous AlCl3 to achieve a quantitative mineralisation producing AlF3 and halide-functionalised graphite, along with gaseous products (HCl and CH4). Mechanistic key steps involve Lewis-acid catalysed C–F bond activation, dehydrofluorination and aromatisation. This approach provides an effective solution for PVDF waste management while offering a promising route for the production of high-value materials from polymer waste streams. Our findings contribute to sustainable practices in polymer recycling and resource recovery, respond to pressing environmental concerns associated with fluoropolymer disposal, and demonstrate the potential to convert polymer wastes into useful products. KW - Mechanochemistry KW - Polyvinylidenfluoride KW - Degradation KW - Ball mill PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-649015 DO - https://doi.org/10.1039/d5sc05783c SN - 2041-6520 VL - 16 IS - 40 SP - 18903 EP - 18910 PB - Royal Society of Chemistry (RSC) AN - OPUS4-64901 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Burek, K. A1 - Dengler, J. A1 - Emmerling, Franziska A1 - Feldmann, Ines A1 - Kumke, M. U. A1 - Stroh, Julia T1 - Lanthanide Luminescence Revealing the Phase Composition in Hydrating Cementitious Systems N2 - The hydration process of Portland cement in a cementitious system is crucial for development of the high-quality cementbased construction material. Complementary experiments of Xray diffraction analysis (XRD), scanning electron microscopy (SEM) and time-resolved laser fluorescence spectroscopy (TRLFS) using europium (Eu(III)) as an optical probe are used to analyse the hydration process of two cement systems in the absence and presence of different organic admixtures. We Show that different analysed admixtures and the used sulphate carriers in each cement system have a significant influence on the hydration process, namely on the time-dependence in the formation of different hydrate phases of cement. Moreover, the effect of a particular admixture is related to the type of sulphate carrier used. The quantitative information on the amounts of the crystalline cement paste components is accessible via XRD analysis. Distinctly different morphologies of ettringite and calcium-silicate-hydrates (C-S-H) determined by SEM allow visual conclusions about formation of these phases at particular ageing times. The TRLFS data provides information about the admixture influence on the course of the silicate reaction. The dip in the dependence of the luminescence decay times on the hydration time indicates the change in the structure of C-S-H in the early hydration period. Complementary information from XRD, SEM and TRLFS provides detailed information on distinct periods of the cement hydration process. KW - Cement admixtures KW - Cement hydration KW - Europium KW - Luminescence KW - SEM KW - X-ray diffraction PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-504842 DO - https://doi.org/10.1002/open.201900249 VL - 8 IS - 12 SP - 1441 EP - 1452 PB - Wiley-VCH AN - OPUS4-50484 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bélombé, M.M. A1 - Nenwa, J. A1 - Emmerling, Franziska T1 - Crystal structure of quinolinium trans-diaquabis(oxalato-O,O')-chromate(III), [C9H8N] [Cr(H2O)2(C2O4)2] PY - 2009 DO - https://doi.org/10.1524/ncrs.2009.0106 SN - 1433-7266 VL - 224 IS - 2 SP - 239 EP - 240 PB - Oldenbourg CY - München AN - OPUS4-19711 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Cakir, Cafer Tufan A1 - Bogoclu, Can A1 - Emmerling, Franziska A1 - Streli, Christina A1 - de Oliveira Guilherme Buzanich, Ana A1 - Radtke, Martin T1 - Machine learning for efficient grazing-exit x-ray absorption near edge structure spectroscopy analysis: Bayesian optimization approach N2 - In materials science, traditional techniques for analyzing layered structures are essential for obtaining information about local structure, electronic properties and chemical states. While valuable, these methods often require high vacuum environments and have limited depth profiling capabilities. The grazing exit x-ray absorption near-edge structure (GE-XANES) technique addresses these limitations by providing depth-resolved insight at ambient conditions, facilitating in situ material analysis without special sample preparation. However, GE-XANES is limited by long data acquisition times, which hinders its practicality for various applications. To overcome this, we have incorporated Bayesian optimization (BO) into the GE-XANES data acquisition process. This innovative approach potentially reduces measurement time by a factor of 50. We have used a standard GE-XANES experiment, which serve as reference, to validate the effectiveness and accuracy of the BO-informed experimental setup. Our results show that this optimized approach maintains data quality while significantly improving efficiency, making GE-XANES more accessible to a wider range of materials science applications. KW - Machine Learning KW - GE-XANES KW - Bayesian Optimization PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-603955 DO - https://doi.org/10.1088/2632-2153/ad4253 VL - 5 IS - 2 SP - 1 EP - 12 PB - IOP Publishing AN - OPUS4-60395 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Cakir, Cafer Tufan A1 - Piotrowiak, T. A1 - Reinholz, Uwe A1 - Ludwig, A. A1 - Emmerling, Franziska A1 - Streli, C. A1 - de Oliveira Guilherme Buzanich, Ana A1 - Radtke, Martin T1 - Exploring the Depths of Corrosion: A Novel GE-XANES Technique for Investigating Compositionally Complex Alloys N2 - In this study, we propose the use of nondestructive, depth-resolved, element-specific characterization using grazing exit X-ray absorption near-edge structure spectroscopy (GE-XANES) to investigate the corrosion process in compositionally complex alloys (CCAs). By combining grazing exit X-ray fluorescence spectroscopy (GE-XRF) geometry and a pnCCD detector, we provide a scanning-free, nondestructive, depth-resolved analysis in a sub-micrometer depth range, which is especially relevant for layered materials, such as corroded CCAs. Our setup allows for spatial and energy-resolved measurements and directly extracts the desired fluorescence line, free from scattering events and other overlapping lines. We demonstrate the potential of our approach on a compositionally complex CrCoNi alloy and a layered reference sample with known composition and specific layer thickness. Our findings indicate that this new GE-XANES approach has exciting opportunities for studying surface catalysis and corrosion processes in real-world materials. KW - Degradation mechanisms KW - Grazin exit XANES KW - Depth resolved XANES KW - Compositional complex alloys KW - Corrosion PY - 2023 DO - https://doi.org/10.1021/acs.analchem.3c00404 VL - 95 SP - 4810 EP - 4818 PB - ACS Publications AN - OPUS4-57823 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Carvalho, José Joao A1 - Emmerling, Franziska A1 - Schneider, Rudolf T1 - 7-(5-Carboxypentyl)-1,3-dimethylxanthine monohydrate N2 - The title compound [systematic name: 6-(1,3-dimethyl-2,6-dioxo-2,3,6,7-tetrahydro-1H-purin-7-yl)hexanoic acid monohydrate, CAS 61444-23-3], C13H18N4O4·H2O, was synthesized and crystallized from ethyl acetate. Hydrogen bonds between xanthine and water molecules contribute to the formation of layers parallel to (10). KW - Kristallstruktur KW - Koffein KW - Antikörperentwicklung KW - Biokonjugate PY - 2007 DO - https://doi.org/10.1107/S1600536807037257 SN - 1600-5368 VL - 63 IS - 9 SP - o3718 PB - Munksgaard CY - Copenhagen AN - OPUS4-15731 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Casali, C. A1 - Feiler, Torvid A1 - Heilmann, Maria A1 - Braga, D. A1 - Emmerling, Franziska A1 - Grepioni, F. T1 - Too much water? Not enough? In situ monitoring of the mechanochemical reaction of copper salts with dicyandiamide N2 - n situ monitoring of mechanochemical reactions between dicyandiamide (DCD) and CuX2 salts (X = Cl−, NO3−), for the preparation of compounds of agrochemical interest, showed the appearance of a number of phases. It is demonstrated that milling conditions, such as the amount of water added in wet grinding and/or the milling frequency, may affect the course of the mechanochemical reactions, and drive the reaction towards the formation of different products. It has been possible to discover by in situ monitored experiments two novel crystalline forms, namely the neutral complexes [Cu(DCD)2(OH2)2(NO3)2] (2) and [Cu(DCD)2(OH2)Cl2]·H2O (4), in addition to the previously known molecular salt [Cu(DCD)2(OH2)2][NO3]2·2H2O (1, DIVWAG) and neutral complex [Cu(DCD)2(OH2)Cl2] (3, AQCYCU), for which no synthesis conditions were available. Compounds 2 and 4 were fully characterized via a combination of solid-state techniques, including X-ray diffraction, Raman spectroscopy and TGA. KW - Mechanochemistry KW - In situ PY - 2022 DO - https://doi.org/10.1039/d1ce01670a VL - 24 IS - 6 SP - 1292 EP - 1298 PB - RSC AN - OPUS4-54344 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Casali, L. A1 - Broll, V. A1 - Ciurili, S. A1 - Braga, D. A1 - Emmerling, Franziska A1 - Gepioni, F. T1 - Facilitating Nitrification Inhibition through Green, Mechanochemical Synthesis of a Novel Nitrapyrin Complex N2 - Nitrapyrin (NP) is applied to cultivated soils to inhibit the enzymatic activity of ammonia monooxygenase (AMO), but its poor aqueous solubility and high volatility severely limit its application. β-Cyclodextrin (β-CD) is commonly used to form inclusion complexes with hydrophobic molecules, improving water solubility and stability upon complexation. Here we report on the mechanochemical synthesis of the inclusion complex β-CD·NP, characterized via a combination of solid-state techniques, including exsitu and in situ X-ray diffraction, Raman and NMR spectroscopies, transmission electron microscopy, and energy dispersive X-ray spectroscopy. The pure inhibitor NP was also structurally characterized. The β-CD·NP complex presents improved solubility and thermal stability, and still inhibits the enzymatic activity of AMO with high efficacy. All results indicate that the inclusion of NP into β-CD represents a viable route for the preparation of a novel class of inhibitors, with improved properties related to stability, water solubility, and good inhibition activity. KW - Mechanochemistry KW - Nitrification PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-537154 DO - https://doi.org/10.1021/acs.cgd.1c00681 SN - 1528-7505 VL - 21 IS - 10 SP - 5792 EP - 5799 PB - ACS Publications AN - OPUS4-53715 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Casali, Lucia A1 - Carta, Maria A1 - Michalchuk, Adam A1 - Delogu, Francesco A1 - Emmerling, Franziska T1 - Kinetics of the mechanically induced ibuprofen–nicotinamide co-crystal formation by in situ X-ray diffraction N2 - Mechanochemistry is drawing attention from the pharmaceutical industry given its potential for sustainable material synthesis and manufacture. Scaling mechanochemical processes to industrial level remains a challenge due to an incomplete understanding of their underlying mechanisms. We here show how time-resolved in situ powder X-ray diffraction data, coupled with analytical kinetic modelling, provides a powerful approach to gain mechanistic insight into mechanochemical reactions. By using the ibuprofen–nicotinamide co-crystal mechanosynthesis as a benchmark system, we investigate the behaviour of the solids involved and identify the factors that promote the reaction. As mechanochemical mechanisms become increasingly clear, it promises to become a breakthrough in the industrial preparation of advanced pharmaceuticals. KW - Mechanochemistry KW - Kinetics PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-608820 DO - https://doi.org/10.1039/D4CP01457J SN - 1463-9084 VL - 26 SP - 22041 EP - 22048 PB - Royal Society of Chemistry (RSC) CY - Cambridge AN - OPUS4-60882 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Chakraborty, Gouri A1 - Das, Prasenjit A1 - Bhattacharya, Biswajit A1 - Prinz, Carsten A1 - Emmerling, Franziska A1 - Thomas, Arne T1 - Room-temperature superprotonic conductivity in COOH-functionalized multicomponent covalent organic frameworks N2 - In solid materials, the development of hydrogen bonding (H-bonding) networks within pores is crucial for efficient proton conductance. In this study, a chemically stable carboxylic acid-functionalized, quinoline-linked 2D microporous covalent organic framework (COF) (Qy-COOH) was synthesized using the Doebner multicomponent reaction (MCR) and compared to a similar framework lacking the –COOH functionality (Qy-H), prepared via an MC Domino reaction. The proton conductivity of the –COOH-functionalized MCR-COF was significantly enhanced, reaching 10−2 S cm−1, attributed to strong H-bonding interactions between water molecules and the dangling –COOH groups within the COF pores. In contrast, the analogous Qy-H framework exhibited a much lower proton conductivity of 10−5 S cm−1, while an imine-based COF showed only 10−6 S cm−1. This work represents the first demonstration of a general strategy to achieve efficient proton conduction in a class of layered 2D –COOH-functionalized COFs, offering superprotonic conductivity without requiring additives at room temperature. The MCR-COF design approach provides a promising pathway for developing highly stable and high-performance proton-conducting materials. KW - Multicomponebt KW - COF KW - Proton Conductivity KW - Superprotonic PY - 2026 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-653526 DO - https://doi.org/10.1039/D5SC06953J SN - 2041-6520 SP - 1 EP - 9 PB - Royal Society of Chemistry (RSC) AN - OPUS4-65352 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Chapartegui-Arias, Ander A1 - Raysyan, A. A1 - Belenguer, A. M. A1 - Jaeger, Carsten A1 - Tchipilov, Teodor A1 - Prinz, Carsten A1 - Abad Andrade, Carlos Enrique A1 - Beyer, S. A1 - Schneider, Rudolf A1 - Emmerling, Franziska T1 - Tailored mobility in a zeolite imidazolate framework (ZIF) antibody conjugate N2 - Zeolitic imidazolate framework (ZIF) hybrid fluorescent nanoparticles and ZIF antibody conjugates have been synthesized, characterized, and employed in lateral-flow immunoassay (LFIA). The bright fluorescence of the conjugates and the possibility to tailor their mobility gives a huge potential for diagnostic assays. An enzyme-linked immunosorbent assay (ELISA) with horseradish peroxidase (HRP) as label, proved the integrity, stability, and dispersibility of the antibody conjugates, LC-MS/MS provided evidence that a covalent link was established between these metal-organic frameworks and lysine residues in IgG antibodies. KW - ZIF KW - ELISA PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-532096 DO - https://doi.org/10.1002/chem.202100803 SN - 0947-6539 SN - 1521-3765 VL - 27 IS - 36 SP - 9414 EP - 9421 PB - Wiley-VCH CY - Weinheim AN - OPUS4-53209 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -