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 - 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 -