TY - JOUR A1 - Fischer, Franziska A1 - Scholz, G. A1 - Batzdorf, Lisa A1 - Wilke, Manuel A1 - Emmerling, Franziska T1 - Synthesis, structure determination, and formation of a theobromine: oxalic acid 2:1 cocrystal JF - CrystEngComm N2 - The structure and the formation pathway of a new theobromine : oxalic acid (2 : 1) cocrystal are presented. The cocrystal was synthesised mechanochemically and its structure was solved based on the powder X-ray data. The mechanochemical synthesis of this model compound was studied in situ using synchrotron XRD. Based on the XRD data details of the formation mechanism were obtained. The formation can be described as a self-accelerated ('liquid like') process from a highly activated species. KW - ssNMR spectroscopy KW - Synchrotron measurements KW - API molecule PY - 2015 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-331567 DO - https://doi.org/10.1039/c4ce02066a SN - 1466-8033 VL - 17 IS - 4 SP - 824 EP - 829 CY - London, UK AN - OPUS4-33156 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Nguyen, Thi Yen A1 - Rademann, K. A1 - Emmerling, Franziska T1 - Direct evidence of polyamorphism in paracetamol JF - CrystEngComm N2 - While polymorphism is a common phenomenon in the crystallization processes of organic compounds, polyamorphism has gained importance only recently. Using sophisticated sample environments and applying in situ scattering methods and vibrational spectroscopy, the complete crystallization process of organic compounds from solution can be traced and characterized. Diffuse scattering from amorphous intermediates can be investigated by analyzing the atomic pair distribution function (PDF) to gain further insights into molecular pre-orientation. The crystallization behavior of paracetamol was studied exemplarily under defined, surface-free conditions. Based on the choice of the solvent, the formation of different polymorphs is promoted. The thermodynamically stable form I and the metastable orthorhombic form II could be isolated in pure form directly from solution. For both polymorphs, the crystallization from solution proceeds via a distinct amorphous precursor phase. PDF analyses of these different amorphous states indicate a specific pre-orientation of the analyte molecules introduced by the solvent. The resulting crystalline polymorph is already imprinted in these proto-crystalline precursors. Direct experimental evidence for the polyamorphism of paracetamol is provided. PY - 2015 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-351366 DO - https://doi.org/10.1039/C5CE01583A SN - 1466-8033 VL - 17 IS - 47 SP - 9029 EP - 9036 PB - Royal Society of Chemistry CY - London, UK AN - OPUS4-35136 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kabelitz, Anke A1 - de Oliveira Guilherme Buzanich, Ana A1 - Joester, Maike A1 - Reinholz, Uwe A1 - Radtke, Martin A1 - Bienert, Ralf A1 - Schulz, K. A1 - Schmack, R. A1 - Kraehnert, R. A1 - Emmerling, Franziska T1 - Time-resolved in situ studies on the formation mechanism of iron oxide nanoparticles using combined fast-XANES and SAXS JF - CrystEngComm N2 - The reaction of iron chlorides with an alkaline reagent is one of the most prominent methods for the synthesis of iron oxide nanoparticles. We studied the particle formation mechanism using triethanolamine as reactant and stabilizing agent. In situ fast-X-ray absorption near edge spectroscopy and small-angle X-ray scattering provide information on the oxidation state and the structural information at the same time. In situ data were complemented by ex situ transmission electron microscopy, wide-angle X-ray scattering and Raman analysis of the formed nanoparticles. The formation of maghemite nanoparticles (γ-Fe2O3) from ferric and ferrous chloride was investigated. Prior to the formation of these nanoparticles, the formation and conversion of intermediate phases (akaganeite, iron(II, III) hydroxides) was observed which undergoes a morphological and structural collapse. The thus formed small magnetite nanoparticles (Fe3O4) grow further and convert to maghemite with increasing reaction time. KW - oxidation state KW - structural information KW - maghemite PY - 2015 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-351376 DO - https://doi.org/10.1039/C5CE01585E SN - 1466-8033 VL - 17 IS - 44 SP - 8463 EP - 8470 CY - London, UK AN - OPUS4-35137 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fischer, Franziska A1 - Scholz, G. A1 - Benemann, Sigrid A1 - Rademann, K. A1 - Emmerling, Franziska T1 - Evaluation of the formation pathways of cocrystal polymorphs in liquid-assisted syntheses JF - CrystEngComm N2 - The synthesis of the polymorphic cocrystal caffeine:anthranilic acid was investigated to obtain a better understanding of the processes leading to the formation of different polymorphic forms. In the case of these cocrystal polymorphs synthesized by liquid-assisted grinding a distinct influence of the dipole moment of the solvent was found. A pre-coordination between the solvent molecules and the caffeine:anthranilic acid cocrystal could be identified in the formation of form II. In the case of form II the solvent can be regarded as a catalyst. The formation pathway of each polymorph was evaluated using synchrotron X-ray diffraction. KW - cocrystal KW - synchrotron X-ray diffraction KW - caffeine PY - 2014 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-313222 DO - https://doi.org/10.1039/c4ce00472h SN - 1466-8033 VL - 16 IS - 35 SP - 8272 EP - 8278 CY - London, UK AN - OPUS4-31322 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Krause, Christina A1 - Zorn, R. A1 - Emmerling, Franziska A1 - Falkenhagen, Jana A1 - Frick, B. A1 - Huber, P. A1 - Schönhals, Andreas T1 - Vibrational density of states of triphenylene based discotic liquid crystals: dependence on the length of the alkyl chain JF - Physical chemistry, chemical physics N2 - The vibrational density of states of a series of homologous triphenylene-based discotic liquid crystals HATn (n = 5, 6, 8, 10, 12) depending on the length of the aliphatic side chain is investigated by means of inelastic neutron scattering. All studied materials have a plastic crystalline phase at low temperatures, followed by a hexagonally ordered liquid crystalline phase at higher temperatures and a quasi isotropic phase at the highest temperatures. The X-ray scattering pattern for the plastic crystalline phase of all materials shows a sharp Bragg reflection corresponding to the intercolumnar distance in the lower q-range and a peak at circa 17 nm-1 related to intracolumnar distances between the cores perpendicular to the columns as well as a broad amorphous halo related to the disordered structure of the methylene groups in the side chains in the higher q-range. The intercolumnar distance increases linearly with increasing chain length for the hexagonal columnar ordered liquid crystalline phase. A similar behaviour is assumed for the plastic crystalline phase. Besides n = 8 all materials under study exhibit a Boson peak. With increasing chain length, the frequency of the Boson peak decreases and its intensity increases. This can be explained by a self-organized confinement model. The peaks for n = 10, 12 are much narrower than for n = 5, 6 which might imply the transformation from a rigid system to a softer one with increasing chain length. Moreover the results can also be discussed in the framework of a transition from an uncorrelated to a correlated disorder with increasing n where n = 8 might be speculatively considered as a transitional state. KW - X-ray scattering KW - Neutron scattering KW - Differential scanning calorimetry PY - 2014 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-304789 DO - https://doi.org/10.1039/c3cp55303e SN - 1463-9076 SN - 1463-9084 VL - 16 IS - 16 SP - 7324 EP - 7333 PB - The Royal Soc. of Chemistry CY - Cambridge AN - OPUS4-30478 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 JF - Faraday discussions 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 - 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 JF - RSC Advances 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 - RPRT A1 - Thünemann, Andreas A1 - Emmerling, Franziska A1 - Hodoroaba, Vasile-Dan T1 - Review of existing calibration or reference T2 - The NanoDefine Consortium N2 - We report on calibration standards of nanoparticles meeting the definition of a nanomaterial given by the European Commission (EU 2011) which are relevant for the characterisation methods applied in the NanoDefine project. We found that the Impact of nanoparticles is outstanding in the scientific literature. A number of 270.000 paper titles on nanoparticles are listed in the Web of Science data base. But surprisingly, the availability of suitable certified standard reference materials is scarce. Only a few sources were found. For example, BAM provides the database Nanoscaled Reference Materials at http://www.nano-refmat.bam.de/en/ in cooperation with the ISO/TC 229 Nanotechnologies. In addition, two publications from 2013 on nanoscale reference materials are available. Candidates of nano-(certified) reference materials from other ongoing or just finished FP6 and FP7 nano-metrology projects have been extracted from the Compendium of Projects in the European NanoSafety Cluster (Compendium NSC, 2013). Recommendations for selection of representative test materials and calibration standards for NanoDefine internal tasks, respectively, are also given. KW - Nanomaterial KW - Reference materials KW - Certified reference materials PY - 2014 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-389836 UR - http://www.nanodefine.eu/index.php/downloads/nanodefine-technical-reports SP - 1 EP - 18 CY - Wageningen, The Netherlands AN - OPUS4-38983 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 JF - CrystEngComm 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 - Kuhlich, Paul A1 - Emmerling, Franziska A1 - Kraus, Werner A1 - Nehls, Irene A1 - Piechotta, Christian T1 - 1-(4-bromo-3,5,5,6,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)ethan-1-one: a precursor for phase-I metabolite of AHTN JF - Acta crystallographica E N2 - The title compound, C18H25BrO, crystallized as a racemate with four independent molecules in the asymmetric unit. In the crystal, three of these four molecules are linked via C-Br...Br-C halogen bonds [Br...Br = 3.662 (2) and 3.652 (2) Å], forming dimers. PY - 2013 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-279935 DO - https://doi.org/10.1107/S1600536813006934 SN - 1600-5368 VL - 69 IS - 4 SP - o545, sup-1 EP - sup-17 PB - Munksgaard CY - Copenhagen AN - OPUS4-27993 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kuhlich, Paul A1 - Emmerling, Franziska A1 - Piechotta, Christian A1 - Nehls, Irene T1 - Methyl 3,5,5,6,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalene-2-carboxylate (AHTN-COOMe) JF - Acta crystallographica E N2 - Crystals of the title compound, C18H26O2, were grown from ethyl acetate. Due to the racemic precursor, the title compound is also obtained as a racemate. Disorder was observed during structure refinement, originating from two possible half-chair conformations of the non-aromatic ring. The disorder was refined by introducing split positions in the cyclo-hexane ring regarding the two possible R and S-enantiomers at the chiral CH group [ratio 0.744 (3):0.256 (3)]. The crystal structure features pairs of inversion-related molecules connected by pairs of non-classical C–H···O hydrogen bonds. KW - AHTN KW - Tonalide KW - Cyclic musk KW - AHTN-COOMe KW - Disinfection by-product KW - Esterification PY - 2011 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-232769 DO - https://doi.org/10.1107/S1600536811002601 SN - 1600-5368 VL - E67 IS - 2 SP - o485, sup-1 EP - sup-11 PB - Munksgaard CY - Copenhagen AN - OPUS4-23276 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -