TY - JOUR A1 - Wilke, Manuel A1 - Akhemtova, Irina A1 - Rademann, K. A1 - Emmerling, Franziska T1 - Mechanochemical synthesis of cerium(IV)-phosphonates JF - Journal of materials science N2 - The syntheses and crystal structures of two cerium(IV) phosphonates are presented. Cerium(IV) bis(phenylphosphonate) Ce(O3PC6H5)2 1 can be formed from precipitation and mechanochemical reaction, whereas cerium(IV) bis(carboxymethylphosphonate) monohydrate Ce(O3PCH2COOH)2 H2O 2 is only accessible via ball milling. All reactions proceed very fast and are completed within a short time span. In situ measurements for the syntheses of 1 show that the product occurs within seconds or a few minutes, respectively. The structures were solved from powder X-ray diffraction data. KW - In situ studies KW - Mechanochemistry KW - XRD PY - 2018 DO - https://doi.org/10.1007/s10853-018-2507-x SN - 0022-2461 SN - 1573-4803 VL - 53 IS - 19 SP - 13733 EP - 13741 PB - Springer Science + Business Media B.V. AN - OPUS4-45672 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tumanov, I. A1 - Tumanov, E. A1 - Michalchuk, Adam T1 - Ball size or ball mass – what matters in organic mechanochemical synthesis? JF - CrystEngComm N2 - Ball mass is an important parameter that is known to have an influence on the outcome of a mechanochemical reaction induced by ball-milling. A standard way of modifying the ball mass is to change the size of the ball made of the same material. In this case, however, a change in mass is accompanied by a simulatneous change in the ball size. It is therefore not possible to disentangle the effects of mass and Surface area in these cases. In the present work we report the results of experiments with specially designed and manufactured balls in which (1) milling ball mass is held constant, but their size differs, and (2) the ball mass is altered, with the diameter of the milling ball being held constant. Using the cocrystallisation of theophylline + nicotinamide as a case study it was found that both diameter and ball mass play crucial roles in determining the rate of a mechanochemical reaction. For comparison, we have also used milling balls with the same size (different mass), and others with the same mass (different size) made of different materials, as would be “traditional”. It was found that, despite having the same size, the lightest milling ball (nylon) was the most efficient in initiating the co-crystallisation, presumably due to the sorption of EtOH. Hence, the results of this manuscript also demonstrate how milling ball material can in fact be the most influential parameter, and potentially counterintuitive to classical mechanics. KW - Mechanochemistry KW - XRD PY - 2019 DO - https://doi.org/0.1039/c8ce02109k VL - 21 SP - 2174 EP - 2179 PB - RSC Royal Society of Chemistry AN - OPUS4-47851 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Surov, Artem O. A1 - Vasilev, Nikita A. A1 - Churakov, Andrei V. A1 - Stroh, Julia A1 - Emmerling, Franziska A1 - Perlovich, German L. T1 - Solid Forms of Ciprofloxacin Salicylate: Polymorphism, Formation Pathways, and Thermodynamic Stability JF - Crystal Growth & Design N2 - The crystallization of ciprofloxacin - an antibacterial fluoroquinolone compound - with salicylic acid resulted in the isolation of five distinct solid forms of the drug, namely, an anhydrous salt, two polymorphic forms of the salt monohydrate, methanol and acetonitrile solvates, and the salt-cocrystal hydrate. The salicylate salts were investigated by different analytical techniques ranging from powder and single crystal X-ray diffractometry, differential scanning calorimetry, thermogravimetric analysis, variable temperature powder X-ray diffraction, dynamic vapor sorption analysis, dissolution, and solubility investigations. Real-time in situ Raman spectroscopy was used to investigate the mechanochemical formation pathways of the different solid polymorphs of ciprofloxacin salicylate. The mechanism of the phase transformation between the crystalline forms was evaluated under mechanochemical conditions. It was found that the formation pathway and kinetics of the grinding process depend on the form of the starting material and reaction conditions. The analysis of the solid-state thermal evolution of the hydrated salts revealed the two-step mechanism of dehydration process, which proceeds through a formation of the distinct intermediate crystalline products. KW - Cocrystal KW - Polymorphism KW - Ciprofloxacin KW - XRD KW - DSC PY - 2019 DO - https://doi.org/10.1021/acs.cgd.9b00185 SN - 1528-7483 VL - 19 IS - 5 SP - 2979 EP - 2990 PB - American Chemical Society AN - OPUS4-47903 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Surov, A. A1 - Vasilev, N. A1 - Voronin, A. A1 - Churakov, A. A1 - Emmerling, Franziska A1 - Perlovich, G. T1 - Ciprofloxacin salts with benzoic acid derivatives: structural aspects, solid-state properties and solubility performance JF - Crystengcomm N2 - n this work, three new pharmaceutical hydrated salts of ciprofloxacin with selected derivatives of benzoic acid, namely 4-hydroxybenzoic acid, 4-aminobenzoic acid and gallic acid, were obtained and systematically investigated by several solid-state analytical techniques. In situ Raman spectroscopy was applied to elucidate the alternative pathways of the solid forms' formation under mechanochemical conditions. Crystal structure analysis and a CSD survey allowed us to establish a distinct supramolecular motif formed by infinite columnar stacks of ciprofloxacin dimers arranged in the “head-to-tail” manner. An alternative “head-to-head” packing arrangement was only observed in the crystal of the hydrated ciprofloxacin salt with 4-aminobenzoic acid. In addition, the pH-solubility behavior of the solid forms was thoroughly investigated. Furthermore, a distinct structure–property relationship between the specific features of the supramolecular organization of the hydrated salts and their solubility was observed and discussed. KW - Mechanochemistry KW - XRD PY - 2020 DO - https://doi.org/10.1039/D0CE00514B VL - 22 IS - 25 SP - 4238 EP - 4249 AN - OPUS4-51818 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Stroh, Julia A1 - Ali, Naveed Zafar A1 - Maierhofer, Christiane A1 - Emmerling, Franziska T1 - Ettringite via Mechanochemistry: A Green and Rapid Approach for Industrial Application JF - ACS Omega N2 - Here, we report on a first mechanochemical synthesis of ettringite, an important cement hydrate phase. The mineral compound ettringite ([Ca3Al(OH)6]2·(SO4)3·26H2O) occurs rarely in nature, but is common for cement-based materials. Ettringite has wide technical application in the ceramic and paper industry. However, its typical wet-chemical synthesis is cumbersome and produces waste water and CO2 emissions. Here, we investigate the first mechanochemical synthesis of ettringite for developing an easy and sustainable alternative for industrial application. The mechanosynthesis was monitored in situ by coupled synchrotron X-ray diffraction (XRD) and infrared thermography (IRT). The consumption of the reactants and the formation of the reaction product were monitored with time-resolved XRD. IRT showed the temperature increase based on the exothermic reaction. The reaction conversion was significantly improved changing the strategy of the mechanosynthesis from a one- to a two-step process. The latter included neat pregrinding of solid reactants followed by a delayed addition of the stoichiometric amount of water. Thus, an increase of reaction conversion from 34 to 94% of ettringite could be achieved. KW - XRD KW - Mechanochemistry KW - Ettringite KW - In situ PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-479016 DO - https://doi.org/10.1021/acsomega.9b00560 SN - 2470-1343 VL - 4 IS - 4 SP - 7734 EP - 7737 PB - ACS Publications CY - Washington, DC AN - OPUS4-47901 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Opitz, P. A1 - Besch, L. A1 - Panthöfer, M. A1 - Kabelitz, Anke A1 - Unger, R. A1 - Emmerling, Franziska A1 - Mondeshki, M. A1 - Tremel, W. T1 - Insights into the In Vitro Formation of Apatite from Mg‐Stabilized Amorphous Calcium Carbonate JF - Advanced Functional Materials N2 - A protein‐free formation of bone‐like apatite from amorphous precursors through ball‐milling is reported. Mg2+ ions are crucial to achieve full amorphization of CaCO3. Mg2+ incorporation generates defects which strongly retard a recrystallization of ball‐milled Mg‐doped amorphous calcium carbonate (BM‐aMCC), which promotes the growth of osteoblastic and endothelial cells in simulated body fluid and has no effect on endothelial cell gene expression. Ex situ snapshots of the processes revealed the reaction mechanisms. For low Mg contents (<30%) a two phase system consisting of Mg‐doped amorphous calcium carbonate (ACC) and calcite “impurities” was formed. For high (>40%) Mg2+ contents, BM‐aMCC follows a different crystallization path via magnesian calcite and monohydrocalcite to aragonite. While pure ACC crystallizes rapidly to calcite in aqueous media, Mg‐doped ACC forms in the presence of phosphate ions bone‐like hydroxycarbonate apatite (dahllite), a carbonate apatite with carbonate substitution in both type A (OH−) and type B (PO43−) sites, which grows on calcite “impurities” via heterogeneous nucleation. This process produces an endotoxin‐free material and makes BM‐aMCC an excellent “ion storage buffer” that promotes cell growth by stimulating cell viability and metabolism with promising applications in the treatment of bone defects and bone degenerative diseases. KW - Total Scattering KW - XRD KW - Mechanochemistry PY - 2020 DO - https://doi.org/10.1002/adfm.202007830 VL - 31 IS - 3 SP - 7830 PB - Wiley VHC-Verlag AN - OPUS4-51761 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lörchner, Dominique A1 - Kraus, Werner A1 - Köppen, Robert T1 - Photodegradation of the novel brominated flame retardant 2,4,6-Tris-(2,4,6-tribromophenoxy)-1,3,5-triazine in solvent system: Kinetics, photolysis products and pathway. JF - Chemosphere N2 - In this study the direct and indirect photolysis of the novel brominated flame retardant 2,4,6-Tris-(2,4,6-tribromophenoxy)-1,3,5-triazine (TTBP-TAZ) in an organic solvent mixture (60:30:10, ACN:MeOH:THF) under UV-(C) and simulated sunlight irradiation was investigated, and the formed photo-transformation products were identified for the first time. TTBP-TAZ was almost completely degraded within 10 min under UV-(C) irradiation. Due to the fast degradation no specific kinetic order could be observed. In comparison, the reaction under simulated sunlight irradiation was much slower and thus, the kinetic first-order could be determined. The observed photolysis rate constant k as well as the half-life time t1/2 were estimated to be k = (0.0163 ± 0.0002) h-1 and t1/2 = 42.3 h, respectively. The addition of 2-propanol and hydrogen peroxide to investigate the influence of indirect photolysis under UV-(C) irradiation causes no influence on the degradation of TTBP-TAZ. Nevertheless, the removal of TTBP-TAZ under UV-(C) and simulated sunlight without additional chemicals (except solvent) indicates that the direct photolysis plays a significant role in the degradation mechanism of TTBP-TAZ. In both irradiation experiments, TTBP-TAZ was quantitatively degraded that involve the formation of previously unknown PTPs. Overall, two main PTPs were determined when irradiated with UV-(C) and eight sequential debromination products were observed when irradiated by simulated sunlight. These were determined by HPLC-DAD and - MS/(MS), respectively. Based on the chosen experimental conditions the consecutive debromination as well as photo-Fries rearrangement was confirmed as the main degradation pathway by high resolution mass spectrometry and X-ray diffraction. KW - XRD KW - Direct/indirect photolysis KW - HRMS KW - Photo-transformation products KW - TTBP-TAZ PY - 2019 DO - https://doi.org/10.1016/j.chemosphere.2019.04.184 SN - 0045-6535 SN - 1879-1298 VL - 229 SP - 77 EP - 85 PB - Elsevier Ltd. CY - Amsterdam AN - OPUS4-48066 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Loges, A. A1 - Scholz, G. A1 - Amadeu de Sosa, Nader A1 - Jingjing, S. A1 - Emmerling, Franziska A1 - John, T. A1 - Paulus, B. A1 - Braun, T. T1 - Studies on the local structure of the F/OH site in topaz by magic angle spinning nuclear magnetic resonance and Raman spectroscopy JF - European journal of mineralogy N2 - he mutual influence of F and OH groups in neighboring sites in topaz (Al2SiO4(F,OH)2) was investigated using magic angle spinning nuclear magnetic resonance (MAS NMR) and Raman spectroscopy. The splitting of 19F and 1H NMR signals, as well as the OH Raman band, provides evidence for hydrogen bond formation within the crystal structure. Depending on whether a given OH group has another OH group or fluoride as its neighbor, two different hydrogen bond constellations may form: either OH···O···HO or F···H···O. The proton accepting oxygen was determined to be part of the SiO4 tetrahedron using 29Si MAS NMR. Comparison of the MAS NMR data between an OH-bearing and an OH-free topaz sample confirms that the 19F signal at −130 ppm stems from F− ions that take part in H···F bonds with a distance of ∼ 2.4 Å, whereas the main signal at −135 ppm belongs to fluoride ions with no immediate OH group neighbors. The Raman OH sub-band at 3644 cm−1 stems from OH groups neighboring other OH groups, whereas the sub-band at 3650 cm−1 stems from OH groups with fluoride neighbors, which are affected by H···F bridging. The integrated intensities of these two sub-bands do not conform to the expected ratios based on probabilistic calculations from the total OH concentration. This can be explained by a difference in the polarizability of the OH bond between the different hydrogen bond constellations or partial order or unmixing of F and OH, or a combination of both. This has implications for the quantitative interpretation of Raman data on OH bonds in general and their potential use as a probe for structural (dis-)order. No indication of tetrahedrally coordinated Al was found with 27Al MAS NMR, suggesting that the investigated samples likely have nearly ideal Al/Si ratios, making them potentially useful as high-density electron microprobe reference materials for Al and Si, as well as for F. KW - Topas KW - NMR KW - XRD PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-561863 DO - https://doi.org/10.5194/ejm-34-507-2022 SN - 1617-4011 VL - 34 IS - 5 SP - 507 EP - 521 PB - Copernicus Publications CY - Göttingen AN - OPUS4-56186 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Emmerling, Franziska A1 - Tumanov, N. A1 - Tumanova, N. A1 - Fischer, Franziska A1 - Morelle, F. A1 - Ban, V. A1 - Robeyns, K. A1 - Filinchuk, Y. A1 - Wouters, J. A1 - Leyssens, T. T1 - Exploring polymorphism and stoichiometric diversity in naproxen/proline cocrystals JF - CrystEngComm N2 - We present naproxen/proline cocrystals discovered when combining enantiopure and racemic naproxen and proline. Using liquid-assisted grinding as the main method to explore the variety of crystal forms in this system, we found 17 cocrystals, of which the structures of only four of them were previously known. The naproxen/proline system exhibited multiple polymorphs of 1 : 1 stoichiometry as well as more rare cocrystals with 1 : 2 and 2 : 3 stoichiometries, two cocrystal hydrates and one cocrystal solvate. In situ ballmilling, used to monitor liquid-assisted grinding reactions, revealed that the solvent dictates the reaction intermediates even if the final reaction product stays the same. Synchrotron X-ray diffraction data collected in situ upon heating allowed us to monitor directly the phase changes upon heating and gave access to pure diffraction patterns of several cocrystals, thus enabling their structure determination from powder X-ray diffraction data; this method also confirmed the formation of a conglomerate in the RS-naproxen/DL-proline system. Proline in cocrystals kept its ability to form charge-assisted head-to-tail N-H⋯O hydrogen bonds, typical of pure crystalline amino acids, thus increasing the percentage of strong chargeassisted interactions in the structure and consequently providing some of the cocrystals with higher melting points as compared to pure naproxen. The majority of drugs are chiral, and hence, these data are of importance to the pharmaceutical industry as they provide insight into the challenges of chiral cocrystallization. KW - In situ KW - Mechanochemistry KW - XRD PY - 2018 UR - https://pubs.rsc.org/en/Content/ArticleLanding/CE/2018/C8CE01338A#!divAbstract DO - https://doi.org/10.1039/c8ce01338a SN - 1466-8033 VL - 20 IS - 45 SP - 7308 EP - 7321 PB - Royal Society of Chemistry CY - London AN - OPUS4-46913 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 JF - Crystengcomm 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 - 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 JF - CrystEngComm 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 - Prinz, Carsten A1 - Scholz, Gudrun A1 - Kemnitz, Erhard A1 - Emmerling, Franziska T1 - Ca-, Sr-, and Ba-Coordination polymers based on anthranilic acid via mechanochemistry JF - Daltron Transaction 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 - 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 JF - Journal of Materials Science 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 -