TY - JOUR A1 - Haferkamp, Sebastian A1 - Fischer, Franziska A1 - Kraus, Werner A1 - Emmerling, Franziska T1 - Mechanochemical Knoevenagel condensation investigated in situ N2 - The mechanochemical Knoevenagel condensation of malononitrile with p-nitrobenzaldehyde was studied in situ using a tandem approach. X-ray diffraction and Raman spectroscopy were combined to yield time-resolved information on the milling process. Under solvent-free conditions, the reaction leads to a quantitative conversion to p-nitrobenzylidenemalononitrile within 50 minutes. The in situ data indicate that the process is fast and proceeds under a direct conversion. After stopping the milling process, the reaction continues until complete conversion. The continuous and the stopped milling process both result in crystalline products suitable for single crystal X-ray diffraction. KW - Mechanochemistry KW - Ball milling KW - C–C coupling KW - In situ KW - Knoevenagel condensation PY - 2017 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-425388 DO - https://doi.org/10.3762/bjoc.13.197 VL - 13 SP - 2010 EP - 2014 PB - Beilstein-Institut AN - OPUS4-42538 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Speight, Isaiah R. A1 - Ardila-Fierro, Karen J. A1 - Hernández, José G. A1 - Emmerling, Franziska A1 - Michalchuk, Adam A1 - García, Felipe A1 - Colacino, Evelina A1 - Mack, James T1 - Ball milling for mechanochemical reactions N2 - Mechanochemistry is an emerging field with the potential to pave the way for sustainable chemistry. Although the use of mechanical force to initiate chemical reactions has been recognized for millennia, it has often taken a backseat to thermal and photonic methods. Over the past 30 years, mechanochemistry has seen a resurgence of interest, attracting researchers across the globe. Despite its proven ability to address numerous challenges within the chemical community, mechanochemistry remains on the periphery. This Primer serves as a valuable guide for conducting mechanochemical reactions by ball milling, offering an overview of the processes, methods, tools and terminology necessary to embark on research in this field. It also highlights persistent hurdles such as equipment standardization, understanding the impact of new discoveries and the lack of predictability of reaction outcomes. The Primer’s focus is on how mechanochemical ball milling is used in various chemical transformations, distinguishing it from other forms of mechanochemistry discussed in the literature. With a promising future, this Primer serves as a gateway for those aspiring to contribute to the field’s advancement. KW - Mechanochemistry KW - Ball milling KW - Upscaling PY - 2025 DO - https://doi.org/10.1038/s43586-025-00401-2 SN - 2662-8449 VL - 5 IS - 1 SP - 1 EP - 18 PB - Springer Science and Business Media LLC AN - OPUS4-63447 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gugin, Nikita A1 - Yusenko, Kirill A1 - King, Andrew A1 - Meyer, Klas A1 - Al-Sabbagh, Dominik A1 - Villajos Collado, José Antonio A1 - Emmerling, Franziska T1 - Lighting up industrial mechanochemistry: Real-time in situ monitoring of reactive extrusion using energy-dispersive X-ray diffraction N2 - Mechanochemistry is an environmentally friendly synthetic approach that enables the sustainable production of a wide range of chemicals while reducing or eliminating the need for solvents. Reactive extrusion aims to move mechanochemistry from its conventional gram-scale batch reactions, typically performed in laboratory ball mills, to a continuous, large-scale process. Meeting this challenge requires in situ monitoring techniques to gain insights into reactive extrusion and its underlying processes. While the effectiveness of in situ Raman spectroscopy in providing molecular-level information has been demonstrated, our study uses energy-dispersive X-ray diffraction to monitor reactive extrusion in real time at the crystalline level. Our results provide previously unavailable control over the reactive extrusion process, promoting its perception as an industrially feasible green alternative to traditional solvent-based syntheses. KW - Mechanochemistry KW - Reactive extrusion KW - Green chemistry KW - In situ studies KW - Time-resolved in situ KW - TRIS KW - Synchrotron radiation KW - Scalable synthesis KW - Solid-state reactions KW - Reaction mechanisms PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-613969 DO - https://doi.org/10.1016/j.chempr.2024.07.033 VL - 10 IS - 11 SP - 1 EP - 16 PB - Elsevier B.V. AN - OPUS4-61396 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Starkholm, A. A1 - Al-Sabbagh, Dominik A1 - Sarisozen, S A1 - von Reppert, A A1 - Rössle, M A1 - Ostermann, Markus A1 - Unger, E A1 - Emmerling, Franziska A1 - Kloo, L A1 - Svensson, P A1 - Lang, F A1 - Maslyanchuk, O. T1 - Green Fabrication of Sulfonium-Containing Bismuth Materials for High-Sensitivity X-Ray Detection N2 - Organic–inorganic hybrid materials based on lead and bismuth have recently been proposed as novel X- and gamma-ray detectors for medical imaging, non-destructive testing, and security, due to their high atomic numbers and facile preparation compared to traditional materials like amorphous selenium and Cd(Zn)Te. However, challenges related to device operation, excessively high dark currents, and long-term stability have delayed commercialization. Here, two novel semiconductors incorporating stable sulfonium cations are presented, [(CH3CH2)3S]6Bi8I30 and [(CH3CH2)3S]AgBiI5, synthesized via solvent-free ball milling and fabricated into dense polycrystalline pellets using cold isostatic compression, two techniques that can easily be upscaled, for X-ray detection application. The fabricated detectors exhibit exceptional sensitivities (14 100–15 190 µC Gyair−1 cm−2) and low detection limits (90 nGyair s−1 for [(CH3CH2)3S]6Bi8I30 and 78 nGyair s−1 for [(CH3CH2)3S]AgBiI5), far surpassing current commercial detectors. Notably, they maintain performance after 9 months of ambient storage. The findings highlight [(CH3CH2)3S]6Bi8I30 and [(CH3CH2)3S]AgBiI5 as scalable, cost-effective and highly stable alternatives to traditional semiconductor materials, offering great potential as X-ray detectors in medical and security applications. KW - Mechanochemistry KW - X-ray detectors PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-630306 DO - https://doi.org/10.1002/adma.202418626 SP - 1 EP - 10 PB - Wiley VHC-Verlag AN - OPUS4-63030 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Go, Eun Sul A1 - Hong, Eun Ji A1 - Lee, Ji Yeong A1 - Stolar, Tomislav A1 - Peterson, Gregory I. A1 - Emmerling, Franziska A1 - Kim, Kyoungsoo A1 - Kim, Jeung Gon T1 - Insights into Mechanochemical Solid-State Ball-Milling Reaction: Monitoring Transition from Heterogeneous to Homogeneous Conditions N2 - As mechanochemical synthesis has advanced significantly, there has been intense interest in understanding the underlying mechanisms of these reactions. Given that many mechanochemical processes are conducted in the solid-state without solvation yet sometimes yield faster reactions than those in solution, we sought to address the following question: Are mechanochemical reactions homo- or heterogeneous? To investigate, we employed a model system involving the mixing and copolymerization of l-lactide (LLA) and d-lactide (DLA), monitored through powder X-ray diffraction (PXRD), nuclear magnetic resonance, and differential scanning calorimetry. In situ and ex situ PXRD analyses of the mixture of LLA and DLA showed that vibratory ball milling rapidly transformed the initially heterogeneous lactide mixture into a homogeneous phase within one min due to collisions between the balls and the jar. By varying the milling conditions, we were able to regulate the level of mixing, which subsequently influenced the copolymerization outcomes. In the solid-state ball-milling copolymerization of LLA and DLA in the presence of a catalyst and initiator, multiblock copolymers of poly(l-lactic acid) and poly(d-lactic acid) were formed within one min during the early stage of the reaction, when incomplete mixing of the monomers led to a process governed by phase heterogeneity. In contrast, prolonged polymerization promoted conditions approaching homogeneity, ultimately yielding atactic poly(lactic acid). This transition from heterogeneous to homogeneous reactions is a distinctive feature compared to conventional homogeneous reactions, potentially leading to mechano-exclusive reaction designs. KW - Mechanochemistry KW - Ball-milling KW - Homogeneous reaction KW - Heterogeneous reaction PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-638008 DO - https://doi.org/10.1021/jacsau.5c00322 SN - 2691-3704 VL - 5 IS - 6 SP - 2720 EP - 2727 PB - American Chemical Society (ACS) AN - OPUS4-63800 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zuffa, Caterina A1 - Cappuccino, Chiara A1 - Casali, Lucia A1 - Emmerling, Franziska A1 - Maini, Lucia T1 - Liquid reagents are not enough for liquid assisted grinding in the synthesis of [(AgBr)(n-pica)]n N2 - This study investigates the mechanochemical reactions between AgBr 3-picolylamine and 4-picolylamine. The use of different stoichiometry ratios of the reagents allows [(AgBr)(n-pica)]n and [(AgBr)2(n-pica)]n to be obtained, and we report the new structures of [(AgBr)2(3-pica)]n and [(AgBr)2(4-pica)]n which are characterized by the presence of the following: (a) infinite inorganic chains, (b) silver atom coordinated only by bromide atoms and (c) argentophilic interactions. Furthermore, we studied the interconversion of [(AgBr)(n-pica)]n/[(AgBr)2(n-pica)]n by mechanochemical and thermal properties. The in situ experiments suggest that [(AgBr)(3-pica)]n is kinetically favoured while [(AgBr)2(3-pica)]n is converted into [(AgBr)(3-pica)]n only with a high excess of the ligand. Finally, the liquid nature of the ligands is not sufficient to assist the grinding process, and the complete reaction is observed with the addition of a small quantity of acetonitrile. KW - Mechanochemistry KW - Complex PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594755 DO - https://doi.org/10.1039/d3cp04791a SN - 1463-9076 SP - 1 EP - 10 PB - Royal Society of Chemistry (RSC) AN - OPUS4-59475 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mishra, Rajesh K. A1 - Minussi, F.B. A1 - Kumari, Priyanka A1 - Shahi, Rohit R. A1 - Yadav, R.P. A1 - Emmerling, Franziska A1 - Araújo, E.B. T1 - Effect of sintering temperature on structural, microstructural, and dielectric properties of (Co0.2Fe0.2Ni0.2Al0.2Ti0.2)3O4 multi-cations high entropy oxides N2 - The study reports the effect of sintering temperature on structural, microstructural, and dielectric properties of (Co0.2Fe0.2Ni0.2Al0.2Ti0.2)3O4 spinel high-entropy oxides (HEOs) synthesized through the solid-state mechanochemistry method. The sintering of the ceramic powders was accomplished at three different temperatures (1000 ◦C, 1100 ◦C, and 1250 ◦C), followed by air quenching. XRD analysis along with Le-Bail refinement confirms that 1100 ◦C and 1250 ◦C sintered oxides comprised of a single cubic spinel phase (Fd3m), while 1000 ◦C sintered oxide contains constituent oxides and a spinel phase. The phase formation of oxides sintered at 1100 ◦C and 1250 ◦C has also been confirmed by Raman spectroscopic analysis. Microstructural analysis revealed that the aggregated particle size increases with the rise in sintering temperature. With the change in sintering temperature, the dielectric behavior of the ceramic changed extensively. The 1100 ◦C sintered ceramic exhibits high frequency-dependent behavior, whereas the 1250 ◦C sintered ceramic yields low frequency-dependent behavior. The 1250 ◦C sintered HEO exhibits low-loss tangent (tan δ = 0.01) with higher dielectric permittivity (εʹ = 44) at high frequency (1 MHz) compared to the 1100 ◦C sintered ceramic and many other conventional dielectrics. Fractal concept and impedance analysis have been employed to correlate the microstructure-dielectric property relation of (Co0.2Fe0.2Ni0.2Al0.2Ti0.2)3O4 spinel HEOs. The found Hurst exponent values for both different temperature-sintered HEOs are less than 0.5, indicating the anti-persistent behavior. This signifies that the height variations at neighboring pixels are negatively correlated. The present work is of fundamental importance in employing fractal analysis for the first time on spinel HEOs and correlating their properties. It also shows that processing conditions can effectively tailor the dielectric properties of the materials. KW - Multi-cations high entropy oxide KW - Mechanochemistry KW - Spinel structure KW - Fractal and impedance spectroscopic analysis PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-647584 DO - https://doi.org/10.1016/j.ceramint.2025.09.256 SN - 0272-8842 VL - 51 IS - 27 SP - 55341 EP - 55354 PB - Elsevier Ltd. AN - OPUS4-64758 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 - Ferreira, Daniela R. A1 - Portet, Anaïs A1 - Alves, Paula C. A1 - Rijo, Patrícia A1 - Gomes, Clara S. B. A1 - Duarte, M. Teresa A1 - Halasz, Ivan A1 - Colacino, Evelina A1 - Emmerling, Franziska A1 - André, Vânia T1 - Modulating the crystalline forms of silver–sulfadiazine complexes by mechanochemistry N2 - Mechanochemical synthesis of pharmaceutical compounds has gained significant attention due to its potential to overcome traditional synthetic challenges while offering the possibility of improving the physicochemical properties of drugs. This study delves into the mechanochemical synthesis of silver sulfadiazine (AgSD) coordination compounds, obtained under different mechanochemical stress and processing conditions. The aim of this work was to investigate the influence of mechanochemical conditions on the selectivity in the preparation of AgSD coordination compounds. Through a series of experiments, we demonstrate the successful synthesis of two different AgSD coordination networks, using high-energy ball milling. By strategically manipulating the starting materials and milling parameters — including milling time, milling frequency, type of mechanical stress (as determined by different milling devices), and the presence of co-milling agents — we were able to control the product outcome. As a result, we achieved two different forms of silver-sulfadiazine metal frameworks, one of which was not previously disclosed. The crystal structure of the new form, obtained from high resolution PXRD synchrotron data, was compared with the previously known structure of a silver sulfadiazine compound. The in-depth antimicrobial activity systematic study of these AgSD forms on the generic systems showed increased antibacterial activity when compared to sulfadiazine. This research sheds light on the mechanochemical synthesis of silver sulfadiazine complexes. The obtained knowledge may guide the development of novel synthetic strategies for other drug molecules, leading to improved drug performance, stability, and therapeutic outcomes. KW - Mechanochemistry KW - Structure solution PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-646099 DO - https://doi.org/10.1039/d5ce00572h SN - 1466-8033 SP - 1 EP - 12 PB - Royal Society of Chemistry (RSC) AN - OPUS4-64609 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lopes, Chrystal A1 - Casali, Lucia A1 - Emmerling, Franziska A1 - Leyssens, Tom A1 - Dupray, Valérie A1 - Brandel, Clement A1 - Cartigny, Yohann T1 - Efficient racemization of the pharmaceutical compound Levetiracetam using solvent-free mechanochemistry N2 - We present the racemization of an active pharmaceutical ingredient Levetiracetam using a novel approach. We demonstrate the design of a 100% solvent-free process that proceeds by high energy milling inside a regular mixer mill. The kinetics of the racemization process is drastically improved compared to the solution-based approach and illustrates the tremendous potential of mechanochemistry. In this study, we highlight the importance of mixing efficiency regarding data reproducibility, and we show, in particular, that water contamination has a negative impact on the reaction rate. Moreover, in situ X-ray diffraction gives us first insights into the mechanisms involved in the solid state during the mechanochemical racemization process. KW - Mechanochemistry PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-646108 DO - https://doi.org/10.1039/d4mr00103f SN - 2976-8683 VL - 2 IS - 1 SP - 83 EP - 90 PB - Royal Society of Chemistry (RSC) AN - OPUS4-64610 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Macchietti, Laura A1 - Casali, Lucia A1 - Emmerling, Franziska A1 - Braga, Dario A1 - Grepioni, Fabrizia T1 - Deriving kinetic insights from mechanochemically synthesized compounds using multivariate analysis (MCR-ALS) of powder X-ray diffraction data N2 - Kinetics information on the progress of the mechanochemical reactions is key to their understanding and subsequent scale-up. For crystalline materials, the most robust and tested method for obtaining kinetic data is the Quantitative Phase Analysis (QPA) via Rietveld refinement. In this work, we tested the feasibility of the Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) method on powder X-ray diffraction (PXRD) data of mechanochemical processes by studying the system theophylline (TP) and malonic acid (MA) in a 1 : 1 stoichiometric ratio at different milling conditions. We have highlighted the strengths and weaknesses of the MCR-ALS method, and we demonstrated why it may be an alternative route to obtain quantitative information on mechanochemical kinetics. KW - Mechanochemistry PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-646115 DO - https://doi.org/10.1039/d3mr00013c SN - 2976-8683 VL - 1 IS - 1 SP - 106 EP - 115 PB - Royal Society of Chemistry (RSC) AN - OPUS4-64611 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 - Lampronti, G. A1 - Michalchuk, Adam A1 - Mazzeo, P. A1 - Belenguer, Ana A1 - Sanders, J. K. M. A1 - Bacchi, A. A1 - Emmerling, Franziska T1 - Changing the game of time resolved X-ray diffraction on the mechanochemistry playground by downsizing N2 - Time resolved in situ (TRIS) monitoring has revolutionised the study of mechanochemical transformations but has been limited by available data quality. Here we report how a combination of miniaturised grinding jars together with innovations in X-ray powder diffraction data collection and state-of-the-art analysis strategies transform the power of TRIS synchrotron mechanochemical experiments. Accurate phase compositions, comparable to those obtained by ex situ measurements, can be obtained with small sample loadings. Moreover, microstructural parameters (crystal size and microstrain) can be also determined with high confidence. This strategy applies to all chemistries, is readily implemented, and yields high-quality diffraction data even using a low energy synchrotron source. This offers a direct avenue towards the mechanochemical investigation of reactions comprising scarce, expensive, or toxic compounds. Our strategy is applied to model systems, including inorganic, metal-organic, and organic mechanosyntheses, resolves previously misinterpreted mechanisms in mechanochemical syntheses, and promises broad, new directions for mechanochemical research. KW - Mechanochemistry KW - Synchrotron radiation KW - Material synthesis PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-535932 DO - https://doi.org/10.1038/s41467-021-26264-1 SN - 2041-1723 VL - 12 IS - 1 SP - 1 EP - 9 PB - Nature Publishing Group CY - London AN - OPUS4-53593 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mazzeo, P. P. A1 - Prencipe, M. A1 - Feiler, Torvid A1 - Emmerling, Franziska A1 - Bacchi, A. T1 - On the mechanism of cocrystal mechanochemical reaction via low melting eutectic: A time-resolved in situ monitoring investigation N2 - Mechanochemistry has become a sustainable and attractive cost-effective synthetic technique, largely used within the frame of crystal engineering. Cocrystals, namely, crystalline compounds made of different chemical entities within the same crystal structure, are typically synthesized in bulk via mechanochemistry; however, whereas the macroscopic aspects of grinding are becoming clear, the fundamental principles that underlie mechanochemical cocrystallization at the microscopic level remain poorly understood. Time-resolved in situ (TRIS) monitoring approaches have opened the door to exceptional detail regarding mechanochemical reactions. We here report a clear example of cocrystallization between two solid coformers that proceeds through the formation of a metastable low melting binary eutectic phase. The overall cocrystallization process has been monitored by time-resolved in situ (TRIS) synchrotron X-ray powder diffraction with a customized ball milling setup, currently available at μ Spot beamline at BESSY-II, Helmholtz-Zentrum Berlin. The binary system and the low melting eutectic phase were further characterized via DSC, HSM, and VT-XRPD. KW - Mechanochemistry KW - In situ KW - Cocrystal PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-552977 DO - https://doi.org/10.1021/acs.cgd.2c00262 SN - 1528-7505 VL - 22 IS - 7 SP - 4260 EP - 4267 PB - ACS Publ. CY - Washington, DC AN - OPUS4-55297 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rautenberg, Max A1 - Bhattacharya, Biswajit A1 - Witt, Julia A1 - Jain, Mohit A1 - Emmerling, Franziska T1 - In situ time-resolved monitoring of mixed-ligand metal–organic framework mechanosynthesis N2 - The mechanism of mixed-ligand metal–organic framework (MOF) formation, and the possible role of intermediate single-ligand metal complexes during mechanosynthesis, have not been explored yet. For the first time, we report here in situ real-time monitoring of the mechanochemical formation mechanism of mixed-ligand MOFs. Our results show that binary phases can act as intermediates or competing products in one-pot and stepwise synthesis. KW - Mechanochemistry KW - Metal-organic-frameworks KW - In situ X-ray diffraction KW - Mixed-ligand MOFs PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-558167 DO - https://doi.org/10.1039/D2CE00803C SP - 1 EP - 4 PB - Royal Society of Chemistry AN - OPUS4-55816 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kadri, Lena A1 - Casali, Lucia A1 - Emmerling, Franziska A1 - Tajber, Lidia T1 - Mechanochemical comparison of ball milling processes for levofloxacin amorphous polymeric systems N2 - This study aimed to investigate the amorphization capabilities of levofloxacin hemihydrate (LVXh), a fluoroquinolone drug, using a polymer excipient, Eudragit® L100 (EL100). Ball milling (BMing) was chosen as the manufacturing process and multiple mill types were utilized for comparison purposes. The product outcomes of each mill were analyzed in detail. The solid-state of the samples produced was comprehensively characterized by Powder X-ray Diffraction (PXRD), In-situ PXRD, Differential Scanning Calorimetry (DSC), Solid-State Fourier Transform Infrared Spectroscopy (FT-IR), and Dynamic Vapor Sorption (DVS). The crystallographic planes of LVXh were investigated by in-situ PXRD to disclose the presence or absence of weak crystallographic plane(s). The mechanism of LVXh:EL100 system formation was discovered as a two-step process, first involving amorphization of LVXh followed by an interaction with EL100, rather than as an instantaneous process. DVS studies of LVXh:EL100 samples showed different stability properties depending on the mill used and % LVXh present. Overall, a more sustainable approach for achieving full amorphization of the fluoroquinolone drug, LVXh, was accomplished, and advancements to the fast-growing world of pharmaceutical mechano- and tribo-chemistry were made. KW - Levofloxacin KW - Eudragit® L100 KW - Mechanochemistry KW - Phase transformation KW - In situ monitoring PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-611129 DO - https://doi.org/10.1016/j.ijpharm.2024.124652 SN - 0378-5173 VL - 665 SP - 1 EP - 16 PB - Elsevier B.V. AN - OPUS4-61112 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 - 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 - Wilke, Manuel A1 - de Oliveira Guilherme Buzanich, Ana A1 - Reinholz, Uwe A1 - Rademann, Klaus A1 - Emmerling, Franziska T1 - The structure and in situ synthesis investigation of isomorphic mononuclear molecular metal phenylphosphonates N2 - We describe a fast and effective synthesis for molecular metal phosphonates. Isomorphic compounds [M(II)(HO₃PPh)₂(H₂O₃PPh)₂(H₂O)₂] (M = Mn (1), Co (2), Ni (3); Ph = C₆H₅) were obtained by grinding. The complexes are mononuclear compounds containing neutral and monodeprotonated phenylphosphonic acid and water as ligands. The crystal structures were determined using powder X-ray diffraction (PXRD) data and validated by extended X-ray absorption fine structure (EXAFS) data. Combined synchrotron XRD measurements and Raman spectroscopy were conducted for investigating the reactions in situ. Based on these data, the intermediates were characterized and the formation mechanism was derived. KW - Mechanochemistry KW - Metal phosphonate KW - In situ KW - XRD PY - 2016 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-363944 DO - https://doi.org/10.1039/c6dt00787b SN - 1477-9226 SN - 1477-9234 SN - 1364-5447 VL - 45 IS - 23 SP - 9460 EP - 9467 AN - OPUS4-36394 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wilke, Manuel A1 - Batzdorf, Lisa A1 - Fischer, Franziska A1 - Rademann, Klaus A1 - Emmerling, Franziska T1 - Cadmium phenylphosphonates: preparation, characterisation and in situ investigation N2 - The successful mechanochemical syntheses of three cadmium phenylphosphonates indicates that mechanochemistry is ideally suited for synthesizing metal phosphonates. With this powerful synthesis tool it is possible to synthesize rapidly and efficiently both known and novel phosphonates. The Crystal structures of the two new compounds, and, were solved from PXRD data. They contain monodeprotonated phenylphosphonate and neutral phenylphosphonic acid ligands. The synthesis pathways of all three compounds were investigated in situ. A diffusion mechanism is corroborated by our findings. Intermediates could be detected and identified. The kinetically favored product (3) could always be detected during the syntheses. The thermodynamic stability of the compounds and the stoichiometric ratio of the starting materials are the two directing factors for the synthesis of the final products. KW - Mechanochemistry KW - Metal phosphonate KW - In situ KW - MOF KW - XRD PY - 2016 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-363322 DO - https://doi.org/10.1039/c6ra01080f SN - 2046-2069 VL - 6 IS - 42 SP - 36011 EP - 36019 PB - Royal Soc Chemistry CY - Cambridge, UK AN - OPUS4-36332 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -