TY - JOUR A1 - Stolar, Tomislav A1 - Pearce, Ben K.D. A1 - Etter, Martin A1 - Truong, Khai-Nghi A1 - Ostojić, Tea A1 - Krajnc, Andraž A1 - Mali, Gregor A1 - Rossi, Barbara A1 - Molčanov, Krešimir A1 - Lončarić, Ivor A1 - Meštrović, Ernest A1 - Užarević, Krunoslav A1 - Grisanti, Luca T1 - Base-pairing of uracil and 2,6-diaminopurine: from cocrystals to photoreactivity N2 - We show that the non-canonical nucleobase 2,6-diaminopurine (D) spontaneously base pairs with uracil (U) in water and the solid state without the need to be attached to the ribose-phosphate backbone. Depending on the reaction conditions, D and U assemble in thermodynamically stable hydrated and anhydrated D-U base-paired cocrystals. Under UV irradiation, an aqueous solution of D-U base-pair undergoes photochemical degradation, while a pure aqueous solution of U does not. Our simulations suggest that D may trigger the U photodimerization and show that complementary base-pairing modifies the photochemical properties of nucleobases, which might have implications for prebiotic chemistry. KW - Mechanochemistry KW - In situ monitoring KW - Cocrystals PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-608622 DO - https://doi.org/10.1016/j.isci.2024.109894 VL - 27 IS - 6 SP - 1 EP - 14 PB - Elsevier Inc. AN - OPUS4-60862 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Davison, Nathan A1 - Hemingway, Jack M. A1 - Wills, Corinne A1 - Stolar, Tomislav A1 - Waddell, Paul G. A1 - Dixon, Casey M. A1 - Barron, Luke A1 - Dawson, James A. A1 - Lu, Erli T1 - Mechanochemical Synthesis of a Sodium Anion Complex [Na+(2,2,2-cryptand)Na] and Studies of Its Reactivity: Two-Electron and One-Electron Reductions N2 - Group 1 metal molecular chemistry is dominated by a +1 oxidation state, while a 0 oxidation state is widespread in the metals. A more exotic, yet still available, oxidation state of group 1 metal is −1, i.e., alkalide. Reported as early as the 1970s, the alkalides appear in every modern inorganic chemistry textbook as an iconic chemical curiosity, yet their reactivity remains unexplored. This is due to their synthetic hurdles. In this work, we report the first facile synthesis of the archetypical alkalide complex, [Na+(2,2,2-cryptand)Na–], which allows us to unveil a versatile reactivity profile of this once exotic species. KW - Mechanochemistry PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-608632 DO - https://doi.org/10.1021/acs.inorgchem.4c02914 VL - 63 IS - 32 SP - 15247 EP - 15258 PB - American Chemical Society (ACS) AN - OPUS4-60863 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Alić, Jasna A1 - Schlegel, Moritz-Caspar A1 - Emmerling, Franziska A1 - Stolar, Tomislav T1 - Meeting the UN Sustainable Development Goals with Mechanochemistry N2 - Chemistry traditionally relies on reactions in solution, but this method is increasingly problematic due to the scale of chemical processes and their economic and environmental impact. Handling residual chemical waste, including solvents, incurs significant costs and environmental pressure. Conversely, novel chemical approaches are needed to address pressing societal issues such as climate change, energy scarcity, food insecurity, and waste pollution. Mechanochemistry, a sustainable chemistry discipline that uses mechanical action to induce chemical reactivity without bulk solvents, is a hot topic in academic research on sustainable and green chemistry. Given its fundamentally different working principles from solution chemistry, mechanochemistry offers more efficient chemical processes and the opportunity to design new chemical reactions. Mechanochemistry has a profound impact on many urgent issues facing our society and it is now necessary to use mechanochemistry to address them. This Minireview aims to provide a guide for using mechanochemistry to meet the United Nations (UN) Sustainable Development Goals (SDGs), thereby contributing to a prosperous society. Detailed analysis shows that mechanochemistry connects with most UN SDGs and offers more cost‐efficiency than other approaches together with a superior environmental performance. KW - Mechanochemistry KW - SDGs PY - 2024 DO - https://doi.org/10.1002/anie.202414745 SP - 1 EP - 3 PB - Wiley AN - OPUS4-61108 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Stolar, Tomislav T1 - Sustainable mechanochemical reaction engineering: from molecular mechanisms to scalable technology N2 - In this talk, I will present about our quest to fundamentally understand mechanochemical reactions by in situ monitoring studies. Another of our interest is scaling up mechanochemistry. For example, we are now working on developing mechanochemical technology to enable a circular economy of plastics. T2 - Korea-Germany Symposium on Mechanochemistry CY - Jeonju, South Korea DA - 02.10.2024 KW - Mechanochemistry KW - Plastic recycling KW - Circular economy PY - 2024 AN - OPUS4-62110 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Stolar, Tomislav T1 - Mechanochemistry: fundamentals to application N2 - In the first part, I will talk about the role of mechanochemistry in prebiotic chemistry. For example, prebiotically plausible pathways to peptides from inactivated amino acids are unclear as most oligomerization approaches rely on thermodynamically disfavored reactions in solution. I will show how a combination of mineral surfaces and mechanochemical activation enables the oligomerization of amino acids to oligopeptides (Figure 1). In the second part, I will show how fundamental studies inspired to use mechanochemistry for the sustainable synthesis of commercially relevant compounds, in line with the United Nations Sustainable Development Goals.2 We developed a solvent-free thermo-mechanochemical approach for the direct coupling of carboxylic acids and amines, which avoids activators and additives. We applied our methodology for the quantitative synthesis of the active pharmaceutical ingredient moclobemide (Figure 2). T2 - Solutions in Chemistry Conference 2024 CY - Sveti Martin na Muri, Croatia DA - 15.11.2024 KW - Mechanochemistry KW - Plastic recycling KW - Circular economy PY - 2024 AN - OPUS4-62111 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Stolar, Tomislav T1 - Sustainable mechanochemical reaction engineering: from molecular mechanisms to scalable technology N2 - In this talk, I will present about our quest to fundamentally understand mechanochemical reactions by in situ monitoring studies. Another of our interest is scaling up mechanochemistry. For example, we are now working on developing mechanochemical technology to enable a circular economy of plastics. T2 - Hokkaido International Workshop on Mechanochemistry CY - Hokkaido, Japan DA - 29.09.2024 KW - Mechanochemistry KW - Plastic recycling KW - Circular economy PY - 2024 AN - OPUS4-62109 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Casali, Lucia A1 - Carta, Maria A1 - Michalchuk, Adam A1 - Delogu, Francesco A1 - Emmerling, Franziska T1 - Kinetics of the mechanically induced ibuprofen–nicotinamide co-crystal formation by in situ X-ray diffraction N2 - Mechanochemistry is drawing attention from the pharmaceutical industry given its potential for sustainable material synthesis and manufacture. Scaling mechanochemical processes to industrial level remains a challenge due to an incomplete understanding of their underlying mechanisms. We here show how time-resolved in situ powder X-ray diffraction data, coupled with analytical kinetic modelling, provides a powerful approach to gain mechanistic insight into mechanochemical reactions. By using the ibuprofen–nicotinamide co-crystal mechanosynthesis as a benchmark system, we investigate the behaviour of the solids involved and identify the factors that promote the reaction. As mechanochemical mechanisms become increasingly clear, it promises to become a breakthrough in the industrial preparation of advanced pharmaceuticals. KW - Mechanochemistry KW - Kinetics PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-608820 DO - https://doi.org/10.1039/D4CP01457J SN - 1463-9084 VL - 26 SP - 22041 EP - 22048 PB - Royal Society of Chemistry (RSC) CY - Cambridge AN - OPUS4-60882 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - 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 - 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 - 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 -