{"title":"Shaken not stirred: procedures in mechanochemical syntheses and how to define them","authors":"James Batteas and Tomislav Friščić","doi":"10.1039/D5MR90005K","DOIUrl":"https://doi.org/10.1039/D5MR90005K","url":null,"abstract":"<p >A graphical abstract is available for this content</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 2","pages":" 175-177"},"PeriodicalIF":0.0,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/mr/d5mr90005k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143553651","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"A mechanochemical synthetic strategy of isoreticular flexible metal–organic frameworks with pre-designed mixed metal clusters†","authors":"Hong Kyu Lee and Hoi Ri Moon","doi":"10.1039/D5MR00010F","DOIUrl":"https://doi.org/10.1039/D5MR00010F","url":null,"abstract":"<p >Mechanochemistry has emerged as a sustainable alternative to traditional solvothermal methods for synthesizing metal–organic frameworks (MOFs), offering reduced solvent usage, shorter reaction times, and scalability. However, the synthesis of flexible MOFs, such as the MIL-88 series, remains challenging due to the difficulty in forming secondary building units (SBUs) under mechanochemical conditions. Herein, we present a novel strategy for the mechanochemical synthesis of the MIL-88 series using pre-assembled mixed-metal clusters as precursors. This approach effectively overcomes limitations in controlling metal ratios and suppressing undesired phase mixtures, enabling the efficient and rapid formation of MIL-88 frameworks under mild conditions. The synthesized MIL-88s, including mixed-metal variants, were comprehensively characterized to confirm phase purity, structural fidelity, and tunable metal compositions. This strategy not only facilitates access to flexible MOFs that were previously difficult to synthesize mechanochemically but also demonstrates the feasibility of precisely controlling metal ratios in mixed-metal systems. These advancements underscore the significant potential of this approach for further expanding the scope and applications of mechanochemical synthesis.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 3","pages":" 426-431"},"PeriodicalIF":0.0,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/mr/d5mr00010f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913673","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kang Xia, Shengtai Hou, Qiang Niu, Kosuke Suzuki and Pengfei Zhang
{"title":"Mechanochemical templated synthesis of mesoporous alumina-supported polyoxometalate catalysts toward selective oxidation of sulfides†","authors":"Kang Xia, Shengtai Hou, Qiang Niu, Kosuke Suzuki and Pengfei Zhang","doi":"10.1039/D4MR00130C","DOIUrl":"https://doi.org/10.1039/D4MR00130C","url":null,"abstract":"<p >Polyoxometalates are important catalysts, but their low surface area and leaching in solutions present challenges. We developed a facile, green, solvent-free mechanochemical method to anchor polyoxometalates on mesoporous alumina. The resulting catalysts showed high activity, selectivity in sulfide oxidation, and reusability for at least seven cycles, achieving gram-scale reactions efficiently.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 3","pages":" 394-398"},"PeriodicalIF":0.0,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/mr/d4mr00130c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913670","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Diandian Wei, Zongwei Li, Heng Li and Bingxin Yuan
{"title":"Stainless-steel-initiated acylation of quinoxalin-2(1H)-ones with aldehydes under mechanochemical conditions†","authors":"Diandian Wei, Zongwei Li, Heng Li and Bingxin Yuan","doi":"10.1039/D4MR00131A","DOIUrl":"https://doi.org/10.1039/D4MR00131A","url":null,"abstract":"<p >Utilizing direct mechanocatalytical conditions, we have developed a C–H acylation of quinoline-2(1<em>H</em>)-one initiated by stainless-steel milling balls. A wide range of functional groups are bearable, affording the desired products in excellent yields. Noteworthy is the short reaction period (30 min) and no requirement for solvent. The late-stage functionalization of pharmaceutical-related molecules illustrates its potential application in drug development. Gram-scale synthesis further demonstrates the scalability and sustainability of this method.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 3","pages":" 468-474"},"PeriodicalIF":0.0,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/mr/d4mr00131a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913677","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sally Nijem, Alexander Kaushansky, Svetlana Pucovski, Elisa Ivry, Evelina Colacino, Ivan Halasz and Charles E. Diesendruck
{"title":"Chemoselectivity switch by mechanochemistry in the base-catalysed dione-acylation†","authors":"Sally Nijem, Alexander Kaushansky, Svetlana Pucovski, Elisa Ivry, Evelina Colacino, Ivan Halasz and Charles E. Diesendruck","doi":"10.1039/D4MR00141A","DOIUrl":"https://doi.org/10.1039/D4MR00141A","url":null,"abstract":"<p >The mechanochemistry of small molecules is an exponentially growing area of investigation relevant to developing sustainable synthesis to reduce waste and energy consumption, with great potential in large-scale chemical manufacturing. Occasionally, mechanochemical processes exhibit different reactivities, resulting in varying product selectivity compared to solution processes. In this study, we investigate the catalytic mechanism of a solvent-free one-pot acylation reaction of dimedone and 3-phenylpropanoic acid using a solvent-free ball-mill approach. The mechanochemical procedure afforded complete chemoselectivity towards a single acylation product after short milling, contrary to solution studies that previously reported product mixtures. Selectivity towards a single acylation product is controlled by the choice of the catalytic base. Under these mechanical process conditions, 4-dimethylaminopyridine (DMAP) is the only base that promotes the formation of the more desirable <em>C</em>-acylation product, whereas other bases exclusively afford the <em>O</em>-acylation product. Based on experimental findings, supported by theoretical modeling, we provide a mechanistic understanding of the base-dependent chemoselectivity, which leads to an enolate esterification that, in the case of DMAP, is converted to the thermodynamic product <em>via</em> Fries rearrangement. Finally, we explore the reaction scope with additional dicarbonyl compounds and carboxylic acids.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 3","pages":" 419-425"},"PeriodicalIF":0.0,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/mr/d4mr00141a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913672","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Diego A. Acevedo-Guzmán, Brian Monroy-Torres, Petra Rudolf, Vladimir A. Basiuk and Elena V. Basiuk
{"title":"Green mechanochemical fabrication of graphite-lanthanide oxide nanocomposites†","authors":"Diego A. Acevedo-Guzmán, Brian Monroy-Torres, Petra Rudolf, Vladimir A. Basiuk and Elena V. Basiuk","doi":"10.1039/D4MR00085D","DOIUrl":"https://doi.org/10.1039/D4MR00085D","url":null,"abstract":"<p >In this study, we explored mechanochemistry as a facile and environmentally friendly approach for the synthesis of graphite-lanthanide oxide nanocomposites. We determined the optimal conditions, namely a milling time of 48 h and milling ball size of 10 mm diameter, for which processing mixtures of graphite and lanthanide oxide in a planetary ball mill resulted in exfoliated graphene nanosheets functionalised with lanthanide oxide particles. The prepared nanocomposites were investigated by a suite of analytical techniques; X-ray photoelectron spectroscopy proved that mechanochemical processing in the presence of lanthanide oxides functionalises the graphene surface. Raman spectroscopy and X-ray diffraction results evidenced that the mechanochemical treatment exfoliates graphite and reduces the size of graphite crystallites. Scanning electron microscopy and scanning transmission electron microscopy confirmed the formation of lanthanide oxide nanoparticles and their uniform distribution on the graphene surface and thermogravimetric analysis gave evidence that the graphite-lanthanide oxide nanocomposites are less thermally stable than pristine graphite. The toxicity of the graphite-lanthanide oxide nanocomposites was also studied; we found that COS-7 monkey kidney cell growth was not inhibited for more than 5% in most of the studies.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 3","pages":" 443-458"},"PeriodicalIF":0.0,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/mr/d4mr00085d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913675","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Reassessing mechanochemical processes in polyatomic systems for smart fabrication of nanocomposites","authors":"Mamoru Senna and Adam A. L. Michalchuk","doi":"10.1039/D4MR00084F","DOIUrl":"https://doi.org/10.1039/D4MR00084F","url":null,"abstract":"<p >A brief review is given to reassess the integrity of the fundamentals and the application in mechanochemistry. The discussion starts from the chemical response of polyatomic systems (PAS) to the mechanical stress, in terms of the extended concept of the Jahn–Teller effects. The interplay between the deformation and the chemical properties was extended to larger scale units toward solid particles or crystallites, which comprise the ensemble and arrangements of PAS. Therefore, the role of disorder of PAS arrangement or defects in solids on the reactivity of solids was discussed. Since the mechanochemical process is based on the introduction and control of the defects in solids, the discussion abridges the fundamental understanding of deformation – chemical property relationship from the basis of molecules with the reactivity of solids and powder masses. By taking the subsequent steps of relaxation in different time scales, the affordability of functional materials <em>via</em> a mechanochemical route has been demonstrated to finalize the entire discussion. A short summary at the end emphasises the importance of learning from the exotic fields.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 3","pages":" 351-369"},"PeriodicalIF":0.0,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/mr/d4mr00084f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913614","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Antonio Manuel Pérez-Merchán, Benjamín Torres-Olea, Marcella Scala, Nikolaos Dimitratos, Irene Malpartida, Cristina García-Sancho, Josefa M. Mérida-Robles, Pedro Maireles-Torres, Ramón Moreno-Tost and Juan Antonio Cecilia
{"title":"Catalytic transfer hydrogenation of furfural using mechanically activated MgO as catalyst†","authors":"Antonio Manuel Pérez-Merchán, Benjamín Torres-Olea, Marcella Scala, Nikolaos Dimitratos, Irene Malpartida, Cristina García-Sancho, Josefa M. Mérida-Robles, Pedro Maireles-Torres, Ramón Moreno-Tost and Juan Antonio Cecilia","doi":"10.1039/D4MR00128A","DOIUrl":"https://doi.org/10.1039/D4MR00128A","url":null,"abstract":"<p >Several MgO materials have been prepared throughout wet flow semi-continuous mechanochemical treatment of the Mg(OH)<small><sub>2</sub></small> precursors and their subsequent calcination. This mechanochemical treatment of the precursors has shown a clear influence on the textural properties and the amount and strength of basic sites of the MgO catalysts after its calcination, obtaining higher values than that observed in a MgO sample synthesized without mechanochemical treatment. An in-depth investigation was conducted on the effects of the mechanochemical treatment on the catalytic performance in the catalytic transfer hydrogenation of furfural, and a positive effect on the activity of the catalysts was found after short mechanochemical treatment times. The highest conversion values at shorter reaction times were obtained after a mechanochemical treatment of 15 min, reaching a furfuryl alcohol yield of 79% after 2 h of reaction at 90 °C, using 2-propanol as both hydrogen donor and solvent. This data notably improves that obtained for the untreated material, which only reaches a conversion of 48% under the same experimental conditions. The stability of the material in the reaction media as well as their reusability were also investigated, and the interaction nature of 2-propanol with the MgO surface has been elucidated by attenuated total reflection spectroscopy and 2-propanol adsorption studies.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 3","pages":" 432-442"},"PeriodicalIF":0.0,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/mr/d4mr00128a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913674","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Access to enzyme@porous organic framework biocomposites based on mechanochemical synthesis","authors":"Qing Chen, Zhi-Wei Li, Siming Huang, Guosheng Chen and Gangfeng Ouyang","doi":"10.1039/D4MR00134F","DOIUrl":"https://doi.org/10.1039/D4MR00134F","url":null,"abstract":"<p >Enzymes serve as highly efficient and selective biological catalysts, essential across diverse fields such as industry, medicine, and biotechnology, and are vital to green chemistry due to their efficacy at ambient temperatures. However, enzymes are sensitive to environmental conditions, which restricts their stability and reusability, limiting their broader practical applications. Porous organic frameworks encompassing metal–organic frameworks, covalent organic frameworks, and hydrogen-bonded organic frameworks have emerged as robust platforms for enzyme immobilization, offering high porosity, tailored pore structures, and strong chemical stability to safeguard encapsulated enzymes. Traditional surface immobilization methods can stabilize enzymes but often encounter low loading efficiency and enzyme leaching issues. <em>In situ</em> embedding methods address these challenges but typically rely on solvent-intensive, high-temperature liquid-phase syntheses that compromise enzyme functionality. This review centers on mechanochemical synthesis as a novel, green approach to creating enzyme-embedded porous organic frameworks, referred to as enzyme@porous organic frameworks. By employing mild mechanical forces, mechanochemical synthesis facilitates enzyme encapsulation under ambient conditions in the absence (or near-absence) of solvents, maintaining enzyme stability while ensuring efficient precursor-enzyme integration. We explore the mechanochemical synthesis principles, influential parameters, and advantages over liquid-phase techniques, underscoring its potential to produce multifunctional biocomposites. This review aspires to pave the way for scalable biocatalytic systems with enhanced stability and performance, advancing biocatalysis in industrial applications.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 3","pages":" 336-350"},"PeriodicalIF":0.0,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/mr/d4mr00134f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913613","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Peng Xu, Ming-Jun Li, Honglin Diao, Ning Shao, Zeng-Yang He, Shi-Zhu Fan, Ze Zhang and Hui Xu
{"title":"Chemodivergent and diastereoselective synthesis of syn- and anti-cyclopentenyl spiroisoxazolones under ball-milling conditions†","authors":"Peng Xu, Ming-Jun Li, Honglin Diao, Ning Shao, Zeng-Yang He, Shi-Zhu Fan, Ze Zhang and Hui Xu","doi":"10.1039/D4MR00125G","DOIUrl":"https://doi.org/10.1039/D4MR00125G","url":null,"abstract":"<p >A new cyclization pattern between arylidene isoxazolones and enamino esters has been demonstrated, efficiently affording various structurally novel cyclopentenyl spiroisoxazolones with high chemoselectivity in a ball mill. Interestingly, the diastereoselectivity of the spiro products is also controllable, with both <em>syn</em>- and <em>anti</em>-isomers generated selectively under different reaction conditions. The mechanochemical protocol features good chemo- and diastereoselectivity, high efficiency, mild reaction conditions and minimal solvent usage, providing rapid, environmentally benign and scalable access to spirocyclopentenes.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 2","pages":" 317-321"},"PeriodicalIF":0.0,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/mr/d4mr00125g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143553685","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}