RSC Mechanochemistry最新文献_第8页

Exploring polymorphism, stoichiometric diversity and simultaneous existence of salt and cocrystal during cocrystallization using mechanochemistry† 利用机械化学方法探索结晶过程中盐和共晶的多态性、化学计量多样性和同时存在性†。

RSC Mechanochemistry Pub Date : 2024-07-09 DOI: 10.1039/D3MR00022B

Diptajyoti Gogoi, Kalyan J. Kalita, Nishant Biswakarma, Mihails Arhangelskis, Ramesh Ch Deka and Ranjit Thakuria

{"title":"Exploring polymorphism, stoichiometric diversity and simultaneous existence of salt and cocrystal during cocrystallization using mechanochemistry†","authors":"Diptajyoti Gogoi, Kalyan J. Kalita, Nishant Biswakarma, Mihails Arhangelskis, Ramesh Ch Deka and Ranjit Thakuria","doi":"10.1039/D3MR00022B","DOIUrl":"https://doi.org/10.1039/D3MR00022B","url":null,"abstract":"We demonstrate here the mechanochemical cocrystallization of trans-aconitic acid (TACA) with nicotinamide (NA) that leads to the formation of multi-component crystal forms with stoichiometric diversity, polymorphism with high Z′′ and the simultaneous existence of salt and cocrystal. During cocrystallization, we obtained a 1 : 1 molecular salt hydrate of TACA with NA and two polymorphic cocrystal hydrates of the same in 1 : 2 ratios, with a Z′′ value of seven, respectively. Manual grinding shows that 1 : 1 molecular salt and 1 : 2 cocrystal polymorphs are interconvertible under appropriate conditions. Moreover, cocrystal dissociation was observed upon heating the 1 : 2 cocrystal and in the presence of excess TACA during the preparation of the form I cocrystal using LAG. Thermal analysis, powder XRD, and DFT calculations establish the relative stability of the multi-component solids. Three-component polymorphic systems with high Z′′ are quite unusual; however, based on mechanochemistry, we have successfully synthesized and characterized them.","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 5","pages":" 452-464"},"PeriodicalIF":0.0,"publicationDate":"2024-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d3mr00022b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142587680","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}

引用次数: 0

Total mechano-synthesis of 2-cyclopropyl-4-(4-fluorophenyl)quinoline-3-acrylaldehyde—a pivotal intermediate of pitavastatin† 2-环丙基-4-(4-氟苯基)喹啉-3-丙烯醛的全机械合成--匹伐他汀†的关键中间体

RSC Mechanochemistry Pub Date : 2024-07-01 DOI: 10.1039/D4MR00036F

Jingbo Yu, Yanhua Zhang, Zehao Zheng and Weike Su

{"title":"Total mechano-synthesis of 2-cyclopropyl-4-(4-fluorophenyl)quinoline-3-acrylaldehyde—a pivotal intermediate of pitavastatin†","authors":"Jingbo Yu, Yanhua Zhang, Zehao Zheng and Weike Su","doi":"10.1039/D4MR00036F","DOIUrl":"https://doi.org/10.1039/D4MR00036F","url":null,"abstract":"Pitavastatin (PTV), a potent cholesterol-lowering agent, holds considerable commercial appeal, driving chemists to fervently pursue its efficient and sustainable synthesis. Despite prolonged efforts over several decades, the quest for a simplified, more efficacious, and environmentally conscious manufacturing process for PTV remains a significant challenge. Our study introduces a three-step total mechano-synthesis, commencing with readily available 4-bromoquinoline, to produce the key intermediate (2-cyclopropyl-4-(4-fluorophenyl)quinoline-3-acrylaldehyde) of PTV. This methodology incorporates an extrusive Suzuki–Miyaura coupling, mechanochemical Minisci C–H alkylation, and extrusive oxidation Heck coupling, each thoroughly presented to display their scalability. Notably, we emphasize the extensive exploration of substrate versatility in Minisci reactions to access cyclopropane-bearing pharmaceutical compounds and natural products. This total mechano-synthesis route distinguishes itself through eco-friendly reaction conditions, exceptional stepwise efficiency, intuitive operability, and pronounced potential for large-scale implementation, paving the way for PTV's streamlined and sustainable manufacture.","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 4","pages":" 367-374"},"PeriodicalIF":0.0,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d4mr00036f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142165110","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}

引用次数: 0

Elucidating tribochemical reaction mechanisms: insights into tribofilm formation from hydrocarbon adsorbates coupled with tribochemical substrate wear† 阐明摩擦化学反应机制：深入了解碳氢化合物吸附物与摩擦化学基体磨损相结合形成的三膜†。

RSC Mechanochemistry Pub Date : 2024-06-19 DOI: 10.1039/D3MR00036B

Yu-Sheng Li, Fakhrul H. Bhuiyan, Jongcheol Lee, Ashlie Martini and Seong H. Kim

{"title":"Elucidating tribochemical reaction mechanisms: insights into tribofilm formation from hydrocarbon adsorbates coupled with tribochemical substrate wear†","authors":"Yu-Sheng Li, Fakhrul H. Bhuiyan, Jongcheol Lee, Ashlie Martini and Seong H. Kim","doi":"10.1039/D3MR00036B","DOIUrl":"https://doi.org/10.1039/D3MR00036B","url":null,"abstract":"Tribochemical reactions, chemical processes that occur by frictional shear at sliding interfaces, lead to tribofilm formation or substrate wear that directly affect the efficiency of machinery. Here, we report tribofilm growth through tribopolymerization and tribochemical wear of a silica surface due to reactions with organic precursors methylcyclopentane, cyclohexane, cyclohexene, and α-pinene. The activation volume determined from the stress dependence of reaction yield is correlated to the chemical reactivity of the precursor molecules. The molecules with higher tribochemical reactivity exhibited smaller activation volume, implying that less mechanical energy was required to initiate tribochemical reactions. Nudged elastic band calculations for the hypothetical pathways for the observed tribochemical reactions suggested that the smaller activation volume could be related to smaller thermal activation energy at the rate-limiting step. The tribofilm formation yield was found to increase with load whereas the load dependence of tribochemical wear was negligible. The environment dependence of the sliding processes was also analyzed. Results showed that, compared to a dry N2 environment, the tribopolymerization reaction yield increased in dry air but decreased in N2 with 40% relative humidity, while the wear rate remained unchanged. This finding suggested that during sliding, the reactive sites exposed at the worn surface could be re-oxidized by even trace amounts of oxygen or water vapor in the environment. This analysis of tribofilm yield and substrate wear in various environments showed that ambient gas can change the tribochemical reactivities of the reactant, which leads to different load dependencies of tribopolymerization and tribochemical wear.","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 4","pages":" 328-341"},"PeriodicalIF":0.0,"publicationDate":"2024-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d3mr00036b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142165141","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}

引用次数: 0

Facile mechanochemical synthesis of hypervalent tin(iv)-fused azo/azomethine compounds showing solid-state emission† 显示固态发射的高价锡(iv)融合偶氮/偶氮亚甲基化合物的简便机械化学合成†

RSC Mechanochemistry Pub Date : 2024-06-17 DOI: 10.1039/D4MR00048J

Masayuki Gon, Taichi Kato, Kazuya Tanimura, Chiaki Hotta and Kazuo Tanaka

引用次数: 0

Mechanochemical transformation of tetraaryl[3]cumulenes to benzofulvenes via electrophilic iodocyclization† 四芳基[3]积雪烯通过亲电碘代环化作用向苯并呋喃的机械化学转化†

RSC Mechanochemistry Pub Date : 2024-06-10 DOI: 10.1039/D4MR00022F

Fumitoshi Yagishita, Shoma Mukai, Sota Abe, Shoko Ueta, Yasushi Yoshida, Yukihiro Arakawa, Keiji Minagawa and Yasushi Imada

引用次数: 0

Atomistic simulations of mechanically activated reactions for oxygen release from polymers† 聚合物释放氧气的机械激活反应的原子模拟†。

RSC Mechanochemistry Pub Date : 2024-06-07 DOI: 10.1039/D4MR00004H

José Cobeña-Reyes, Fakhrul H. Bhuiyan and Ashlie Martini

{"title":"Atomistic simulations of mechanically activated reactions for oxygen release from polymers†","authors":"José Cobeña-Reyes, Fakhrul H. Bhuiyan and Ashlie Martini","doi":"10.1039/D4MR00004H","DOIUrl":"https://doi.org/10.1039/D4MR00004H","url":null,"abstract":"Singlet oxygen molecules are useful in several therapeutic applications involving photo-activated release of oxygen from carrier molecules toward targeted cells. However, the drawbacks of existing photo-activated methods encourage the development of alternatives, particularly polymer mechanophores that act as oxygen carriers. Here, we present a reactive molecular dynamics simulation-based study of an endoperoxide-based polymer for which oxygen release can be activated either thermally or mechanochemically. Simulations of the polymers heated are compared to simulations of the polymers subject to compression and shear at room temperature. Results show that oxygen release is preceded by deformation of the anthracene ring in both thermal and mechanochemical reactions. However, in the mechanically activated reaction, this deformation is imposed directly by chemical bonding between the oxygen and atoms in the shearing surfaces, eliminating the need for high temperature to initiate the oxygen release. These results could be useful in the development of alternative therapeutic protocols that do not rely on photo-activated reactions.","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 4","pages":" 361-366"},"PeriodicalIF":0.0,"publicationDate":"2024-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d4mr00004h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142165109","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}

引用次数: 0

Mechanochemical synthesis of β-cyclodextrin urea derivatives under reactive CO2 atmosphere by Staudinger aza-Wittig reaction† 在活性 CO2 气氛下通过 Staudinger aza-Wittig 反应机械化学合成 β-环糊精脲衍生物†。

RSC Mechanochemistry Pub Date : 2024-06-04 DOI: 10.1039/D4MR00020J

Sawssen Nasri, Maxime Lestoquoy, Anne Ponchel, Eric Monflier and Stéphane Menuel

引用次数: 0

A hybrid density functional study on the mechanochemistry of silicon carbide nanotubes 碳化硅纳米管机械化学的混合密度泛函研究

RSC Mechanochemistry Pub Date : 2024-05-30 DOI: 10.1039/D4MR00043A

Aabiskar Bhusal, Kapil Adhikari and Qian Sun

{"title":"A hybrid density functional study on the mechanochemistry of silicon carbide nanotubes","authors":"Aabiskar Bhusal, Kapil Adhikari and Qian Sun","doi":"10.1039/D4MR00043A","DOIUrl":"https://doi.org/10.1039/D4MR00043A","url":null,"abstract":"The constrained geometries simulate the external force (CoGEF) method mimics the application of external stress on molecules. Herein, we used the CoGEF method at the hybrid density functional theory level to investigate the behavior of silicon carbide nanotubes (SiCNTs) under longitudinal stress. When the SiCNTs are under longitudinal stress, we observe a gradual decrease in the binding energy and the frontier orbital gap with the applied strain until a critical threshold is reached. Beyond this threshold, a sudden increase in both parameters occurs, indicating the formation of some kind of stable structure. The higher binding energy of the larger SiCNTs makes them more resistant to rupture under strain, suggesting their increased mechanical strength. Additionally, we observed a rapid initial increase of Young's modulus of SiCNTs and convergence to a constant magnitude with further increase in their diameter. Therefore, CoGEF analysis provides invaluable insights into the changes occurring in the structural and electronic properties of SiCNTs when subjected to stress.","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 4","pages":" 413-421"},"PeriodicalIF":0.0,"publicationDate":"2024-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d4mr00043a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142165147","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}

引用次数: 0

Revealing the mechanism of reductive, mechanochemical Li recycling from LiFePO4† 揭示从磷酸铁锂（LiFePO4†）中还原性机械化学回收锂的机制

RSC Mechanochemistry Pub Date : 2024-05-18 DOI: 10.1039/D4MR00014E

David Geiß, Oleksandr Dolotko, Sylvio Indris, Christian Neemann, Andrei Bologa, Thomas Bergfeldt, Michael Knapp and Helmut Ehrenberg

{"title":"Revealing the mechanism of reductive, mechanochemical Li recycling from LiFePO4†","authors":"David Geiß, Oleksandr Dolotko, Sylvio Indris, Christian Neemann, Andrei Bologa, Thomas Bergfeldt, Michael Knapp and Helmut Ehrenberg","doi":"10.1039/D4MR00014E","DOIUrl":"https://doi.org/10.1039/D4MR00014E","url":null,"abstract":"In order to mitigate the risks associated with cobalt supply, a safe and affordable LiFePO4-based (LFP) cathode for Li-ion batteries can be a significant solution to meet the rapidly growing battery market. However, economical and environmentally friendly recycling of LFP is impossible with currently available recycling technologies. In this study, an acid-free mechanochemical approach is applied to reclaim Li from LFP using Al as a reducing agent. The reaction mechanism involved in reductive ball-milling followed by water leaching has been elucidated through the examination of various milling times and molar ratios of components, fostering a deeper understanding of the process. Assessing the yield and purity of the final products provides insights into potential enhancements for this technology. Utilizing Al as the material of the current collector eliminates the need for additional external additives, thereby simplifying the recycling workflow. Continued research into this process has the potential to facilitate efficient and economical recycling of LFP materials.","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 4","pages":" 349-360"},"PeriodicalIF":0.0,"publicationDate":"2024-05-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d4mr00014e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142165108","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}

引用次数: 0

Mechanochemical synthesis of Zn-bionanohybrids: size effect at the nanoscale to improve their enzyme-like activity† Zn 生物杂化物的机械化学合成：通过纳米尺度的尺寸效应提高其酶样活性†。

RSC Mechanochemistry Pub Date : 2024-05-16 DOI: 10.1039/D4MR00019F

Carla Garcia-Sanz, Laura Guijarro, Mirosława Pawlyta and Jose M. Palomo

{"title":"Mechanochemical synthesis of Zn-bionanohybrids: size effect at the nanoscale to improve their enzyme-like activity†","authors":"Carla Garcia-Sanz, Laura Guijarro, Mirosława Pawlyta and Jose M. Palomo","doi":"10.1039/D4MR00019F","DOIUrl":"https://doi.org/10.1039/D4MR00019F","url":null,"abstract":"The mechanochemical synthesis of nanomaterials for catalytic applications is a growing research field owing to its simplicity, scalability, and eco-friendliness. In this work, we synthesised new zinc bionanohybrids via a mechanochemical method involving a size effect at the nanoscale and microscale levels of the final nanostructure. This effect translates into an improvement in the catalytic properties of this nanomaterial, such as enzyme-like activities, compared to that synthesized in an aqueous media. One-pot synthesis was performed by combining Candida antarctica lipase B (CALB) solution, solid zinc salts and phosphate or bicarbonate salts using the ball-milling approach, where overall reaction times were drastically reduced in comparison with the traditional aqueous method. The reaction was carried out at r.t. and the synthesis process was evaluated by considering the use of steel balls with different sizes, completely dry conditions or in the presence of a very small amount of water as an additive (2 mL), and incubation methods (planetary or horizontal ball milling). The final nanostructure of the Zn biohybrids was determined using XRD, FT-IR, TEM and SEM analysis, demonstrating changes in metal species and drastic changes in the nanostructure conformation of the biohybrids obtained through the mechanical approach compared to those obtained through the aqueous method. The size effect at the nanoscale was also demonstrated in the final species, showing a reduced size. This nanoscale effect of the material had a positive impact on the catalytic properties of the materials, in some cases showing up to 2000 times greater activity compared to the counterpart synthesised under aqueous conditions.","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 3","pages":" 219-227"},"PeriodicalIF":0.0,"publicationDate":"2024-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d4mr00019f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141583705","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}

引用次数: 0