Molecular Catalysis最新文献

{"title":"Electrochemical C–H silylation of azauracils with hydrosilanes","authors":"Zhihua Zhang ,&nbsp;Jingfang Wang ,&nbsp;Changsheng Qin ,&nbsp;Shuai Zhang ,&nbsp;Yi Sun ,&nbsp;Chenxu Li ,&nbsp;Xinyue Li ,&nbsp;Fanxu Meng ,&nbsp;Fanghua Ji ,&nbsp;Guangbin Jiang","doi":"10.1016/j.mcat.2025.115218","DOIUrl":"10.1016/j.mcat.2025.115218","url":null,"abstract":"<div><div>Polysubstituted azauracils represent highly important nitrogen-containing heterocyclic compounds that are widely found in biologically active molecules. Current synthetic methods primarily rely on expensive transition metals or often toxic photocatalysts to achieve C<img>H functionalization of azauracils, making it imperative to develop simpler and more practical synthetic approaches. Electroorganic synthesis offers an excellent alternative strategy. Herein, we disclose an electrochemical C<img>H silylation method for the synthesis of various silicon-substituted azauracils using azauracils and hydrosilanes as starting materials. This transformation is conducted in an undivided cell, offering operational simplicity, excellent substrate compatibility, and scalability to gram-scale synthesis. Furthermore, this strategy enables the late-stage derivatization of valuable molecules. Mechanistic studies reveal that azauracils capture silicon radicals through three distinct pathways, ultimately generating diverse polysubstituted azauracil derivatives.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"583 ","pages":"Article 115218"},"PeriodicalIF":3.9,"publicationDate":"2025-05-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144123941","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanistic study on the conversion of primary alcohols and butadiene into branched ketones using a rhodium catalyst","authors":"Chaiyaporn Lakmuang ,&nbsp;Natcha Prommoon ,&nbsp;Natnicha Namwong ,&nbsp;Vudhichai Parasuk ,&nbsp;Boodsarin Sawatlon","doi":"10.1016/j.mcat.2025.115237","DOIUrl":"10.1016/j.mcat.2025.115237","url":null,"abstract":"<div><div>The direct formation of saturated branched ketones from primary alcohols and butadiene in the absence of premetalated intermediates or other hydrogen sources is a mechanistically intriguing transformation. Catalyzed by a rhodium(I) catalyst (Rh(COD)₂BAr^F₄/PPh₃) under basic conditions, this reaction proceeds with moderate to high experimental yields. Applying density functional theory, we investigate the mechanism of the conversion of 3-methoxybenzyl alcohol and butadiene into (branched) isobutyl ketone. This reaction involves four key steps: (i) oxidation of the alcohol to the corresponding aldehyde, with the generation of an Rh(I) hydride complex as an active catalyst, (ii) hydrogenation of butadiene to form an allyl–Rh(I) complex, (iii) carbonyl addition from the allylic carbon, forming an Rh(I) alkoxide intermediate, and (iv) an intramolecular hydrogen-transfer processes to generate the desired ketone product. The rate-determining states correspond to the carbonyl addition, involving both the intermediate and transition states, with an energy barrier of +30.4 kcal/mol. We found that two PPh₃ ligands are coordinated to the Rh center throughout the reaction. Therefore, carbonyl addition to the linear ketone is inhibited by steric hindrance around the metal center. Stereoisomerism among intermediates has a negligible effect on the reaction energetics and does not affect the configuration of the final product, which is released in an enolate form. Calculated positions of the transferred hydrogens align with the experimental deuterium labeling results, highlighting a hydrogen (auto)transfer mechanism in the transformation of primary alcohols to branched ketones.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"583 ","pages":"Article 115237"},"PeriodicalIF":3.9,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144123940","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Single-point mutation to realize the switch between “specificity” and “promiscuity” in glucose dehydrogenase","authors":"Yunye wang ,&nbsp;Mengting Li ,&nbsp;Yinan Li ,&nbsp;Jiuming Zhang ,&nbsp;Di Wang ,&nbsp;Qingyu Wang ,&nbsp;Jingping Ouyang ,&nbsp;Song You","doi":"10.1016/j.mcat.2025.115233","DOIUrl":"10.1016/j.mcat.2025.115233","url":null,"abstract":"<div><div>Glucose dehydrogenase (GDH) typically demonstrates unique preference toward glucose, leaving tiny space for catalytic promiscuity and displaying no activity toward other saccharide substrates. Enzyme engineering centering on sites with low conservation is distressingly weak on altering this situation. In this context, we came up with a “single-point mutation regulation strategy” to realize the switch between “specificity” and“promiscuity”, which was based on highly conserved residues, namely E96 and W152. This strategy was successfully achieved with a single mutation and manageable screening through 96-well plate, yielding three best-performing variants, namely DN46-W152N, DN46-E96Q and DN46-E96V, toward mannose, xylose and ribose, respectively. Among these variants, DN46-W152N displayed a k_cat/K_m value 260 times higher than that of <em>Bs</em>GDH towards mannose, and a 360-fold increasement was observed in the case of DN46-E96Q toward xylose. Meanwhile, DN46–96 V demonstrated a meaningful yet rarely achievable activity toward ribose. Above results facilitated one step forward in the promiscuity engineering of GDH, paving the way for further enriching the functionality of dehydrogenase.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"583 ","pages":"Article 115233"},"PeriodicalIF":3.9,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144123939","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enhancing ursodeoxycholic acid synthesis: Overcoming multi-step reaction barriers with a cofactor self-cycling cascade system","authors":"Xiubing Xie ,&nbsp;Runyi Huang ,&nbsp;Wenchi Zhang ,&nbsp;Rongzhen Zhang","doi":"10.1016/j.mcat.2025.115219","DOIUrl":"10.1016/j.mcat.2025.115219","url":null,"abstract":"<div><div>Traditional biosynthesis of ursodeoxycholic acid (UDCA) relies on microbial transformation and multi-enzyme catalysis, but its yield is often limited by the complexity of the process and the high demand for cofactors. In this study, we optimized the linker between <em>Hs</em>7β-HSDH and <em>Bm</em>7α-HSDH, and developed an efficient cascade catalytic system through strategies such as co-expression and enzyme fusion. The engineered system, <em>Hs</em>7β-HSDH-(GGGGS)₂-<em>Bm</em>7α-HSDH, enabled a one-pot synthesis of chenodeoxycholic acid (CDCA) to UDCA with significantly improved efficiency. The recombinant bacteria expressing the fusion protein, <em>E. coli</em>/<em>Hs</em>7β-HSDH-(GGGGS)₂-<em>Bm</em>7α-HSDH, achieved a 95.4 % yield within 2 h at 10 g/L CDCA and 0.5 mM NAD⁺. By implementing a fed-batch strategy, a yield of 91.6 % was obtained at a substrate concentration of 50 g/L, with a theoretical space-time yield of 110 g/L/d. This study presents an efficient, environmentally friendly, one-pot cascade reaction system that simplifies UDCA biosynthesis while reducing the need for additional cofactors and co-substrates, offering significant potential for industrial-scale production.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"583 ","pages":"Article 115219"},"PeriodicalIF":3.9,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144115398","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Direct Z-scheme HfS2/Ga2SSe heterojunction: A strain-tunable and full pH-tolerant high-efficiency photocatalyst for hydrogen production","authors":"Qilin Luo,&nbsp;Yongchao Liang,&nbsp;Xiaoxiao Li,&nbsp;Wenqiang Li,&nbsp;Qian Chen","doi":"10.1016/j.mcat.2025.115227","DOIUrl":"10.1016/j.mcat.2025.115227","url":null,"abstract":"<div><div>Photocatalytic water splitting for hydrogen production holds significant importance for green renewable energy. However, the fabrication of suitable photocatalysts has persistently hindered its development. Therefore, this study constructs a HfS₂/Ga₂SSe van der Waals heterostructure using HfS₂ and Ga₂SSe, and employs first-principles calculations to systematically investigate the heterostructure's stability, electronic structure, optical properties, and photocatalytic mechanisms. The results demonstrate that the heterostructure exhibits structural stability and satisfies the redox potential requirements for water splitting across the full pH range of 0–14. The type-II staggered band alignment enables Z-scheme migration of photogenerated electron-hole pairs, establishing this configuration as a Z-scheme hetero structure. The heterostructure's superior carrier mobility significantly enhances photocatalytic efficiency. The heterostructure achieves a remarkable solar-to-hydrogen conversion efficiency of 33.70 % under AM1.5 G solar irradiance. Biaxial strain engineering positively modulates the hetero structure's electronic and optical properties, enhancing optical absorption, optimizing bandgap alignment, and improving photocatalytic performance. Analysis of Gibbs free energy demonstrates that the hydrogen evolution reaction can proceed spontaneously under irradiation. This confirms the HfS₂/Ga₂SSe heterostructure as a promising candidate material for photocatalytic water splitting applications.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"583 ","pages":"Article 115227"},"PeriodicalIF":3.9,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144106290","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemical CH Thiocyanation/Halogenation of 4-Arylthioazol-2-ones","authors":"Swayamprava Swain,&nbsp;Niranjan Panda","doi":"10.1016/j.mcat.2025.115210","DOIUrl":"10.1016/j.mcat.2025.115210","url":null,"abstract":"<div><div>Direct thiocyanation of 4-arylthioazol-2-one was performed by electrochemical process using ammonium thiocyanate as the thiocyanating agent at room temperature without any supportive electrolyte. From control experiments, it is clear that the reaction proceeds through a radical pathway. A similar process was also employed for the C5-halogenation of 4-arylthioazol-2-one using ammonium halides as the halogen sources. Further, the thiocyanated 4-thioazol-2-ones were transformed to sulfenyl derivatives.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"583 ","pages":"Article 115210"},"PeriodicalIF":3.9,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144106289","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"DFT investigation of photocatalytic contra-thermodynamic alkene isomerization in α-substituted alkenylazaarenes","authors":"Shang Gao ,&nbsp;Mingwei Yang ,&nbsp;Yanyan Zhu ,&nbsp;Jinshuai Song","doi":"10.1016/j.mcat.2025.115215","DOIUrl":"10.1016/j.mcat.2025.115215","url":null,"abstract":"<div><div>Photocatalytic olefin isomerization is a promising method for enhancing the yield of thermodynamically unfavorable products, though its mechanism is not fully understood. In this study, we propose a mechanism for asymmetric photocatalytic olefin isomerization using density functional theory (DFT). This mechanism involves hydrogen atom transfer, single electron transfer, and proton transfer processes. By performing linear regression of the intrinsic and formal Gibbs energy changes (Δ<em>G</em> and Δ<em>G</em>_form) across various substrates, we define a quantitative descriptor of effective input energy, Δ<em>G</em>_eff, in photocatalysis. We found that a driving force of -0.92 kcal/mol is derived from light, which alters isomer selectivity by changing the reactivity of intermediates. Compared to radical species, the carbanion intermediate exhibits greater local nucleophilicity at C_γ than at C_α, resulting in a lower barrier for protonation and product accumulation. This study provides a quantitative understanding of the photocatalytic thermodynamically unfavorable olefins isomerization.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"583 ","pages":"Article 115215"},"PeriodicalIF":3.9,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144106288","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Selective oxidation of glycerol to lactic acid catalyzed by Cu-based MOFs","authors":"Xinshu Xie,&nbsp;Shuangming Li,&nbsp;Hanqu Fu,&nbsp;Yiwen Wang,&nbsp;Feng Chen,&nbsp;Shuang Ren,&nbsp;Jili Zhang,&nbsp;Sansan Yu","doi":"10.1016/j.mcat.2025.115209","DOIUrl":"10.1016/j.mcat.2025.115209","url":null,"abstract":"<div><div>The researchers synthesized four copper-based MOFs (Cu-MOF, Cu-MOF-74, Cu-PTA-MOF, and NH₂-Cu-MOF) and used them for the first time in the selective catalytic oxidation of glycerol to lactic acid. The crystal phase, morphology, crystal structure and chemical state of surface elements of the catalysts were characterized by XRD, SEM, TEM and XPS. The results show that the active sites of Cu-based MOFs are all Cu²⁺. Cu-MOF has the largest specific surface area and the smallest lattice spacing. From this, it can be seen that Cu-MOF has the most active catalytic sites, promotes charge transfer and increases electron mobility, effectively improving glycerol adsorption capacity. The Cu-MOF with spherical morphology has the strongest catalytic ability. Glycerol conversion is as high as 97.15 %, and the lactic acid selectivity is 82.02 %. The adsorption properties of glycerol on the surface of Cu-based MOFs were studied by density functional theory (DFT) calculations. The results show that Cu-MOF has the largest adsorption energy, which is favorable for the bonding of glycerol on its surface. Cycling experiments demonstrated that Cu-MOF showed good stability during the catalytic process and no significant changes in the crystalline phase and valence state of the reacted Cu-MOF were observed by XRD and XPS.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"583 ","pages":"Article 115209"},"PeriodicalIF":3.9,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144106287","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exploring molecular catalysis in the enzymatic synthesis of biolubricants: A comprehensive review and bibliometric assessment","authors":"Francisco Simão Neto ,&nbsp;Patrick da Silva Sousa ,&nbsp;Rafael Leandro Fernandes Melo ,&nbsp;Viviane de Castro Bizerra ,&nbsp;Dayana Nascimento Dari ,&nbsp;Kaiany Moreira dos Santos ,&nbsp;Paulo Gonçalves de Sousa Junior ,&nbsp;Jessica Lopes da Silva ,&nbsp;Jesús Fernández-Lucas ,&nbsp;Francisco Izaias da Silva Aires ,&nbsp;Maria Alexsandra de Sousa Rios ,&nbsp;Mohammad J. Taherzadeh ,&nbsp;José Cleiton Sousa dos Santos","doi":"10.1016/j.mcat.2025.115191","DOIUrl":"10.1016/j.mcat.2025.115191","url":null,"abstract":"<div><div>Biolubricants are produced from renewable biological raw materials using sustainable methods, such as enzymatic catalysis and the esterification of vegetable oils and animal fats, representing a promising alternative. Enzymatic biocatalysts, in particular, have high specificity in synthesizing new products, making them a fundamental tool in producing biolubricants. This study aims to conduct a detailed bibliometric analysis to evaluate the primary studies on the enzymatic synthesis of biolubricants. It also identifies prominent countries, authors, journals, and research areas contributing to the topic. Describe the characteristics, advantages, and challenges associated with biolubricants, including the types of enzymes, substrates, and raw materials used, the mechanisms of enzymatic synthesis, and the techniques used for production, optimization, and characterization. The keywords \"biofuel\", \"biolubricant\" and \"enzyme\" were used for the database. The search was carried out in Scopus, covering the period from 2014 to June 2024. The analysis returned 358 articles and revealed significant international collaboration, especially between Brazil, India, and China. Brazil leads the field, contributing 19.27 % of the publications. Brazilian institutions have shown remarkable specialization in producing lubricants, using the country's rich biodiversity and biomass resources to promote research and innovation. Thus, this study presents a complete contextualization of the production of biolubricants, with an overview of world production in the area and a literature review that addresses relevant topics such as production routes and product analysis.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"583 ","pages":"Article 115191"},"PeriodicalIF":3.9,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144106222","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Multi-enzyme cascade reaction for stereoconvergent synthesis of (R)-decalactones","authors":"Shuo Wang ,&nbsp;Binhao Wang ,&nbsp;Guochao Xu,&nbsp;Ye Ni","doi":"10.1016/j.mcat.2025.115193","DOIUrl":"10.1016/j.mcat.2025.115193","url":null,"abstract":"<div><div>Chiral lactones are valuable aroma compounds which have wide applications in food and fragrance industries. However, the synthesis of chiral lactones often faces challenges such as low yield, poor stereoselectivity, high production costs and harsh reaction conditions. To overcome these issues, a novel multi-enzyme cascade reaction was designed to achieve dynamic resolution of decalactones through stereoconvergent preparation of hydroxydecanoic acids. Utilizing lactonase <em>Rpa</em>3624 for hydrolysis, <em>Hb</em>KR for stereoselective oxidation, and <em>Sm</em>CR_V4 for stereoselective reduction, 50 mM racemic <em>γ</em>-decalactone was stereoselectively converted into (<em>R</em>)-<em>γ</em>-decalactone with 96.5 % <em>ee</em> and 89.2 % yield in 1 h. By replacing <em>Sm</em>CR_V4 with <em>Sm</em>CR_M5, 50 mM racemic <em>δ</em>-decalactone was also efficiently converted into (<em>R</em>)-<em>δ</em>-decalactone with excellent stereoselectivity of 95.5 % and 84.9 % yield. The one-pot process could be operated under mild conditions, enhanced atom economy and reduced production costs, and provides a sustainable approach for the synthesis of chiral decalactones. This work demonstrates the potential of multi-enzyme systems in synthesis of chiral lactones for industrial application.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"583 ","pages":"Article 115193"},"PeriodicalIF":3.9,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144106285","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}