化学•材料最新文献

{"title":"One-Pot Synthesis of Tricyclic Benzoxazines and Benzoxazepine by Heterogeneous Biochemo Multienzyme Cascade Reaction.","authors":"Eliana Capecchi,Elisabetta Tomaino,Bruno M Bizzarri,Raffaele Saladino","doi":"10.1021/acs.joc.4c02868","DOIUrl":"https://doi.org/10.1021/acs.joc.4c02868","url":null,"abstract":"Benzoxazine and benzoxazepine derivatives with tricyclic five-, six-, and seven-membered lactone and lactam rings were synthesized in one-pot conditions by using biochemo multienzyme cascade of lipase M and tyrosinase. The reaction involves tyrosinase-mediated ortho-hydroxylation of the phenolic moiety, followed by 1,6-Michael addition and tandem intramolecular ring closure. The method achieves high atom economy, minimizes purification steps, and provides a sustainable alternative to conventional multistep syntheses. Enzymes showed excellent reusability, further enhancing the green approach.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"7 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872109","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":"Synthesis of Thienoacenes via Cascade Copper-Catalyzed C–S Coupling and Thienannulation Reactions and Their Thermoelectric Properties","authors":"Jiaxuan Dong, Yifan Lv, Yiyang Li, Kexin Xu, Xinrui Cui, Cun-Yue Guo, Baolin Li","doi":"10.1021/acs.joc.4c03182","DOIUrl":"https://doi.org/10.1021/acs.joc.4c03182","url":null,"abstract":"Thienoacenes are a prominent class of fused-ring conjugated organic compounds and have attracted considerable attention due to their high coplanarity, good stability, high charge-carrier mobility, etc. However, most current synthetic methods toward thienoacenes require costly starting materials and reagents, as well as a lengthy synthetic procedure with low overall yields. Herein, a nonprecious copper-catalyzed system without additional ligands was developed to facilitate C–S coupling and 5-endo-dig thienannulation reaction, leading to the synthesis of a range of thienoacenes including dithieno[3,2-<i>b</i>:2′,3′-<i>d</i>]thiophenes (DTTs) and thieno[2′,3′:4,5]thieno[3,2-<i>b</i>]thiophene[2,3-<i>d</i>]thiophene (TTAs) with yields of up to 90% (for single-sided thienannulation reactions) and 65% (for double-sided thienannulation reactions). In addition, three π-extended DTTs were studied as potential thermoelectric materials, and their composites with single-walled carbon nanotubes (SWCNTs) exhibited high thermoelectric performance with the power factor up to 399.01 ± 16.26 μW m^–1 K^–2 at room temperature, which is the highest reported for thermoelectric composites comprising small-molecule thiophene derivatives and SWCNTs, signifying a step forward in the development of high-performance thermoelectric composites based on thiophene derivatives.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867123","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":"Platinum Carbonyl Chini Clusters as Catalysts for Photocatalytic H2 Generation","authors":"Aleksander Senderowski, Ana Andrea Méndez-Medrano, Isabelle Lampre, Hynd Remita, Dorota Rutkowska-Zbik","doi":"10.1021/acs.jpcc.5c00212","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00212","url":null,"abstract":"Platinum Chini clusters with a general formula [Pt₃(CO)₆]_<i>n</i>^2– are formed by stacked Pt₃ units. They have fascinating electronic and optical properties that can be tuned with <i>n</i>. In the current manuscript, the electronic, photochemical, and charge transport properties of the platinum Chini clusters are studied with the density functional theory (PBE and CAM-B3LYP/6-31G(d,p)+LANL2DZ) as a function of their nuclearity number <i>n</i>. Our theoretical predictions are supported by experimental proof of concept, in which synthesized Chini clusters are deposited as cocatalysts on TiO₂ for photocatalytic hydrogen generation. We demonstrate that smaller clusters (<i>n</i> = 4) are more effective than larger ones (<i>n</i> = 7–8), and that composites having lower Pt content perform better.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"13 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862312","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Formation and Transport of Polarons in β-Ga2O3: an Ab Initio Study","authors":"Zhimeng Hao, Taifeng Liu","doi":"10.1021/acs.jpcc.5c01741","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01741","url":null,"abstract":"We investigated the formation of small-hole polarons in β-Ga₂O₃ from first-principles, accounting for their coupling to all phonon modes. Our results reveal that small-hole polarons can form at multiple oxygen sites, namely, O_I, O_II, and O_III, with the O_II site being the most stable. The phonons involved in the coupling for polaron formation at these three oxygen sites exhibit minimal differences. However, at the O_II site, the localized hole originates from entire highest valence band (EHVB), whereas at the O_I and O_III sites, the localized hole state is a hybridization of the EHVB and lower-lying bands. This distinction results in the lower contribution of electronic weight of small hole polarons on the O_II site, which leads the lowest formation energy for the polaron at this site. The hopping of small-hole polarons between O_II sites occurs via an adiabatic process, with an activation energy of 0.37 eV. Additionally, we investigated electron polarons in β-Ga₂O₃ using the same approach but observed no evidence of polaronic states, either large or small. This study provides new insights into polaron physics in β-Ga₂O₃ and offers guidance for understanding and exploring polarons in related materials.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"7 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862581","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unintended Consequences of Aquatic Enrichment in Experimental Biology","authors":"Tamzin A. Blewett, Kerri Lynn Ackerly, Josefin Sundin, Timothy D. Clark, Lauren E. Rowsey, Robert A. Griffin, Moa Metz, Luis Kuchenmüller, Robine H. J. Leeuwis, Marie Levet, Sidney Martin, Ben Speers-Roesch, Fredrik Jutfelt, Shira Joudan","doi":"10.1021/acs.est.4c11276","DOIUrl":"https://doi.org/10.1021/acs.est.4c11276","url":null,"abstract":"Enrichment in aquatic animal studies is important for promoting welfare and maintaining animal health and can be categorized by physical, sensory, social, occupational, and dietary enrichment. However, the risk of potential chemical leaching associated with physical enrichment items has been largely overlooked (i.e., artificial plants or shelter). Most enrichment items lack information on their chemical composition and have not undergone testing for plastic or metal leachates that can alter water chemistry and impair animal physiology. In fish and invertebrate research, these leachates have the potential to modify the health of aquatic animals or their reproductive processes. Moreover, in toxicology research, altered chemical exposure concentrations and interactive effects with leachates could invalidate toxicity assays and lead to misleading results. We identify key contaminants associated with common enrichment items and highlight the substantial lack of empirical research focusing on the confounding factors associated with aquatic enrichment. We explore the mechanisms through which relevant leachates can complicate experimental outcomes, detailing the pathways by which these substances may interact with both the experimental environment and the animals themselves. We conclude that there is widespread potential for serious complications to research outcomes and chronic toxicity from enrichment materials. Therefore, we advocate for the establishment of standardized regulations and a global certification system for aquatic enrichment items to ensure the validity of studies and to safeguard animal welfare. We encourage researchers to critically consider the implications of leaching from aquatic enrichment when designing experimental systems.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"40 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866566","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Fucoidan-chitosan nanocarriers for anticancer therapy through chemodynamic, photothermal, and glucose starvation strategies","authors":"Da Yeong Choi ,&nbsp;Chang Hyeon Ha ,&nbsp;Su Jeong Lee,&nbsp;Se Hwa Cheon,&nbsp;Gi Hun Seong","doi":"10.1016/j.colsurfb.2025.114726","DOIUrl":"10.1016/j.colsurfb.2025.114726","url":null,"abstract":"<div><div>The tumour microenvironment (TME) presents a distinctive set of challenges and opportunities in the context of targeted cancer therapies, offering potential avenues for reducing non-specific cell death and side effects on normal cells. By combining chemodynamic therapy, starvation therapy, and photothermal therapy, our approach aims to activate drug release and generate reactive oxygen species within the TME. Specifically, we developed a fucoidan-chitosan (F/CS) nanocarrier loaded with 3,3′,5,5′-tetramethylbenzidine (T), Prussian blue (P), and glucose oxidase (GOx) (F/CS@TPGOx). It has been reported that fucoidan and chitosan target P-selectin and the glucose-rich microenvironment of pathological cancer. Furthermore, F/CS@TPGOx at a concentration of 4 µg/mL was observed to reduce cancer cell viability to less than 20 % following a four-hour incubation period. This indicates that fucoidan, the carrier, exhibits anticancer activity that is more pronounced than that observed in conventional anticancer nanocarriers. The findings demonstrated the efficacy of F/CS@TPGOx in cancer cell death in both in vitro and in vivo settings. This suggests F/CS@TPGOx as a promising material for targeted cancer therapy with the potential to be used in clinical biomedicine as a therapeutic platform with high efficacy and minimal side effects.</div></div>","PeriodicalId":279,"journal":{"name":"Colloids and Surfaces B: Biointerfaces","volume":"253 ","pages":"Article 114726"},"PeriodicalIF":5.4,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143874933","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Opposing Visual Impairments Induced by Structurally Similar Organophosphate Flame Retardants TPHP and CDP in Zebrafish Larvae","authors":"Yiqun Song, Ting Xu, Hongchang Zhang, Shuangqing Hu, Sheng Wei, Miao Cao, Huan Wang, Daqiang Yin","doi":"10.1021/acs.est.5c00663","DOIUrl":"https://doi.org/10.1021/acs.est.5c00663","url":null,"abstract":"Vision is the primary sensory function for most animals and is also a sensitive toxic target of environmental pollutants. A new class of organophosphate flame retardants (OPFRs) termed emerging OPFRs (eOPFRs) with limited toxicological information is rapidly developed into the substitutes of traditional OPFRs. In this study, we investigated the visual toxicity of triphenyl phosphate (TPHP, one traditional OPFR) and cresyl diphenyl phosphate (CDP, one emerging OPFR) on zebrafish larvae at environmentally relevant concentrations (3 and 30 nM). After 5 days of exposure, an opposite toxicity was found between the two OPFRs, manifested in the light perception and the gene expressions of visual opsins. CDP caused a weak reaction to light and overall inhibition of opsin expression (0.7- to 0.8-fold) in the larvae, while TPHP tended to stimulate these events (1.2- to 2.4-fold). Besides, we identified a key transcription factor, <i>tbx2a</i>, that was significantly disrupted in both OPFRs’ exposure. The differing ways in which both OPFRs bind to Tbx2a may be the reason behind their opposite effects. These findings provided new clues for the toxicological mechanisms of OPFRs and revisited the question regarding safe substitutes for those emerging contaminants.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"48 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866568","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ruminant methane mitigation: microbiological mechanisms and integrated strategies for sustainable livestock production in the context of climate change","authors":"Mingming Wang ,&nbsp;Tian Yang ,&nbsp;Ru Wang ,&nbsp;Xingqiang Fang ,&nbsp;Jikang Zheng ,&nbsp;Junyin Zhao ,&nbsp;Shengnan Zhao ,&nbsp;Zhipeng Sun ,&nbsp;Yongju Zhao","doi":"10.1016/j.rser.2025.115741","DOIUrl":"10.1016/j.rser.2025.115741","url":null,"abstract":"<div><div>Ruminant methane (CH₄) emissions not only cause serious environmental problems but also reduce the energy efficiency of animal feed. Rumen microbial fermentation is a major source of CH₄ emissions, and understanding the diversity and community structure of rumen microbes, and the relationship between feed efficiency and CH₄ emissions, is key to reducing CH₄ emissions. Strategies such as feed modification, microbial regulation and additive application have shown some CH₄ mitigation. For example, the addition of fats and fatty acids to the diet composition and the use of probiotics and microbial repellents can change the rumen microbial community structure and improve feed digestibility. Meanwhile, specific chemical analogues and plant secondary metabolites as additives can specifically inhibit the growth of methanogenic archaea and reduce CH₄ production. Although multiple CH₄ mitigation strategies have been evaluated for reducing CH₄ emissions from ruminants, there has been no comprehensive discussion in unravelling the molecular mechanisms of microbial fermentation processes and specific CH₄ inhibitors targeting metabolic pathways of methanogens. Therefore, this paper discusses the diversity and community structure of microorganisms in the rumen, methanogenic pathways, and the molecular mechanisms underlying the role of various CH₄ mitigation strategies in metabolic reactions and CH₄ production pathways in ruminants. This in-depth understanding can help develop more effective CH₄ mitigation strategies that can improve the productivity and sustainability of livestock operations while reducing greenhouse gas emissions. The article concludes by outlining important prospects and directions for future research targeting rumen microbial CH₄ mitigation and livestock sustainability.</div></div>","PeriodicalId":418,"journal":{"name":"Renewable and Sustainable Energy Reviews","volume":"217 ","pages":"Article 115741"},"PeriodicalIF":16.3,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143864074","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis of 3-Amino-β-lactams through Selective Imination of 3-Oxo-β-lactams","authors":"Sari Deketelaere, Emma Vandenheede, Nicola Piens, Lore Cools, Lieselotte Crul, Lotte Demeurisse, Karen Mollet, Christian V. Stevens, Matthias D’hooghe","doi":"10.1021/acs.joc.5c00205","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00205","url":null,"abstract":"3-Oxo-β-lactams are known to deliver different types of reaction products upon treatment with primary amines, predominantly governed by the nature of the C4 substituent. In this work, a C4 substituent-independent protocol for the conversion of 3-oxo-β-lactams to the corresponding 3-imino-β-lactams was developed. By using primary amine hydrochloric acid salts in combination with 2,4,6-collidine, or free primary amines in combination with acetic acid, the undesired ring opening of 4-aryl- and (<i>S</i>)-4-((<i>S</i>)-2,2-dimethyl-1,3-dioxolan-4-yl)azetidine-2,3-diones toward ethanediamides and α-aminoamides, respectively, is avoided, enabling the smooth transformation of any 3-oxo-β-lactam into its imine counterpart. As demonstrated by the ensuing synthesis of 3-alkylamino-β-lactams, 3-imino-β-lactams serve as building blocks for the construction of functionalized 3-amino-β-lactams, with the latter being key motifs in drug discovery.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"7 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862530","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":"An Accurate and Transferable ReaxFF Parameter Set toward the Simulation of a Plasma Etching Process in Semiconductor Manufacturing","authors":"Jinhuan Zhong, Qinhao Sun, Zhipeng Gao, Junting Li, Pengfei Shi, Huajie Xu, Yang Wang","doi":"10.1021/acs.jpcc.4c08709","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08709","url":null,"abstract":"The plasma etching mechanisms of silicon- and carbon-based materials using fluorine atoms are significant for guiding the semiconductor manufacturing processes; however, the fundamental studies are hindered by the difficulty of experimentally measuring what happens in the etching process at the atomic scale. Although reactive molecular dynamics simulation is a strong tool to study the reaction dynamics of a plasma etching process, there are still no available reactive potentials to study the fluorine-etching process. In this work, we developed a suite of accurate and transferable reactive force field (ReaxFF) parameter set for the C/H/O/Si/F systems, by using a multiobjective global optimization strategy combining the simulated annealing algorithm (SA) and particle swarm optimization (PSO) algorithms. Besides, we demonstrated that the developed ReaxFF parameter set is very precise and valid for describing various properties, including the reaction dynamics of F-containing small molecules, gas–liquid transition, and the F-etching process of various silicon/carbon-containing solids. The above findings indicate that the developed ReaxFF parameters can accurately describe the reactions and phenomena involving C/H/O/Si/F elements, which is expected to contribute greatly to future research endeavors on the etching process.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"7 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867148","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}