Accounts of Chemical Research最新文献

{"title":"Quantum Tunneling of Photogenerated Charges for Artificial Photosynthesis.","authors":"Ying Wang, Shuowen Wang, Xianzhi Fu, Jinlin Long","doi":"10.1021/acs.accounts.5c00295","DOIUrl":"10.1021/acs.accounts.5c00295","url":null,"abstract":"<p><p>ConspectusPhotocatalytic conversion of CO<sub>2</sub> and H<sub>2</sub>O to high-value chemicals or fuels provides a crucial pathway for efficiently achieving the conversion and storage of solar-to-chemical energy; however, the overall efficiency is severely restricted by the spatial separation of photogenerated charges. The lifetime of charges in a photoexcited semiconductor particle is mismatched utterly with the rate of interfacial redox reactions, locking kinetically the target reactions. To maximize the availability of photogenerated charges for artificial photosynthesis, constructing various types of heterojunctions including Schottky, p-n, and Z/S-scheme is widely used to manipulate the directional migration of photogenerated charges toward surface active sites, where photoredox catalysis proceeds. Even so, it is unavoidable for the recombination of initially separated charges at the interfacial heterojunctions composed of several atomic layers with less than 1.0 nm thickness, where the Coulomb force remains dominant, leading to the quadratic loss of charges on the surface or interface of catalyst particles. How to eliminate the Coulomb confinement for charges has been a highly interesting topic and yet a formidable challenge in the domain of photocatalysis and solar energy conversion.In this Account, aiming to suppress the recombination of initially separated charges, we introduced a novel strategy of charge tunneling separation to design efficient artificial photosystems for CO<sub>2</sub> conversion. An insulator is inserted between the semiconductor and metal to form the metal-insulator-semiconductor (MIS) structure, where the charge donor and acceptor are spatially separated by the insulating layer with a thickness of a few nanometers, different completely from the conventional Schottky junction with a direct contact M/S interface. Photoexcitation of the semiconductor unit generates a large population of hot electrons and holes, and then they immediately tunnel to the metal catalyst for redox reactions across the two M/I and I/S interfaces and the insulating layer. The tunneling separation proceeds within a few attoseconds at a mean free path. These tunneled electrons or holes are trapped, concentrated, and localized on the catalytic units consisting of metallic single atoms, nanoclusters (NCs), or nanoparticles (NPs), and thus the emphasis of this Account will be put on three aspects: (1) understanding the physical fundamentals of quantum tunneling of photogenerated charges for artificial photosynthesis, (2) smartly designing the chemical components and structures of functional units including photoabsorbers, insulators, catalytic active centers and interfaces to maximize the tunneling probability, and (3) constructing a MIS-type all-solar-driven artificial photosynthetic system, where the functional units responsible for CO<sub>2</sub> reduction and water oxidation are spatially segregated to enable efficient conversion of sol","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"2145-2156"},"PeriodicalIF":16.4,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144323794","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"","authors":"Feng Xie, Hao Wang* and Jing Li*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 13","pages":"962–968 XXX-XXX"},"PeriodicalIF":16.4,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.accounts.5c00217","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144516724","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"","authors":"Tonglin Yang, Yanwei Tang, Ying Wei*, Linghai Xie* and Wei Huang*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 13","pages":"962–968 XXX-XXX"},"PeriodicalIF":16.4,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.accounts.5c00180","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144516725","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"","authors":"Zi-Chao Wang,  and , Shi-Liang Shi*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 13","pages":"962–968 XXX-XXX"},"PeriodicalIF":16.4,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.accounts.5c00304","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144516726","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"","authors":"Ben Mao, Jun Yan, Yin Wei and Min Shi*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 13","pages":"962–968 XXX-XXX"},"PeriodicalIF":16.4,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.accounts.5c00228","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144516734","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"","authors":"Ying Wang, Shuowen Wang, Xianzhi Fu and Jinlin Long*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 13","pages":"962–968 XXX-XXX"},"PeriodicalIF":16.4,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.accounts.5c00295","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144516739","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Light-Driven C(sp³)-C(sp³) Bond Functionalizations Enabled by the PCET Activation of Alcohol O-H Bonds.","authors":"Danny Q Thach, Robert R Knowles","doi":"10.1021/acs.accounts.5c00246","DOIUrl":"10.1021/acs.accounts.5c00246","url":null,"abstract":"<p><p>ConspectusMethods that enable the selective functionalization of C-C bonds offer unique opportunities for the skeletal diversification of complex molecules and provide access to unique structures without the need for <i>de novo</i> synthesis. While considerable advances have been made in transition-metal-based approaches, much recent work has focused on alternative strategies for C-C bond cleavage enabled by transient free radicals. In particular, alkoxy radicals derived from simple alcohols are known to significantly destabilize adjacent C-C bonds, enabling spontaneous cleavage to eject a carbon-centered radical and afford carbonyl products via β-fragmentation. While this reactivity has long been recognized, its applications in synthesis have been limited, in part, by the challenges associated with generating the key alkoxy radical intermediates. The high bond dissociation free energies (BDFEs) of aliphatic alcohol O-H bonds (∼105 kcal/mol) preclude direct homolytic activation by hydrogen atom transfer, and most established strategies rely instead on stoichiometric prefunctionalization of the O-H bond. These approaches often further limit the scope of amenable chemistries that can be applied for postcleavage alkyl radical functionalization. Methods that could overcome these constraints have considerable synthetic potential, enabling straightforward access to reconfigured carbon frameworks from an abundant class of starting materials, as well as modular opportunities for radical functionalization. In this Account, we present our efforts toward the development of proton-coupled electron transfer (PCET) as a general mechanism for alkoxy radical generation from simple alcohols. In turn, this advance enabled us to develop a suite of novel methods for editing complex carbon frameworks via the cleavage and functionalization of C(sp<sup>3</sup>)-C(sp<sup>3</sup>) bonds. We first discuss the development of catalytic ring-opening isomerization reactions of cyclic benzylic carbinols to access linear aryl ketone products through a redox-relay approach. In these reactions, single electron oxidation of the substrate arene by an excited-state Ir(III) photocatalyst generates an arene radical cation that serves as an internal oxidant for an intramolecular PCET event, furnishing the alkoxy radical intermediate. This intermediate then undergoes C-C β-scission to provide the isomerized linear ketone products. We next present the discovery of an improved catalytic system for the direct activation of simple aliphatic alcohols. We then apply these chemistries for the light-driven depolymerization of lignin biopolymers, commercial phenoxy resins, hydroxylated polymers, and thiol epoxy thermosets. Notably, many of these redox isomerization reactions are thermodynamically unfavorable, providing isomerization products that are thermodynamically less stable than their corresponding starting materials. We then discuss the application of O-H PCET for the reconfiguratio","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"2061-2071"},"PeriodicalIF":16.4,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12258532/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144281648","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Improving interprofessional handover on labor and delivery: A needs assessment study.","authors":"Wynne I Leung, Crystal Emery, Rylan Egan","doi":"10.1080/13561820.2021.1888901","DOIUrl":"10.1080/13561820.2021.1888901","url":null,"abstract":"<p><p>Handover is the transfer of important clinical information between health providers. The current report describes a needs assessment of interprofessional labor and delivery handover at an urban hospital in Canada. The goal of this study was to explore the perceptions of the current handover meeting and opportunities for improvement. Using a constructivist paradigm, we conducted 28 semi-structured inter- views with handover participants. We used a recruitment grid to ensure we included the voices of participants representing each profession involved in interprofessional handover meetings. An inductive process was used to code the interview transcripts and theme the data. Major themes identified were: (1) Interprofessional handover contributes positively to team situational awareness, interprofessional relationships, and team communication; (2) Handover could be better if it had a more defined process; (3) Interprofessional handover can lead to feelings of intimidation; and (4) Interprofessional handovers on the labor and delivery unit in our setting need increased inclusivity of midwives. From these themes, continued development of interprofessional handover meetings on labor and delivery should be aimed at a formal definition of the scope and process for these meetings reducing feelings of intimidation, increased integration of Midwifery providers, and continued improvement of relationships between different professions and practitioners on labor and delivery.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"620-626"},"PeriodicalIF":16.4,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"39231223","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Analysis of the Efficacy and Safety of Intratymapanic Dexamethasone for Treating Meniere's Disease: A Randomized Controlled Trial.","authors":"Gendi Yin, Zhicheng Li, Shuqi Zhang, Xinyi Wang, Jiali Yang, Hao Cai, Xiangli Zeng","doi":"10.1177/01455613221120729","DOIUrl":"10.1177/01455613221120729","url":null,"abstract":"<p><p>ObjectivesOur objective was to study the efficacy and safety of intratymapanic dexamethasone (ITD) for treating in Méniere's disease in southern China.MethodsA total of 124 patients with Méniere's disease were randomly divided into 2 groups: ITD group (n = 62) and intratympanic lidocaine (ITL) group (n = 62). The ITD group was further randomly divided into 2 groups based on dexamethasone dosage: ITD1 (2 mg/ml) (n = 31) and ITD2 (5 mg/ml) group (n = 31). Symptom alleviation and complications were recorded after every treatment.ResultsVertigo was improved in 65% of patients who received ITD compared with 55% of patients who received ITL patients (<i>P</i> < .05). Three patients in the ITD2 group had from otomycosis, and 2 of these patients had a perforation; no tympanic membrane perforation was observed in the ITL and ITD1 group.ConclusionsCompared with lidocaine, dexamethasone is more effective in alleviating vertigo, and a lower concentration of dexamethasone can reduce the occurrence of complications.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"431-437"},"PeriodicalIF":16.4,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"33481599","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"","authors":"Danny Q. Thach,&nbsp; and ,&nbsp;Robert R. Knowles*,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 13","pages":"962–968 XXX-XXX"},"PeriodicalIF":16.4,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.accounts.5c00246","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144516740","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}