Journal of the American Chemical Society最新文献_第10页

Tetrapyridophenazine-BasedVinylene-Linked CovalentOrganic Frameworks for Efficient Sequential Photocatalysis and Continuous-FlowSynthesis 四吡啶吩嗪基乙烯键共价有机框架的高效顺序光催化和连续流合成

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2026-10-15 DOI: 10.1021/jacs.6c15006

Minghao Liu,Chensheng Wang,Yingguo Li,Honglin Wen,Zhiyao Li,Ju Liu,Mengmeng Fu,Xiaoyi Yue,Hao Chen,Danfeng Jiang,Xiao Chen,Guozan Yuan,Chao Yu,Yong Cui

{"title":"Tetrapyridophenazine-Based\u0000Vinylene-Linked Covalent\u0000Organic Frameworks for Efficient Sequential Photocatalysis and Continuous-Flow\u0000Synthesis","authors":"Minghao Liu,Chensheng Wang,Yingguo Li,Honglin Wen,Zhiyao Li,Ju Liu,Mengmeng Fu,Xiaoyi Yue,Hao Chen,Danfeng Jiang,Xiao Chen,Guozan Yuan,Chao Yu,Yong Cui","doi":"10.1021/jacs.6c15006","DOIUrl":"https://doi.org/10.1021/jacs.6c15006","url":null,"abstract":"Abstract Vinylene-linked covalent organic frameworks (COFs) are promising photocatalysts because their conjugated sp2-carbon frameworks combine exceptional chemical stability with efficient charge transport. However, the limited reversibility of C═C bond formation narrows the scope of polymerizable monomers, restricting the structural diversity and electronic tunability of vinylene-linked COFs. Here, we report a molecular design strategy based on a planar, electron-deficient, nitrogen-rich tetrapyridophenazine (TTPhz) building block for constructing vinylene-linked COFs. Knoevenagel polycondensation of a polymerizable TTPhz monomer with aromatic dialdehydes affords three highly crystalline COFs with tunable donor–acceptor interactions and electronic structures. The optimized fluorinated framework, TTPhz-COF-3, exhibits efficient charge separation and transport, enabling a previously unreported one-pot sequential photocatalytic synthesis of 2,3-dihydrobenzofuran derivatives from arylboronic acids through tandem aerobic hydroxylation and oxidative [3 + 2] cycloaddition. The catalyst displays broad substrate scope, excellent recyclability, and enables gram-scale continuous-flow synthesis of a key intermediate of the natural product (±)-conocarpan with a 4-fold higher turnover frequency than the corresponding batch process. This work expands the structural and functional scope of vinylene-linked COFs and establishes molecular building-block design as a general strategy for developing advanced crystalline organic photocatalysts.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"25 3 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209613","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}

引用次数: 0

Photocatalytic Three-ComponentRadical Addition ofAromatic Compounds 芳香化合物的光催化三组份加成

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2026-10-15 DOI: 10.1021/jacs.6c17373

Huijun Qian,Jing Liu,Yuting Feng,Yujuan Gui,Xingwei Guo,Zhiping Li

引用次数: 0

Divergent BioinspiredTotal Syntheses of CaryophylleneSesquiterpenoids: Nigrosporinol Sulfoxide B, Punctaporonins C andU, and Desuccinoylpunctaporonin C 石竹烯类半萜类物质：黑孢素醇亚砜B、点状钙蛋白C和u和去琥珀酰点状钙蛋白C的生物合成

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2026-10-15 DOI: 10.1021/jacs.6c15184

John Park,Luis F. Porras-Santos,Masaya Owa,John L. Wood

引用次数: 0

InterfacialQuantum States in ZrO2 QuantumDots as a Strategy to Activate Photocatalytic Efficiency ZrO2量子点的界面量子态作为激活光催化效率的策略

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2026-10-15 DOI: 10.1021/jacs.6c13799

Loukas Belles,Areti Zindrou,Nikolaos Effraim Papamatthaiakis,Szymon Smykała,Giannis Mpourmpakis,Yiannis Deligiannakis

{"title":"Interfacial\u0000Quantum States in ZrO2 Quantum\u0000Dots as a Strategy to Activate Photocatalytic Efficiency","authors":"Loukas Belles,Areti Zindrou,Nikolaos Effraim Papamatthaiakis,Szymon Smykała,Giannis Mpourmpakis,Yiannis Deligiannakis","doi":"10.1021/jacs.6c13799","DOIUrl":"https://doi.org/10.1021/jacs.6c13799","url":null,"abstract":"Abstract Ultrasmall quantum dots (QDs) exhibit electronic behavior inaccessible to bulk counterparts, yet the role of structurally disordered interfaces remains unresolved, particularly in wide-band gap oxides. Herein, using the flame spray pyrolysis (FSP) technology, we engineered ZrO2/ZrO2–x QDs comprising tetragonal ZrO2 QDs (2–5 nm) tightly interfaced with a semiamorphous, subnanometric ZrO2–x layer. Rather than forming a conventional heterojunction, electronic coupling between a {surface distorted hydroxylated ZrO2–x}, and the {quantum-confined crystalline core} generates shallow interfacial quantum states (IQS). This single-metal-oxide architecture elucidates the synergistic contributions of quantum confinement and interfacial states to photocatalytic H2 evolution. The ZrO2/ZrO2–x QDs exhibit an unprecedented H2 production rate of 32,943 μmol g–1 h–1 and an apparent quantum yield of 3.49% at 252 nm, outperforming bulk-like ZrO2. Experimental results indicate that IQS activate otherwise photoinactive ZrO2, while density functional theory (DFT) calculations elucidate their origin and electronic character. Photoelectrochemical measurements reveal a negative shift in flat-band potential and enhanced interfacial charge conductivity. X-ray photoelectron spectroscopy identifies a highly reduced, hydroxylated surface environment in the ZrO2 QDs, whereas electron paramagnetic resonance (EPR) reveals that {ZrO2/ZrO2–x QDs} form photoactive Zr3+ centers. Additionally, reversible photoinduced (g &lt; 2) and (g &gt; 2) signals consistent with electron and hole trapping, respectively. These findings establish IQS engineering as a novel interphase concept, beyond the quantum-dot limit, to promote charge separation and H2 evolution even in wide-band gap metal oxides. More broadly, coupling metal-oxide QDs with subnanometric, oxygen-deficient layers of the same metal offer a simple chemical route to activate otherwise inefficient oxide photocatalysts.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"17 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209612","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}

引用次数: 0

Regioselective andStereodivergent C–H Functionalizationof Internal Alkenes 内烯烃的区域选择性和立体发散C-H功能化

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2026-10-15 DOI: 10.1021/jacs.6c17366

Elizabeth A. Ryutov,Peter J. Verardi,Song N. Dang,Karina Targos,Leah C. Garman,Zachary K. Wickens

引用次数: 0

Iron Intermediatesin Aminoquinoline-Directed C(sp2)–H Activation/C–CCoupling 氨基喹啉定向C(sp2) -H活化/C偶联中的铁中间体

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2026-10-15 DOI: 10.1021/jacs.6c18131

Emily L. Nolan,Ziyan Wang,Fengrui Qu,Paul Oyala,Melanie S. Sanford

{"title":"Iron Intermediates\u0000in Aminoquinoline-Directed C(sp2)–H Activation/C–C\u0000Coupling","authors":"Emily L. Nolan,Ziyan Wang,Fengrui Qu,Paul Oyala,Melanie S. Sanford","doi":"10.1021/jacs.6c18131","DOIUrl":"https://doi.org/10.1021/jacs.6c18131","url":null,"abstract":"Abstract Over the past two decades, iron-catalyzed aminoquinoline-directed C–H functionalization has attracted significant attention due to the low cost and sustainability of iron, the mild conditions required for catalysis, and the novel mechanistic manifolds compared to those with other first row metals. This report describes organometallic studies that provide insights into FeII, FeIII, and FeIV intermediates involved in an aminoquinoline-directed C(sp2)–H activation/C(sp2)–C(sp2) coupling reaction to yield a dimeric product. These investigations reveal that 2,3,4,5-tetrafluoro-N-(quinolin-8-yl)benzamide reacts with Fe(OAc)2 and Cs2CO3 to afford a high spin octahedral FeII coordination complex featuring two bidentate aminoquinoline ligands along with a k2-acetate. This intermediate does not react with acetate or carbonate salts (bases that promote C(sp2)–H activation at analogous first row transition metal complexes); furthermore, an intractable mixture is formed with PhMgBr (a common base in iron C–H functionalization catalysis). However, treatment with sodium hexamethyldisilazide (NaHMDS) results in rapid cyclometalation of both coordinated aminoquinoline ligands to yield a low spin octahedral FeII product. Two sequential single electron oxidations then enable C–C bond-forming reductive elimination from this complex via a putative FeIV intermediate. The isolated FeII and FeIII complexes from these organometallic studies serve as viable catalysts for this oxidative dimerization reaction with NaHMDS as base and AgOAc as oxidant, validating the feasibility of this pathway in catalytic C–H functionalization.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"23 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209644","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}

引用次数: 0

UnilateralFunctionalization of Covalent Organic Frameworks:Local Electronic Modulation and Morphology-Enabled Mass Transportfor Electrocatalytic Hydrogen Peroxide Production 共价有机框架的单侧功能化：电催化过氧化氢生产的局部电子调制和形态支持的质量传递

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2026-10-15 DOI: 10.1021/jacs.6c17269

Xueqing Xi,Chao Wang,Yali Xing,Lili Li,Daohao Li,Ziyan Dong,Yunqing Chen,Xiaojing Long

{"title":"Unilateral\u0000Functionalization of Covalent Organic Frameworks:\u0000Local Electronic Modulation and Morphology-Enabled Mass Transport\u0000for Electrocatalytic Hydrogen Peroxide Production","authors":"Xueqing Xi,Chao Wang,Yali Xing,Lili Li,Daohao Li,Ziyan Dong,Yunqing Chen,Xiaojing Long","doi":"10.1021/jacs.6c17269","DOIUrl":"https://doi.org/10.1021/jacs.6c17269","url":null,"abstract":"Abstract Achieving high selectivity and activity in the two-electron oxygen reduction reaction (2e– ORR) pathway critically depends on the synergistic modulation of a catalyst’s electronic structure and mass diffusion channels. This work proposes an asymmetric modulation strategy via unilateral functionalization, in which −CH3, −CN, −SO3H, and −NO2 moieties are incorporated into a series of covalent organic frameworks (COFs), systematically unraveling the multilevel regulatory mechanisms exerted by functional groups from molecular to macroscopic morphological scales. The research demonstrates that introducing strong electron-withdrawing −NO2 groups can effectively enhance charge transfer at adjacent carbon active sites, reduce the formation barrier of OOH* intermediates, and induce efficient 2e– ORR activity. Concurrently, the polarity and steric effects of functional groups induce structural evolution in COFs from spherical, rod-like to spiderweb-like architectures, wherein the interconnected network of COF-NO2 substantially enhances the diffusion efficiency of reactants and products. This synergy between electronic structure and macroscopic morphology enables COF-NO2 to achieve 94% H2O2 selectivity and a high production rate of 10.5 mol gcat–1 h–1 with sustained stability. This work not only provides outstanding catalysts for efficient electrochemical H2O2 synthesis but also clarifies functional group-induced electronic and morphological modulation, offering a novel paradigm for the rational design of porous catalytic materials.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"63 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209615","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}

引用次数: 0

Excited-State Engineeringof Viologen Photocatalystsvia Synergistic Through-Space and Through-Bond Electronic Coupling 紫紫光催化剂的协同穿越空间和穿越键电子耦合激发态工程

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2026-10-15 DOI: 10.1021/jacs.6c17009

Yihua Zhang,Yi Qiao,Yawen Li,Chen Li,Ni Yan,Ze-Hua Wu,Zishun Liu,Gang He

{"title":"Excited-State Engineering\u0000of Viologen Photocatalysts\u0000via Synergistic Through-Space and Through-Bond Electronic Coupling","authors":"Yihua Zhang,Yi Qiao,Yawen Li,Chen Li,Ni Yan,Ze-Hua Wu,Zishun Liu,Gang He","doi":"10.1021/jacs.6c17009","DOIUrl":"https://doi.org/10.1021/jacs.6c17009","url":null,"abstract":"Abstract Precise manipulation of excited-state charge dynamics represents a fundamental challenge in the molecular design of organic photocatalysts. Herein, we introduce a synergistic electronic coupling strategy for engineering long-lived charge separation states by integrating through-space and through-bond electronic coupling in viologen-based photocatalysts. A family of through-space-conjugated viologens (TSCVs) featuring a dumbbell-shaped donor–acceptor architecture was constructed by integrating extended π-conjugated scaffolds with TSCV units. This unique architecture establishes an electronically cooperative framework that accelerates photoinduced charge separation, promotes charge delocalization, and suppresses charge recombination. Spectroscopic, electrochemical, and theoretical investigations reveal that the synergistic coupling pathway enables persistent charge-separated excited states with enhanced charge-carrier utilization. Consequently, TSCV-T-c functions as a highly efficient metal-free photocatalyst for tandem C(sp3)-H functionalization/annulation of N,N-dimethylanilines with maleimides, affording tetrahydroquinoline products in yields up to 98%. Beyond demonstrating an effective photocatalytic system, this work establishes electronic coupling engineering as a molecular strategy for controlling excited-state dynamics and unlocking enhanced photocatalytic reactivity in organic semiconducting molecules.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"14 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209639","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}

引用次数: 0

Super-Cross-ReactiveRecognition Enables PreclinicalDiagnosis of Alzheimer’s Disease 超交叉反应识别技术可用于阿尔茨海默病的临床前诊断

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2026-10-15 DOI: 10.1021/jacs.6c14717

Wen-Bo Li,Jing Li,Xin-Yu Ning,Jia-Hong Tian,Fang-Yuan Chen,Shu-Xin Zhang,Ze-Han Wang,Yu-Chen Pan,Wei Zhang,Dong-Sheng Guo

{"title":"Super-Cross-Reactive\u0000Recognition Enables Preclinical\u0000Diagnosis of Alzheimer’s Disease","authors":"Wen-Bo Li,Jing Li,Xin-Yu Ning,Jia-Hong Tian,Fang-Yuan Chen,Shu-Xin Zhang,Ze-Han Wang,Yu-Chen Pan,Wei Zhang,Dong-Sheng Guo","doi":"10.1021/jacs.6c14717","DOIUrl":"https://doi.org/10.1021/jacs.6c14717","url":null,"abstract":"Abstract Early diagnosis of Alzheimer’s disease (AD) is impeded by the subtle, heterogeneous nature of fluid biomarkers during the disease’s initial phases. Current detection tools, which target single biomarkers, often lack the necessary sensitivity and specificity for presymptomatic screening. To address this, we develop a machine learning-informed supramolecular sensor array that leverages a holistic design to overcome the limitations of “lock-and-key” recognition. By engineering macrocyclic receptors with semiselective properties, we generate a competitive signal transduction process characterized by multiple equilibria and nonlinear responses. This design confers high-dimensional cross-reactivity, delineating distinct fluorescent fingerprints for specific AD stages. The array achieves 100% diagnostic accuracy in cerebrospinal fluid from 1-month-old rat models─predating conventional ELISA detection by 3 months and behavioral symptoms by 4 months. Crucially, the array identifies human patients at the subjective cognitive decline stage with &gt;95% accuracy. This work presents a clinically viable tool for early AD diagnosis and establishes a generalizable, modular framework for multiplexed biomarker analysis in neurodegenerative diseases.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"1 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209643","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}

引用次数: 0

Functionalized Olefin-LinkedCovalent Organic Frameworksfor Selective Mercury Capture and Recovery from Vinyl Chloride-RichGas Streams 功能化烯烃-共价有机框架对富氯乙烯气体中汞的选择性捕获和回收

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2026-10-15 DOI: 10.1021/jacs.6c13542

Mingming Wang,Haomiao Xu,Yurui Fan,Chaobin Shi,Jun Lei,Jiawei Lai,Weiwei Li,Qinyuan Hong,Wenjun Huang,Zan Qu,Yong Cui,Xing Han,Naiqiang Yan

{"title":"Functionalized Olefin-Linked\u0000Covalent Organic Frameworks\u0000for Selective Mercury Capture and Recovery from Vinyl Chloride-Rich\u0000Gas Streams","authors":"Mingming Wang,Haomiao Xu,Yurui Fan,Chaobin Shi,Jun Lei,Jiawei Lai,Weiwei Li,Qinyuan Hong,Wenjun Huang,Zan Qu,Yong Cui,Xing Han,Naiqiang Yan","doi":"10.1021/jacs.6c13542","DOIUrl":"https://doi.org/10.1021/jacs.6c13542","url":null,"abstract":"Abstract The calcium carbide-derived acetylene hydrochlorination route for vinyl chloride monomer (VCM, C2H3Cl) production remains a major source of mercury consumption and emission owing to its reliance on HgCl2/activated carbon catalysts. Selective removal of elemental mercury (Hg0) from crude VCM streams is intrinsically challenging because Hg0 must be captured from C2H3Cl-rich and HCl-containing atmospheres without coadsorbing valuable C2H3Cl. Here, we report a pore-engineered covalent organic framework (COF) platform in which olefin-linked sp2-carbon-conjugated frameworks suppress nonspecific C2H3Cl adsorption, while Cu-coordinated 2-(methylthio)ethoxy side chains create well-defined Cu–O2S2 pockets for selective Hg0 capture. These structural features afford an ideal adsorbed solution theory-predicted Hg0/C2H3Cl selectivity exceeding 20,000. Notably, dynamic breakthrough experiments under simulated industrial conditions containing 5 vol % HCl further revealed a Hg0 breakthrough time of over 10,000 min g–1 in C2H3Cl-rich streams, with a separation factor of approximately 52, demonstrating exceptional resistance to acid-induced deactivation. Treatment of the spent adsorbent with Na2S solution enables regeneration over 30 consecutive cycles and converts captured mercury into chemically stable HgS. This work establishes a molecularly precise removal–recovery platform for elemental mercury from chemically complex industrial gas streams, highlighting the power of programmed pore microenvironments to discriminate trace toxic species from abundant value-added molecules under chemically aggressive conditions.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"12 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209638","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}

引用次数: 0