Journal of the American Chemical Society最新文献_第2页

Paired Pulsed Decarboxylative Hydroxylation Designed by Online Electrochemistry–Mass Spectrometry 在线电化学-质谱法设计的配对脉冲脱羧羟基化反应

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-10-02 DOI: 10.1021/jacs.5c12895

Adarsh Koovakattil Surendran, Jana Roithová

引用次数: 0

Site-Specific Profiling of RNA-Binding Proteins Enabled by Isotopic Signature-Enhanced Mass Spectrometry. 通过同位素特征增强质谱法实现rna结合蛋白的位点特异性分析。

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-10-02 DOI: 10.1021/jacs.5c11224

Yicheng Liu,Guogeng Jia,Chengxi Li,Tianyu Feng,Weidi Xiao,Chu Wang

{"title":"Site-Specific Profiling of RNA-Binding Proteins Enabled by Isotopic Signature-Enhanced Mass Spectrometry.","authors":"Yicheng Liu,Guogeng Jia,Chengxi Li,Tianyu Feng,Weidi Xiao,Chu Wang","doi":"10.1021/jacs.5c11224","DOIUrl":"https://doi.org/10.1021/jacs.5c11224","url":null,"abstract":"RNA-binding proteins (RBPs) ubiquitously regulate RNA throughout their lifespan, being extensively involved in cellular metabolism and genetic evolution. Therefore, comprehensive identification of the RNA-protein interactions, especially their interfaces with site-specific resolution, is significant to elucidate the intricate biological activities governed by RNA. Nevertheless, it remains challenging for data-dependent acquisition (DDA)-based proteomics to identify the RNA-cross-linked peptides in depth due to the low abundance and negative charge of modified peptides. To address such limitations, we developed an innovative method named \"isoRIC\" for profiling RNA-binding proteomes with site-specific resolution, which combines the metabolic labeling of isotopic nucleotides for photo-cross-linking of RNA-binding proteins and the real-time targeted LC-MS/MS analysis of RNA-cross-linked peptides. This method shows a dramatic improvement of sensitivity in identifying RNA-cross-linked peptides with low abundance as compared to the DDA-based proteomic approaches, enabling the discovery of novel RNA-binding proteins and precise mapping of RNA-protein binding interfaces at single amino acid resolution. We applied isoRIC in the context of pathogenic mutations and post-translational modifications to highlight the critical role of RNA-binding sites in modulating the RNA-binding ability.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"35 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203730","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

Bambusuril Small-Molecule Ionic Isolation Lattices for Exciton Coupled Dimers and Dicationic Fluorophores 激子偶联二聚体和指示荧光团的Bambusuril小分子离子隔离晶格

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-10-02 DOI: 10.1021/jacs.5c11141

Andrew H. Olsson, Vikrant Tripathy, Nobuyuki Yamamoto, Junichi Usuba, Jeno S. Leavitt, Elizabeth A. Kambas, Katherine L. VanDenburgh, Krishnan Raghavachari, Grace G. D. Han, Bo W. Laursen, Amar H. Flood

{"title":"Bambusuril Small-Molecule Ionic Isolation Lattices for Exciton Coupled Dimers and Dicationic Fluorophores","authors":"Andrew H. Olsson, Vikrant Tripathy, Nobuyuki Yamamoto, Junichi Usuba, Jeno S. Leavitt, Elizabeth A. Kambas, Katherine L. VanDenburgh, Krishnan Raghavachari, Grace G. D. Han, Bo W. Laursen, Amar H. Flood","doi":"10.1021/jacs.5c11141","DOIUrl":"https://doi.org/10.1021/jacs.5c11141","url":null,"abstract":"Ionic self-assembly of molecular fluorophores is a promising avenue to program properties into optical materials. Controllable optical energies, lifetimes, exciton hopping and energy transfer have been engineered in small-molecule, ionic isolation lattices (SMILES) by using preferred binding stoichiometries that pair singly charged complexes (−1) with singly charged fluorophores (+1) to isolate them on lattice sites. We hypothesize that these rules can be generalized if charge balance can be expanded from one anion and one cation to pair of each ion, i.e., from 1:1 to 2:2. If true, opportunities emerge to instead bring two cations together as discrete isolated dimers potentially turning on new optical states. We tested these ideas by exchanging cyanostar receptors for bambusuril receptors known to host two chloride anions. When charge matched with two monocationic cyanines in a 2:2 ratio, the crystal structure reveals π-stacked dimers form into isolated emitters that pack charge-by-charge with (bambusuril)·(chloride)2 complexes. New red-shifted emission at 615 nm from cyanine–cyanine dimers and DFT calculations agree with Kasha’s theory of exciton coupling as offset H-dimers. The bambusuril can also host single anions leading to isolation of single cyanines with monomer emission at 507 nm. In addition, we also discovered a SMILES material using dicationic fluorophores (+2) in the form of styryldipyrylium and a new packing stoichiometry with bambusuril. Stoichiometry, anion identity and charge define crystal engineering rules of bambusuril SMILES. Thus, we add valence control to the rules for isolation of discrete dye dimers and inclusion of discrete dicationic dyes in emissive SMILES materials.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"95 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209866","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

Determination of the Generation Efficiency and Reductive Reactivity of the Upconverted Hot Electrons from Mn-Doped Quantum Dots under Weak Visible Light 弱可见光下mn掺杂量子点上转换热电子产生效率和还原反应性的测定

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-10-02 DOI: 10.1021/jacs.5c12004

Connor Orrison, Ian C. Schulze, Zefan Zhang, Dallas Freitas, Ian Murray, Xin Yan, Christian Hilty, Dong Hee Son

{"title":"Determination of the Generation Efficiency and Reductive Reactivity of the Upconverted Hot Electrons from Mn-Doped Quantum Dots under Weak Visible Light","authors":"Connor Orrison, Ian C. Schulze, Zefan Zhang, Dallas Freitas, Ian Murray, Xin Yan, Christian Hilty, Dong Hee Son","doi":"10.1021/jacs.5c12004","DOIUrl":"https://doi.org/10.1021/jacs.5c12004","url":null,"abstract":"Hot electrons generated via Mn-mediated Auger upconversion in Mn-doped quantum dots (QDs) have been shown to be highly effective for reduction reactions that require high reduction potentials and long-range electron transfer. Due to their high energy, these electrons can drive reduction reactions in the solution phase through multiple pathways, including interfacial hot electron transfer on the QD surface and reduction by presolvated and solvated electrons within the solvent. Despite their demonstrated ability to drive challenging reactions, the efficiency of generating upconverted hot electrons under continuous-wave (cw) visible light excitation remains largely unknown. Here, we quantified the quantum yield of hot electron generation from Mn-doped CdSSe/ZnS QDs under continuous white light (455 nm) in aqueous media using the reductive dechlorination of monochloroacetate (MCA) as a hot electron-selective reaction. We found that the quantum yield for hot electron upconversion can reach 35–40% at an excitation intensity of ∼0.1 W/cm2, highlighting the high efficiency of Mn-doped QDs as a source of hot electrons. Furthermore, we observed a dependence of the product yield on the photoexcitation history, suggesting a possible excitation-induced surface charge affecting the local concentration of reactants near the QDs, thereby altering the reaction kinetics. These findings provide important insights into the design of more efficient Mn-doped QD structures and reaction conditions for hot electron-enabled photocatalysis using visible light-driven hot electron sources.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"55 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209904","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

Enantioselective Synthesis of Atropisomeric 3-Arylindoles via Cobalt-Catalyzed Electroreductive Cross-Coupling. 钴催化电还原交叉偶联对映选择性合成atropisomer 3- arlindoles。

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-10-02 DOI: 10.1021/jacs.5c11094

Shi-Shuo Xu,Jian-Feng Guo,Cong Ma,Ping Fang,Tian-Sheng Mei

引用次数: 0

Coacervate Droplets Drive Organocatalyzed Aqueous C-C Bond Formation via Interfacial Activation. 凝聚液滴通过界面活化驱动有机催化的C-C键形成。

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-10-02 DOI: 10.1021/jacs.5c10731

Kevin Peyraud-Vicré,Charline Dechamps,Nicolas Martin,Valérie Desvergnes

{"title":"Coacervate Droplets Drive Organocatalyzed Aqueous C-C Bond Formation via Interfacial Activation.","authors":"Kevin Peyraud-Vicré,Charline Dechamps,Nicolas Martin,Valérie Desvergnes","doi":"10.1021/jacs.5c10731","DOIUrl":"https://doi.org/10.1021/jacs.5c10731","url":null,"abstract":"Compartmentalization is central to the regulation of biochemical reactions in living systems, with membraneless organelles formed by liquid-liquid phase separation (LLPS) offering dynamic environments that influence biochemical reactivity. Inspired by this principle, coacervate microdroplets have emerged as promising synthetic analogues for modulating both enzymatic and nonenzymatic reactions in water. Here, we report that coacervates can actively promote aqueous N-heterocyclic carbene (NHC) organocatalysis, enabling base-free carbon-carbon (C-C) bond formation via the Stetter reaction. Using a newly designed amphiphilic thiazolium precatalyst, we show that model polyelectrolyte coacervates not only sequester organic droplets containing the Stetter reactants, creating a unique coacervate/organic droplet interface, but also directly facilitate carbene generation. Remarkably, this activation arises from a strong electrostatic interaction between the thiazolium salt and the polyanion, which spontaneously coacervate together to form catalytically active droplets. These coacervates act as sacrificial reaction compartments, dissolving upon carbene formation while driving C-C bond formation in the absence of added base, highlighting the capacity of coacervates to restructure and respond dynamically during catalysis. Together, our results uncover a previously unrecognized mode of organocatalyst activation within LLPS-based materials, expanding the functional scope of phase-separated systems and suggesting broader potential for leveraging multiphase systems to modulate reactivity through emergent interfacial phenomena in water.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"78 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203721","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

Effective Ammonia Production from Nitrogen and Water under Ambient Conditions through Proton-Coupled In Situ Radiolytic Electron Transfer 在环境条件下通过质子耦合的原位辐射分解电子转移从氮和水有效地生产氨

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-10-02 DOI: 10.1021/jacs.5c11505

Changjiang Hu, Junyi Zhao, Ruisi Chang, Hui Dong, Zhiwen Jiang, Xiang Li, Shinichi Yamashita, Pengfei Zheng, Degao Wang, Qing Huang, Xiaoping Ouyang, Yuxiang Bu, Shuao Wang, Jun Ma

{"title":"Effective Ammonia Production from Nitrogen and Water under Ambient Conditions through Proton-Coupled In Situ Radiolytic Electron Transfer","authors":"Changjiang Hu, Junyi Zhao, Ruisi Chang, Hui Dong, Zhiwen Jiang, Xiang Li, Shinichi Yamashita, Pengfei Zheng, Degao Wang, Qing Huang, Xiaoping Ouyang, Yuxiang Bu, Shuao Wang, Jun Ma","doi":"10.1021/jacs.5c11505","DOIUrl":"https://doi.org/10.1021/jacs.5c11505","url":null,"abstract":"Ammonia (NH3) is a vital component for sustaining global food supplies and fuel production, but its industrial production via the Haber–Bosch process remains energetically demanding and carbon-intensive. Here, we report an electron-beam-activated NH3 synthesis strategy that utilizes only atmospheric N2 and water as feedstocks under ambient conditions. This approach achieves an industrially relevant rate of 83.6 μmol g–1 s–1 with a substantially improved energy efficiency of 0.53 MJ/mol, which surpasses most laboratory-scale technologies and is comparable to that of the Haber–Bosch process. Time-resolved operando spectroscopic experiments, combined with theoretical calculations, reveal that this distinct activation mode enables rapid N2→NH3 conversion through a proton-coupled transfer of an in situ generated energetic hydrated electron. Furthermore, techno-economic analysis and life-cycle assessment demonstrate that the operational simplicity and exceptional throughput of the present N2 fixation approach could promote nitrogen circularity in the sustainable chemical industry.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"11 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209867","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

Temperature-Controlled Cyclic Polyester Molecular Weights in Ring-Expansion Polymerization. 温控环状膨胀聚合中循环聚酯分子量的研究。

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-10-02 DOI: 10.1021/jacs.5c13840

Jinxing Jiang,Ge Yao,Yaqin Cui,Luya Cao,Yadong Zhang,Kun Yuan,Xiaobo Pan,Yu Tang,Jincai Wu

引用次数: 0

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-10-02 DOI: 10.1021/jacs.5c08751

Dhyllan A. Skiba, Aaron M. Melemed, Betar M. Gallant

{"title":"Correlated Calorimetric and Potentiometric Titration Elucidates Quantitative Lithium Cation Coordination Thermodynamics","authors":"Dhyllan A. Skiba, Aaron M. Melemed, Betar M. Gallant","doi":"10.1021/jacs.5c08751","DOIUrl":"https://doi.org/10.1021/jacs.5c08751","url":null,"abstract":"Understanding the thermodynamics of interactions within the coordination environment of Li+ ions is critical for rational electrolyte design. Drawing a physical analogy to ligand–receptor binding in biological systems, in this work, we introduce a combined isothermal titration calorimetry (ITC) and potentiometric titration (PT) framework to quantitatively determine the Gibbs free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) associated with solvent displacement─an exemplar coordination sphere reaction that powerfully reports on the underlying energetics─in nonaqueous Li-based electrolytes. The physical understanding behind the solvent displacement scheme is first validated with Raman spectroscopy, such that the heat measured during ITC is confirmed to arise predominantly from differential changes in coordinated solvent as the bulk electrolyte composition is systematically modified. A statistical binding model is then developed to interpret the thermodynamic data and parametrize single-site displacement enthalpy and equilibrium constants in a set of exemplar dual-solvent electrolytes. The framework is tested across systems with both dissimilar (DMSO:acetonitrile or DMSO:PC) and structurally similar (EC:PC) solvents, revealing how subtle differences in solvent–cation interaction enthalpy and entropy govern coordination preferences. These results provide new experimental insight into the driving forces behind microscopic coordination sphere changes and offer a powerful approach to guide electrolyte formulation.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"157 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209903","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

Precise Synthesis of Racemate-Based One-Handed Helical Polymers as Recyclable Homogeneous Chiral Catalysts for Multiple Asymmetric Reactions 精确合成外消旋酸基单手螺旋聚合物作为多重不对称反应的可回收均相手性催化剂

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-10-02 DOI: 10.1021/jacs.5c12015

Run-Tan Gao, Jia-Xin Yu, Qi-Hui Ti, Ming-Yang Mo, Na Liu, Zong-Quan Wu

{"title":"Precise Synthesis of Racemate-Based One-Handed Helical Polymers as Recyclable Homogeneous Chiral Catalysts for Multiple Asymmetric Reactions","authors":"Run-Tan Gao, Jia-Xin Yu, Qi-Hui Ti, Ming-Yang Mo, Na Liu, Zong-Quan Wu","doi":"10.1021/jacs.5c12015","DOIUrl":"https://doi.org/10.1021/jacs.5c12015","url":null,"abstract":"Developing chiral catalysts from racemic materials while retaining the merits of both homogeneous and heterogeneous catalysts is a highly desirable yet formidable challenge to date. In this work, we synthesized optically active, one-handed helical polycarbenes from racemic monomers using chiral Pd(II) catalysts. The living polymerization of enantiomeric diazo acetate monomers (L- and D-1) bearing tert-butyloxycarboryl-protected L-prolinol ester using chiral Pd(II)/LR,or,S catalysts coordinated with R- or S-bidentate phosphine ligand showed high enantioselectivity (kfast/kslow = 142). Interestingly, the living polymerization of racemic D/L-1 shows high helix-sense selectivity and affords left- and right-handed helices by using Pd(II)/LR,and,S catalysts, respectively. Removing the tert-butyloxycarboryl-protected groups on prolinol esters, the racemate-based helical polycarbenes bearing amine pendants showed excellent catalytic activity and enantioselectivity in asymmetric Aldol reaction, Michael addition, and Domino oxa-Michael/Aldol condensation. All of the reactions gave the target products in high yields (>78%) with enantiomeric excess (ee) up to 99%. Surprisingly, enantioselectivity is solely determined by the backbone helicity, regardless of the pendant chirality; thus, enantiomeric products are easily obtained using helical polymer-based catalysts in opposite handedness. The polymer catalysts could be recovered from the homogeneous reaction solution via solvent precipitation and were recycled at least 5 times while maintaining excellent activity and enantioselectivity, confirming that these racemate-based helical polymers have the merits of both homogeneous and heterogeneous catalysts.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"39 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209716","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