Journal of the American Chemical Society最新文献

{"title":"Correction to “Redox-Switchable Tristable 1,3,2,4,5-Triboradiazoles”","authors":"Yu Mu,Yuyang Dai,Taisong Zhao,Haotian Wu,Chen-Ho Tung,Lingbing Kong","doi":"10.1021/jacs.6c20285","DOIUrl":"https://doi.org/10.1021/jacs.6c20285","url":null,"abstract":"","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"32 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221702","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":"Selective Methylation of Phenol with CO2/H2 to o-Cresol and 2,6-Xylenol","authors":"Changxin He,Jiaxin Zhang,Junqi Tian,Jun Yuan,Hongfang Yang,Ruihui Zhang,Zhihe Mao,Xiaojing Wu,Jieyun Zhang,Jianian Cheng,Hao Wang,Chengyuan Liu,Zelong Li,Can Li","doi":"10.1021/jacs.6c16522","DOIUrl":"https://doi.org/10.1021/jacs.6c16522","url":null,"abstract":"Employing CO2/H2 as a sustainable methylating agent offers a transformative strategy for advancing conventional methylation processes, yet achieving controllable C–C coupling with high efficiency remains a formidable challenge. Here, we report a novel tandem process that integrates CO2 hydrogenation with phenol methylation over a Zr-doped In2O3 solid-solution catalyst. The optimized In7Zr3Ox catalyst exhibits >95% selectivity toward ortho-methylation with tunable product distribution, ranging from 92% o-cresol at 16% conversion to 86% 2,6-xylenol at 97% conversion, while maintaining stable operation for 140 h. Mechanistic studies identify surface formaldehyde species (CH2O*) generated from CO2 hydrogenation as the active methylating intermediates that kinetically couple CO2 reduction to phenol methylation. This pathway exhibits a markedly lower apparent activation energy of 58.8 kJ mol–1 than the conventional methanol-mediated route of 116.3 kJ mol–1. Continuous consumption of CH2O* also shifts the CO2 hydrogenation equilibrium, imparting a thermodynamic driving effect absent in CO2 hydrogenation alone. These findings demonstrate the potential of CO2-based methylation for selective C–C bond formation and expand opportunities for CO2 valorization.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"45 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221777","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":"Thiol-Mediated Hydrazide Installation from Diazo in the Biosynthesis of Spinamycin","authors":"Haoran Pang,Wenni Zhang,Wenjun Zhang","doi":"10.1021/jacs.6c14252","DOIUrl":"https://doi.org/10.1021/jacs.6c14252","url":null,"abstract":"Natural products featuring nitrogen–nitrogen (N–N) bonds often possess potent bioactivities, and their architectures frequently reveal novel enzymatic mechanisms. Current understanding for acylhydrazide installation is limited to a “hydrazine-first” strategy, wherein an activated acyl donor is nucleophilically attacked by a preassembled hydrazine intermediate. Spinamycin, an antifungal hydrazide-containing aryl polyene from Streptomyces albospinus, challenges this convention. Its biosynthetic machinery utilizes SpiA7, an ATP-dependent, nitrite-utilizing N-nitrosylase, to synthesize a highly transient diazo intermediate rather than a hydrazine core. How this unstable diazo compound is converted into a stable hydrazide has remained a long-standing biosynthetic mystery. Herein, we report the in vitro reconstitution of the activity of SpiA7 in conversion of the amine substrate into its mature succinylhydrazide form. Mechanistic characterization revealed that the electrophilic diazo intermediate is initially captured by thiol reagents to generate a covalent azo-sulfide intermediate (R–N═N–S–R′). This species likely undergoes a noncanonical four-electron reduction driven cooperatively by disulfide bond formation and the oxidative decarboxylation of α-ketoglutarate (αKG), which serves as the succinyl donor. Furthermore, site-directed mutagenesis identifies Cys453 of SpiA7 as a likely active-site thiol donor orchestrating this transformation. Collectively, our findings unveil an unprecedented chemical strategy for hydrazide assembly that completely bypasses a free hydrazine intermediate, expanding nature’s known catalytic repertoire for building complex N–N linkages.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"1 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221794","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":"Secondary-Sphere Control of Electronic Structure and Ligand Basicity in Mo-Nitrogenase: A QM/MM Analysis Guided by Se K-Edge HERFD XAS","authors":"Gursahib Singh Sethi,Justin P. Joyce,Christina Roemelt,Kushal Sengupta,Serena DeBeer","doi":"10.1021/jacs.6c16459","DOIUrl":"https://doi.org/10.1021/jacs.6c16459","url":null,"abstract":"Molybdenum nitrogenase catalyzes biological nitrogen fixation using a complex metallocofactor (FeMoco) containing three μ2-“belt”sulfides that exhibit distinct reactivity during catalysis. In particular, protonation at the S2B site imparts lability that facilitates substrate binding and may enable this sulfide to act as a proton donor. Although FeMoco is inactive outside its protein environment, how secondary-sphere residues tune its geometric and electronic structure to enable function remains unclear. We have previously shown that site-selective Se substitution of the μ2-sulfides provides a direct probe of the ligand environment using Se K-edge high-energy-resolution fluorescence-detected X-ray absorption spectroscopy (HERFD XAS). Despite the cofactor’s approximate C3 symmetry, Se-substituted sites display pronounced differences in Se HERFD XAS pre-edge intensities. Utilizing QM/MM calculations, we show that hydrogen-bonding (H-bonding) residues polarize the S3A and S5A sulfides, reducing metal–ligand covalency and attenuating pre-edge intensity, whereas hydrophobic residues surrounding S2B localize electron density and enhance its pre-edge intensity. These results demonstrate how hydrophobicity and H-bonding within the secondary coordination sphere modulate FeMoco electronic structure. More broadly, they show how the protein environment tunes ligand basicity to favor selective S2B protonation and provide design principles for controlling enzymatic function.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"62 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221779","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":"Bridging Ionic Field Strength Disparity in O3-Type Layered Oxides for High-Voltage Sodium-Ion Batteries","authors":"Ziheng Zhang,Zixin Liang,Yixiang Zhao,Jiangtao Yu,Mengchen Zhang,Ji Kong,Yanxia Deng,Zhiwei Yu,Machuan Hou,Peixin Jiao,Feiran Shen,Lunhua He,Limin Zhou,Kai Zhang","doi":"10.1021/jacs.6c11691","DOIUrl":"https://doi.org/10.1021/jacs.6c11691","url":null,"abstract":"O3-type layered oxides represent an attractive class of sodium-ion battery cathodes, combining high theoretical specific capacity and high pristine Na content. However, their deeply desodiated frameworks at high voltages (≥4.0 V) are prone to redox-coupled distortion of TMO6 octahedra within the transition metal (TM) slabs, leading to severe structural degradation. Here, we originally define an ionic field strength disparity coefficient (η), which enables quantitative evaluation of the local chemical-field heterogeneity. The η is derived from the ratio between the standard deviation and the average value of ionic field strength (Φ) of all TM ions, defined as Φ= Z/r2, where Z and r correspond to the ionic charge and ionic radius, respectively. Introducing compensatory cations with an intermediate Φ value between two cations featuring largely disparate Φ values effectively reconciles local chemical-field discrepancy and lowers the η parameter upon charge–discharge processes. Moreover, synchrotron X-ray absorption spectroscopy, strain mapping analyses, and first-principles calculations reveal that the low-η sample demonstrates the reduced lattice strain and enhanced structural reversibility. Consistently, electrochemical evaluation shows that it retains more than 80% of its capacity after 500 cycles at 10C, markedly outperforming the unmodified counterpart with only 22% retention. This work establishes the η as a quantitative descriptor for inactive dopant selection and provides a general strategy for developing highly stable layered oxide cathodes.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"2 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221792","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":"Physically Grounded Descriptors for Machine-Learning-Guided Diluent Design in Lithium Metal Batteries","authors":"Myeongjun Kim,Chihyun Nam,Hyunmin Lee,Seyeon Shin,Songha Seo,Woojin Chong,Yejin Lee,Munsoo Song,Jongwoo Lim","doi":"10.1021/jacs.6c16379","DOIUrl":"https://doi.org/10.1021/jacs.6c16379","url":null,"abstract":"Localized high-concentration electrolytes require diluents that avoid direct Li+ coordination and preserve Li+-anion aggregates while remaining miscible with the primary solvent. Rational discovery has remained difficult because these competing requirements arise from chemically distinct interactions that have lacked computable molecular design coordinates. Fluorination has therefore been widely used to suppress electron donation, but the environmental persistence and synthetic burden of fluorinated molecules motivate alternative strategies for controlling diluent functionality. Here, we resolve the key interaction requirements of diluents using two complementary descriptors: BF3 affinity for specific electron-pair donation and the molecular polarity index (MPI) for distributed nonspecific electrostatic interactions. These descriptors reproduce established donor-number and Kamlet–Taft π* trends and, more importantly, distinguish noncoordinating yet miscible diluents from solvating and immiscible solvents. Coupling this interaction-based framework with uncertainty-aware machine learning enabled screening of 1.32 million nonfluorinated molecules and identified 368 candidates while recovering false negatives and excluding false positives near the decision boundaries. Newly selected aromatic hydrocarbons, including 1,2,4-trimethylbenzene and 2-ethyltoluene, sustained stable cycling in Li-metal full cells for more than 200 cycles, whereas a descriptor-excluded analogue underwent rapid capacity decay. These results establish specific coordination and distributed electrostatics as predictive design coordinates for diluent discovery.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"82 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221798","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":"A New Paradigm for Computational Chemistry","authors":"Raphael T. Husistein,Markus Reiher","doi":"10.1021/jacs.6c06653","DOIUrl":"https://doi.org/10.1021/jacs.6c06653","url":null,"abstract":"Computational chemistry has become an indispensable tool for generating data and insights, pervading all branches of experimental chemistry. Its most central concept is the potential energy hypersurface, which is key to all chemistry and materials science, as it assigns an energy to a molecular structure, the necessary ingredient for reaction mechanism elucidation and reaction rate calculation. Density functional theory (DFT) has been the most important method in practice for obtaining such energies, which is reflected in the use of high-performance computing hardware. In the last two decades, a new class of surrogate potential energy functions has evolved with remarkable properties: quantum accuracy combined with force-field speed. Until very recently, their application was hampered by the fact that they needed to be trained on truly large system-specific data sets, generated before a computational chemistry study could be started (in sharp contrast to DFT, which, as a first-principles method, works out of the box but at a far higher price of computational cost). Very recently, this roadblock has been overcome by so-called foundation machine learning interatomic potentials, which are poised to completely change the way we do computational chemistry, likely prompting us to abandon DFT as the prime method of choice for this purpose in less than a decade.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"497 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221776","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":"Physics-Informed Site-Specific Molecular Interaction Learning Framework for Liquid–Liquid Phase Diagram Reconstruction and Extraction Process Design","authors":"Jinlin Ye,Shuohan Wang,Hongchang Zhang,Yankang Liu,Junhao Wang,Ziyang Zhang,Xin Yang,Kai Li,Shouhang Yuan,Liang Yang,Yu Wang,Lang Jiang,Buxing Han,Xinchen Kang,Wei Zhang","doi":"10.1021/jacs.6c11644","DOIUrl":"https://doi.org/10.1021/jacs.6c11644","url":null,"abstract":"Liquid–liquid phase behavior is governed by the collective balance of intermolecular interactions and is central to predicting component partitioning and designing extraction-based separation processes. Existing thermodynamic and data-driven approaches can predict phase-equilibrium properties, but provide limited resolution of the molecular-interaction-to-phase-topology relationship underlying coupled binodal boundaries and tie-line families. Here, PSMI is proposed as a physics-informed site-specific molecular interaction learning framework that reconstructs ternary liquid–liquid phase diagrams directly from molecular structures. PSMI learns chemically meaningful intermolecular interaction sites through molecular representation learning and integrates chemical-potential consistency regularization to guide thermodynamically reliable phase reconstruction. The framework predicts coexisting extract and raffinate compositions along continuous phase paths and enables reconstruction of binodal boundaries and tie-line families. Across benchmark tests, PSMI accurately predicts coexisting extract and raffinate compositions and recovers phase-diagram topology, including both binodal shapes and tie-line directions. Interpretability analysis shows that PSMI identifies transferable molecular drivers underlying liquid–liquid phase separation, including chemically meaningful interaction patterns. Industrial case studies, together with a locally deployable web application, further demonstrate the practical utility and accessibility of PSMI for solvent screening and extraction process design. By resolving site-specific intermolecular interactions together with their macroscopic phase-partitioning consequences, PSMI provides a molecular-level perspective on how local chemical environments contribute to liquid–liquid phase behavior. This connection between localized molecular interactions and continuous phase-diagram topology provides a framework for understanding and designing complex liquid–liquid separation systems.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"13 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221789","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":"Deoxygenative Metal Carbenation: A Strategy for Stereocontrolled Olefin Metathesis via an Oxo-Ruthenium Precursor","authors":"Samantha K. Cormier,Harrison C. Max,Eliza-Jayne Y. Boisvert,Michael J. Ferguson,Deryn E. Fogg","doi":"10.1021/jacs.6c12046","DOIUrl":"https://doi.org/10.1021/jacs.6c12046","url":null,"abstract":"Dithiolene metathesis catalysts have enabled breakthroughs in materials and medicinal contexts in which control of cis/trans alkene stereochemistry translates into control over function. Their extreme air-sensitivity, however, impedes widespread uptake. Building on the discovery that air-exposure selectively decomposes the leading catalyst Ru(S–S)(H2IPr)(═CHAr) (Ru-1a; S–S = 1,2-S2C6H2-3,6-Cl2, Ar = C6H4-2-OiPr) into four-coordinate oxo complex Ru-2 Ru(O)(S–S)(H2IPr), we demonstrate that the latter offers convenient access to Ru-1a and related catalysts via reaction with phosphorus ylides (Ph3P═CHR; R = Ar, Ph, H). This “deoxygenative metal carbenation” (DMC) strategy opens new opportunities in olefin metathesis. Beyond regeneration of Ru-1a after decomposition, it enables direct, tunable access to more active on-cycle species (potentially including tagged benzylidenes) from a robust, shelf-stable precursor. In situ generation of these well-defined active species confers metathesis activity and stereocontrol comparable to or better than pristine, meticulously handled Ru-1a, and far superior to samples of Ru-1a even briefly exposed to air in solution. In eliminating the need for production, shipping, and storage of air-sensitive Ru-1a, this advance is anticipated to expand the uptake of olefin metathesis for production of stereodefined alkenes.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"11 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221791","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":"Isotope Tuning of Fermi Resonance and Vibrational Hybridization in Surface-Adsorbed CO2 Probed by Tip-Enhanced Raman Spectroscopy","authors":"Zhi-Jing Zhang,Wen-Cheng Jia,Yun-Jie Yu,Cheng-Qian Jiao,Zhi-Peng Dong,Yang Zhang,Chao Zhang,Yao Zhang,Zhen-Chao Dong","doi":"10.1021/jacs.6c14567","DOIUrl":"https://doi.org/10.1021/jacs.6c14567","url":null,"abstract":"Fermi resonance in CO2 serves as a prototypical example of anharmonic vibrational coupling, where the fundamental vibrational mode of C–O symmetric stretching (v1) mixes quantum-mechanically with the nearly degenerate overtone (2v2) of C–O bending, resulting in energy level splitting, spectral peak shifting, intensity redistribution, and band bifurcation in vibrational spectra. Here, we carry out a comprehensive investigation of this cubic anharmonic interaction in surface-adsorbed CO2 clusters using low-temperature ultrahigh-vacuum Tip-Enhanced Raman Spectroscopy (TERS), in combination with isotope tuning. In addition to clear observation of well-resolved Fermi dyads for both C16O2 and C18O2 isotopologues, TERS enables direct observation of the Raman-inactive bending mode (v2) by breaking the conventional Raman selection rule. As a result, comprehensive and important Fermi resonance parameters of CO2 can be determined from the frequency domain directly, including, e.g., the frequency detuning, the Fermi coupling strength, and the mixing angle for the vibrational hybridization. Furthermore, isotope substitution from C16O2 to C18O2 is found to reduce and even reverse the frequency detuning, which modifies the quantum mixing significantly through the change in the mixing angle and leads to a redistribution of vibrational character between the Fermi dyad states. Such an isotope-induced shift in the mixing angle modifies the balance between constructive and destructive interference, resulting in the observed intensity asymmetry of the Fermi dyads. In addition, these Fermi dyads are found to be somewhat sensitive to cluster morphologies and local adsorption environment. These results demonstrate that TERS is a powerful tool for quantitatively probing anharmonic vibrational interactions such as Fermi resonance at the nanoscale, while isotope substitution can provide an effective route to tune vibrational hybridization and quantum interference for molecules adsorbed on surfaces.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"203 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210913","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}