Journal of the American Chemical Society最新文献

{"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}

{"title":"Star-Shaped Multivalent Molecular Scavengers for Neutrophil Extracellular Trap-Associated Chromatin Neutralization and Sepsis Treatment","authors":"Chuanxu Cheng,Quanxin Ning,Juan Du,Jianati Dawulieti,Chenyang Guo,Madi Sun,Kunbao Zhang,Haijun Li,Qunjie Bi,Jian Li,Zhen Wu,Ziping Wu,Li-Li Li,Hanyao Huang,Zhi-Liang Ji,Jin-Zhi Du,Chao Yang,Kam W. Leong,Dan Shao","doi":"10.1021/jacs.6c15992","DOIUrl":"https://doi.org/10.1021/jacs.6c15992","url":null,"abstract":"Extracellular chromatin is a composite DNA–protein assembly that is difficult to recognize selectively using conventional cationic nucleic acid scavengers. Inspired by the spatially organized recognition of biomacromolecular assemblies, we developed a library of valency-programmed poly(ethylene glycol)-aminoglycoside conjugates that preferentially recognize neutrophil extracellular trap (NET)–associated chromatin while retaining antibacterial activity. Screening aminoglycoside identity and scaffold valency identified 8-arm poly(ethylene glycol)-netilmicin (8-arm Netil) as the lead construct. Its flexible multivalent architecture enabled simultaneous contacts with DNA phosphates and histone-associated sites, generating cooperative electrostatic and hydrogen-bonding interactions. At equal netilmicin equivalents, 8-arm Netil retained stronger chromatin binding than free netilmicin and the 2- and 4-arm conjugates, whereas cationic poly(amidoamine) dendrimers failed to reproduce its combined affinity and selectivity. 8-arm Netil bound DNA–histone chromatin with a dissociation constant of 5.73 × 10–8 M, and showed substantially weaker interactions with isolated DNA, histones, and serum albumin. This multivalent recognition suppressed NET-induced Toll-like receptor 4 and 9 signaling while preserving antibacterial activity. In bacterial peritonitis and polymicrobial sepsis models, 8-arm Netil reduced bacterial dissemination, extracellular chromatin burden, inflammation, and mortality. This work establishes valency-programmed aminoglycoside presentation as a chemical strategy for recognizing and neutralizing composite extracellular chromatin.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"57 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210912","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":"Enantioselective Total Synthesis of Sestermobaraene F","authors":"Manuel J. Scharf,Sander Folkerts,Moritz E. Hansen,Lorenzo A. A. Fitze,Douglas Strasoldo-Graffemberg,Claudia S. Zhang,Erick M. Carreira","doi":"10.1021/jacs.6c14482","DOIUrl":"https://doi.org/10.1021/jacs.6c14482","url":null,"abstract":"We report the first and enantioselective total synthesis of the bacterial sesterterpene natural product sestermobaraene F, featuring a highly substituted cyclopropane embedded in a 5/3/7/6/5-pentacyclic skeleton. The route involves preparation of a key bicyclo[3.1.0]hexane building block through a Lewis acid-mediated photochemical rearrangement of a quinol benzoate, which was investigated mechanistically. Convergent fragment coupling set the stage for installment of the central ring through a 6-endo-trig cycloisomerization. In this regard, the generation of a substituted formal 3° cyclopropyl radical from a methylenecyclopropane under Co-catalysis is novel. The subsequent challenging chemo- and stereoselective reduction of the tetrasubstituted enone was accomplished by employing Yamamoto’s sterically demanding ATPH Lewis acid. In the final steps, regioselective ring expansion allowed for completion of the natural product. Notably, the study presents a potential strategy to access other 5/3/7/6/5-pentacyclic sesterterpenes.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"33 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218936","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":"Programming Symmetry in Colloidal Crystal Engineering with DNA Using Four-Way Junction-Dendrons","authors":"Ana Clara Zampirolli Leal,Domagoj Fijan,Kaitlin M. Landy,Kyle J. Gibson,Byeongdu Lee,Sajib Barua,Xiaobing Zuo,Sharon C. Glotzer,Chad A. Mirkin","doi":"10.1021/jacs.6c15674","DOIUrl":"https://doi.org/10.1021/jacs.6c15674","url":null,"abstract":"DNA-mediated colloidal crystal engineering enables the construction of highly ordered three-dimensional nanoparticle superlattices. Traditionally, anisotropic programmable atom equivalents (PAEs) have been employed to introduce directional bonding interactions needed to form lower-symmetry, more complex lattices, whereas isotropic, spherical PAEs typically yield high-symmetry structures. Here, we design programmable DNA junction-dendrons that impart directional interactions between isotropic gold nanoparticle-core PAEs, with a four-way junction (4WJ), rather than the nanoparticle shape, governing assembly directionality. This strategy decouples directional DNA bonding from nanoparticle-core geometry. Unlike prior junction-dendron systems, the defined geometry of rigid 4WJs enables direct interrogation of how junction-imposed directionality influences crystallization. In this system, DNA 4WJs serve as dendron cores and coassemble with isotropic gold nanoparticle-core PAEs. By systematically varying junction size and conformational rigidity, we establish structure–directionality relationships that govern crystal symmetry and lattice parameters. Molecular dynamics simulations and small-angle X-ray scattering (SAXS) reveal that rigid 4WJs adopt a stacked Holliday conformation, promoting anisotropic bonding and enabling the formation of simple hexagonal (SH, P6/mmm) and distorted hexagonal close-packed (distorted HCP, P63/mmc) lattices, dictated by the dendron-to-nanoparticle size ratio. Coarse-grained molecular dynamics simulations further show that junction-accessible binding topologies, determined by junction size, govern this transition. In contrast, flexible junctions drive a symmetry transition from P6/mmm to P63/mmc at constant size ratios. These results establish 4WJ rigidity and conformation as primary determinants of crystal symmetry and demonstrate that junction geometry can program and resolve directional bonding, expanding the structural and compositional diversity of colloidal crystals.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"11 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218940","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":"1,3-cis-Disubstituted Cycloalkanes by Iridium-Catalyzed Enantio-convergent Migratory Hydroheteroarylation","authors":"En-Ze Lin,Jun-Kai Shi,Xin Sun,Bi-Jie Li","doi":"10.1021/jacs.6c16551","DOIUrl":"https://doi.org/10.1021/jacs.6c16551","url":null,"abstract":"Enantioenriched 1,3-disubstituted cycloalkanes are important structural motifs in pharmaceuticals and natural products, yet their stereoselective synthesis remains challenging owing to difficulties in remote control of regio- and stereoselectivities. Herein, we report an iridium-catalyzed enantio-convergent hydroheteroarylation of racemic unactivated cyclic alkenes through a dynamic kinetic asymmetric transformation (DYKAT). Racemic cyclohexenes, cycloheptenes, and cyclooctenes undergo hydroheteroarylation with excellent regio-, diastereo-, and enantioselectivity, providing 1,3-cis-disubstituted cycloalkanes in an enantio-convergent manner. The method enables the efficient construction of both tertiary–tertiary and quaternary–tertiary stereogenic relationships within saturated carbocyclic frameworks.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"163 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218947","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":"Local Symmetry Breaking Facilitates Near-Infrared Circularly Polarized Lanthanide Emission in Perovskite Nanocrystals","authors":"Tyler Wang,Fangyuan Liu,Yan Zhou,Joseph A. Adewuyi,Zhengjie Li,Mingwei Ge,Haiyan Tan,Gaël Ung,Cong Su,Mengxia Liu","doi":"10.1021/jacs.6c15479","DOIUrl":"https://doi.org/10.1021/jacs.6c15479","url":null,"abstract":"Imparting chiroptical activity of lanthanide transitions provides an attractive route to circularly polarized luminescence. However, obtaining intense emission from their Laporte-forbidden f–f transitions while also generating significant rotatory strength remains a formidable challenge in materials design. This work establishes a platform for efficient near-infrared (NIR) circularly polarized luminescence (CPL), centered on the telecom-relevant C-band around 1550 nm, from lanthanide dopants (Yb3+/Er3+) embedded in chiral perovskite nanocrystal (CsPbX3) hosts. Atomic-scale structural analyses reveal a preferential enrichment of lanthanide concentration near the nanocrystal surfaces, where chiral ligands distort the lattice, lowering the local symmetry. Spectroscopic measurements confirm the highly efficient host-to-dopant energy transfer, facilitating strong CPL, with a luminescence dissymmetry factor (glum) of 0.36 and a CPL brightness (BCPL) of 4.2 × 105 M–1 cm–1 at 1550 nm, representing nearly four orders of magnitude above the previous benchmark. With improved photostability, these results establish lanthanide-doped chiral perovskite nanocrystals as a promising route to telecom-relevant CPL.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"56 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218934","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}