Journal of the American Chemical Society最新文献

{"title":"Formation and Reactivity of a MnIV(O)(μ-O)CeIV Species: A Closest Mimic of Photosystem II","authors":"Sikha Gupta, Pragya Arora, Zahra Aghaei, Baghendra Singh, Timothy A. Jackson, Apparao Draksharapu","doi":"10.1021/jacs.4c12523","DOIUrl":"https://doi.org/10.1021/jacs.4c12523","url":null,"abstract":"Understanding the basic structure of the oxygen-evolving complex (OEC) in photosystem II (PS-II) and the water oxidation mechanism can aid in the discovery of more efficient and sustainable catalysts for water oxidation. In this context, we present evidence of the formation of a [(TPA)Mn^IV(O)(μ-O)Ce^IV(NO₃)₃]⁺ (<b>2</b>) complex (TPA = tris(pyridyl-2-methyl)amine) by adding aqueous ceric ammonium nitrate to an acetonitrile solution of the [(TPA)Mn^II]²⁺ (<b>1</b>) complex. This unique intermediate (<b>2</b>) was analyzed by using various spectroscopic techniques and electrospray ionization mass spectrometry. Remarkably, <b>2</b> closely mimics the structure of Mn^V(O)(μ-O)Ca^II(OH₂) proposed in the OEC of PS-II. Notably, <b>2</b> reacts effectively with ferrocene derivatives, indicating that redox-active Ce^IV binding enhances the electron transfer efficiency. Additionally, <b>2</b> demonstrated the ability to perform oxygen atom transfer and hydrogen atom abstraction reactions. The discovery of this reactive [(TPA)Mn^IV(O)(μ-O)Ce^IV(NO₃)₃]⁺ species provides exciting opportunities for investigating the structure of the Mn^V(O)(μ-O)Ca^II(OH₂) unit in the OEC.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"4 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832910","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":"Data-Efficient Multifidelity Training for High-Fidelity Machine Learning Interatomic Potentials","authors":"Jaesun Kim, Jisu Kim, Jaehoon Kim, Jiho Lee, Yutack Park, Youngho Kang, Seungwu Han","doi":"10.1021/jacs.4c14455","DOIUrl":"https://doi.org/10.1021/jacs.4c14455","url":null,"abstract":"Machine learning interatomic potentials (MLIPs) are used to estimate potential energy surfaces (PES) from <i>ab initio</i> calculations, providing near-quantum-level accuracy with reduced computational costs. However, the high cost of assembling high-fidelity databases hampers the application of MLIPs to systems that require high chemical accuracy. Utilizing an equivariant graph neural network, we present an MLIP framework that trains on multifidelity databases simultaneously. This approach enables the accurate learning of high-fidelity PES with minimal high-fidelity data. Employing the generalized gradient approximation (GGA) and meta-GGA as low- and high-fidelity approaches, respectively, we tested this framework on the Li₆PS₅Cl and In_<i>x</i>Ga_1–<i>x</i>N systems. The results show that using a high-fidelity training set with a size approximately 10% of the low-fidelity set, the multifidelity training framework achieves excellent accuracy, with Li-ion conductivity predictions within 10% error and In_<i>x</i>Ga_1–<i>x</i>N mixing energy showing an <i>R</i>² of 0.98 compared to the reference high-fidelity MLIP results. It indicates that geometric and compositional spaces not covered by the high-fidelity meta-GGA database can be effectively inferred from low-fidelity GGA data, thus enhancing accuracy and molecular dynamics stability. We also developed a general-purpose MLIP that utilizes both GGA and meta-GGA data from the Materials Project, significantly enhancing MLIP performance for high-accuracy tasks such as predicting energies above hull for crystals in general. Furthermore, we demonstrate that the present multifidelity learning is more effective than transfer learning or Δ-learning and that it can also be applied to learn higher-fidelity up to the coupled-cluster level. We believe this methodology holds promise for creating highly accurate bespoke or universal MLIPs by effectively expanding the high-fidelity data set.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"46 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832958","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":"Palladium Bisphosphine Monoxide Complexes: Synthesis, Scope, Mechanism, and Catalytic Relevance","authors":"Shenghua Yang, Min Deng, Ryan A. Daley, Andrea Darù, William J. Wolf, David T. George, Senjie Ma, Bryn K. Werley, Erika Samolova, Jake B. Bailey, Milan Gembicky, Jonathan Marshall, Steven R. Wisniewski, Donna G. Blackmond, Keary M. Engle","doi":"10.1021/jacs.4c10718","DOIUrl":"https://doi.org/10.1021/jacs.4c10718","url":null,"abstract":"Recent studies in transition metal catalysis employing chelating phosphines have suggested a role for partial ligand oxidation in formation of the catalytically active species, with potentially widespread relevance in a number of catalytic systems. We examine the internal redox reaction of Pd^II(bisphosphine)X₂ (X = Cl, OAc, <i>etc.</i>) complexes to reveal previously underexplored aspects of bisphosphine monoxides (BPMOs), including evaluation of ligand structure and development of general reaction conditions to access a collection of structurally diverse BPMO precatalysts based on organopalladium oxidative addition complexes. In particular, a series of Pd^II(BPMO)(R)(X) (R = aryl, alkyl; X = I, Br) oxidative addition complexes bearing 24 different BPMO ligands were characterized by NMR and X-ray crystallography. Comparison of the catalytic performance of the oxidative addition complexes of bisphosphine versus bisphosphine monoxides as precatalysts is demonstrated to be an enabling diagnostic tool in Pd catalytic reaction development. Finally, the differences in catalytic behavior between bisphosphine and bisphosphine monoxide complexes were rationalized through solid-state parametrization and stoichiometric experiments.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"87 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832663","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":"Borenium-Catalyzed “Boron Walking” for Remote Site-Selective Hydroboration","authors":"Zheng Zhu, Wing Chun Chan, Bin Gao, Guanwen Hu, Peiqi Zhang, Yiyi Fu, Kit San Ly, Zhenyang Lin, Yangjian Quan","doi":"10.1021/jacs.4c13726","DOIUrl":"https://doi.org/10.1021/jacs.4c13726","url":null,"abstract":"Remote functionalization through progressive olefin isomerization enables site-selective modification at a distal position, diversifying the synthetic approaches. However, the developed protocols have long relied on transition metal catalysis. Transition metal catalysts are deemed irreplaceable, albeit facing challenges in metal residue and catalyst poisoning. In this work, we present a pioneering approach that employs a borenium ion as a catalyst for site-selective, remote borylation, eliminating the need for metal catalysts. As the reaction progresses, borylation isomers at different positions emerge, gradually and ultimately converging into the predominant α-borylation product. This process is akin to a “walking” of a boron moiety along a carbon skeleton toward an aryl terminus. Detailed mechanistic studies and DFT calculations substantiate the borenium-catalyzed, stepwise migration via a reversible B–H insertion/elimination sequence. This remote borylation exhibits good functional group compatibility, complementing those methods reliant on transition metals. Furthermore, this metal-free protocol permits the convenient synthesis of silyl-remote-boryl compounds, demonstrating an opposite regioselectivity to that observed in transition-metal-catalyzed tandem silylation-borylation reactions. This discovery therefore contributes to site-selective, remote difunctionalization via sequential C–B and C–Si derivatizations, exemplified by the synthesis of amino-remote-alcohol bioactive molecules.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"136 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832915","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":"Correction to “Modulated Cell Internalization Behavior of Icosahedral DNA Framework with Programmable Surface Modification”","authors":"Kui Huang, Qiulan Yang, Min Bao, Shengwen Wang, Luming Zhao, Qian Shi, Yang Yang","doi":"10.1021/jacs.4c16945","DOIUrl":"https://doi.org/10.1021/jacs.4c16945","url":null,"abstract":"In the original publication, we inadvertently omitted acknowledgment of the Shanghai Pujiang Program (Grant No. 22PJ1409400) as a funding source for this research. The complete acknowledgment statement is shown below. The authors apologize for this oversight and confirm that this correction does not affect the results or conclusions of the study. This work was financially supported by National Natural Science Foundation of China grants (21977069, 22277077), the Shanghai Pujiang Program (22PJ1409400), the Ministry of Science and Technology of China (2018YFA0902600), and Innovative research team of high level local universities in Shanghai (SHSMU-ZLCX20212602). This article has not yet been cited by other publications.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"6 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841611","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":"Hyperpolarized 13C NMR Metabolomics of Urine Samples at Natural Abundance Applied to Chronic Kidney Disease","authors":"Victor Ribay, Benoît Charrier, Mikaël Croyal, Bertrand Cariou, Samy Hadjadj, Julien Boccard, Claire Cannet, Jean-Nicolas Dumez, Marine P. M. Letertre, Patrick Giraudeau","doi":"10.1021/jacs.4c12607","DOIUrl":"https://doi.org/10.1021/jacs.4c12607","url":null,"abstract":"NMR is a central tool in the field of metabolomics, thanks to its ability to provide valuable structural and quantitative information with high precision. Most NMR-based metabolomics studies rely on 1D ¹H detection, which is heavily limited by strong peak overlap. ¹³C NMR benefits from a wider spectral dispersion and narrower signal line width but is barely used in metabolomics due to its low sensitivity. Dissolution dynamic nuclear polarization (d-DNP) offers an opportunity to improve ¹³C NMR sensitivity by several orders of magnitude. Here, we show that this emerging hyperpolarized metabolomics approach can provide meaningful information about clinical samples. Achieving sub-mM limits of detection with ¹³C at natural abundance in urine samples was made possible by a meticulous design of the experimental workflow. The analysis of human urine samples from patients with different stages of chronic kidney disease (CKD) was performed using ¹³C d-DNP NMR and benchmarked to conventional ¹H NMR metabolomics at a high magnetic field to explore the complementarity between the two methods. Multivariate analysis of the d-DNP ¹³C NMR dataset provided a statistical model able to distinguish patients with CKD from control patients. Moreover, ¹³C d-DNP NMR spectra highlighted several biomarkers known to be biologically relevant. Some of them were in agreement with those obtained with conventional ¹H NMR, and the results also highlighted the complementarity of biomarker coverage between hyperpolarized and conventional NMR metabolomics. In particular, ¹³C hyperpolarized NMR allowed the annotation of two biomarkers that could not be detected by ¹H NMR because of peak overlap (i.e., guanine and guanidoacetate).","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"52 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841610","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":"Contrasteric Glycosylations of Cotylenol and 1,2-Diols by Virtual Linker Selection","authors":"Dylan W. Snelson, Stephen I. Ting, Ryan A. Shenvi","doi":"10.1021/jacs.4c15719","DOIUrl":"https://doi.org/10.1021/jacs.4c15719","url":null,"abstract":"Many terpene glycosides exhibit contrasteric patterns of 1,2-diol glycosylation in which the more hindered alcohol bears a sugar; protection of the less hindered alcohol only increases steric repulsion. Here, we report a method for contrasteric glycosylation using a new sugar-linker that forms a cleavable, 10-membered ring with high efficiency, leading to syntheses of cotylenin E, J, and ISIR-050. Linker selection was aided by DFT calculations of side reactions and stereoselectivity, as well as conformational analyses using autoDFT, a Python script that converts SMILES strings to DFT-optimized conformational ensembles.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"30 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832952","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":"Iridium-Catalyzed Enantioconvergent Construction of Piperidines and Tetrahydroisoquinolines from Racemic 1,5-Diols","authors":"Huanlin Diao, Kexin Liu, Rong Yu, Jilin Chen, Yongbing Liu, Bin-Miao Yang, Yu Zhao","doi":"10.1021/jacs.4c12466","DOIUrl":"https://doi.org/10.1021/jacs.4c12466","url":null,"abstract":"We report herein a one-step synthesis of valuable enantioenriched piperidines and tetrahydroisoquinolines from readily available racemic 1,5-diols. Key to the success is the development of new iridacycle catalysts that enable efficient redox-neutral construction of two C–N bonds between diols and amines in an enantioconvergent fashion. Mechanistic studies identified an intriguing preferential oxidation of secondary versus primary alcohol in the diol substrate by the iridacycle catalyst, which set a challenging intermolecular amination of aryl–alkyl-substituted alcohol as the enantiodetermining step for this catalytic <i>N</i>-heterocycle synthesis. Application of this catalytic method to the preparation of important drugs and bioactive compounds is also demonstrated.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"32 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832909","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":"Disulfide-Directed Multicyclic Peptides with N-Terminally Extendable α-Helices for Recognition and Activation of G-Protein-Coupled Receptors","authors":"Shihui Fan, Jie Li, Jie Zhuang, Qingtong Zhou, Yiting Mai, Bingni Lin, Ming-Wei Wang, Chuanliu Wu","doi":"10.1021/jacs.4c12808","DOIUrl":"https://doi.org/10.1021/jacs.4c12808","url":null,"abstract":"Many peptide hormones adopt long α-helical structures upon interacting with their cognate receptors but often exhibit flexible conformations when unbound. Strategies that can stabilize long α-helices without disrupting their binding to receptors are still lacking, which hinders progress in their biological applications and drug development. Here, we present an approach that combines rational design with library screening to create and identify a unique disulfide-directed multicyclic peptide (DDMP) scaffold, which could effectively stabilize N-terminally extendable α-helices while displaying exceptional efficiency in disulfide pairing and oxidative folding. This DDMP scaffold was then utilized for stabilizing the α-helical structure of glucagon-like peptide-1 (GLP-1), resulting in a potent GLP-1 receptor (GLP-1R) agonist with a significantly improved α-helicity and proteolytic stability. By incorporating external α-helices into the DDMP scaffold, we can effectively preserve the native N-terminal α-helical structures while allowing for extensive evolution of the C-terminal disulfide-rich domain for enhancing target binding, as demonstrated by the generation of the DDMP-stabilized GLP-1 (g1:Ox). The cryo-electron microscopy structure of the g1:Ox–GLP-1R in complex with heterotrimeric G_s reveals the molecular basis for the potent binding between g1:Ox and GLP-1R. Specifically, the DDMP moiety establishes additional interactions with the extracellular domain of GLP-1R, which are absent in the case of GLP-1. Thus, this work offers a novel and effective approach for engineering therapeutic peptides and other peptide α-helices, ensuring that both the N- and C-terminal regions remain essential for target recognition and activation.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"23 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832912","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":"Cooperative Regulation of ns2 Lone-Pair Expression Realizes Distinct Excitonic Emissions in Hybrid Germanium, Tin, and Lead Halides","authors":"Jiang Han, Yawen Li, Peijie Zhang, Bin Xu, Xiaofan Xu, Zewei Quan","doi":"10.1021/jacs.4c15554","DOIUrl":"https://doi.org/10.1021/jacs.4c15554","url":null,"abstract":"Lone-pair expression is significantly influenced by geometric constraints in hybrid metal halides (HMHs). Two-dimensional (2D) HMHs possess reduced structural dimensionality, allowing for a wide range of off-center displacement of the metal center. However, the effect of lone-pair-induced off-center distortion on the geometric configuration of inorganic units, electronic properties, and exciton emissions in 2D HMHs remains unclear. In this study, 2D DMPMBr₄ (DMP = <i>N</i>,<i>N</i>′-dimethylpiperazine) HMHs of group 14 elements (M = Ge, Sn, and Pb) are developed, exhibiting pronounced stereochemical activity of <i>n</i>s² lone-pair electrons. Such 2D HMHs are chosen as a model system to demonstrate the influence of the stereochemical activity of <i>n</i>s² lone-pair electrons on the geometric configuration of inorganic units, electronic properties, and exciton emissions. The off-center distortion <i><b>D</b></i> is introduced to describe the degree of lone-pair expression in these HMHs, and a quantitative relationship between the <i><b>D</b></i> and FE/STE emissions is established. When the <i><b>D</b></i> is reduced to less than 0.24, the off-center distortion of the units is sufficiently suppressed to limit the lone-pair expression, facilitating the excitonic transition from the STE state to the FE state upon compression. Substituting metal cations with those having more inactive <i>n</i>s² lone-pair electrons exerts a similar effect to pressure in promoting the excitonic transitions in the DMPMBr₄ series. This study uncovers the relationship between the stereochemical activity of <i>n</i>s² lone-pair electrons and excitonic emissions, which could accelerate the development of HMHs with the desired optical properties.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"19 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832919","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}