Journal of the American Chemical Society最新文献

{"title":"Ultratough Thermoplastic Elastomers Based on Chemically Recyclable Cycloalkyl-Substituted Polyhydroxyalkanoates","authors":"Hao-Yi Huang, Min Xie, Si-Qi Wang, Yu-Ting Huang, Yong-Hong Luo, Da-Gang Yu, Zhongzheng Cai, Jian-Bo Zhu","doi":"10.1021/jacs.4c17703","DOIUrl":"https://doi.org/10.1021/jacs.4c17703","url":null,"abstract":"It remains a long-standing challenge for chemical recycling of polyhydroxyalkanoates (PHAs) to propiolactone-based monomers due to the high ring strain and many inevitable side reactions. In this contribution, a novel α-spiro-cyclohexyl-propiolactone (SHPL) has been designed with high reactivity toward ring-opening polymerization even at a catalyst loading of &lt;1 ppm. The resulting poly(3-hydroxy-2-spiro-cyclohexylpropionate) (P3HSHP) exhibited high thermal stability with a <i>T</i>_d of 364 °C and a high <i>T</i>_m of 272 °C. Meanwhile, it could be depolymerized back to SHPL in 86% yield without decarboxylation or elimination side products. Notably, SHPL could be exploited to construct high-performance thermoplastic elastomers (TPEs) via one-pot copolymerization with ε-caprolactone (CL). Particularly, the resulting gradient P(CL₂₀₀₀-<i>grad</i>-SHPL₅₀₀) showcased an ultimate tensile strength of 58.8 ± 4.0 MPa, high stretchability of 1959 ± 53%, a record toughness of 600 MJ/m³, and high elastic recovery (&gt;90%). This superior performance of SHPL could advance the development of new sustainable high-performance TPEs.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"81 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462780","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":"Porous and Amorphous MnxMo3S13 Chalcogel Electrode for High-Capacity Conversion-Based Lithium-Ion Batteries","authors":"Taohedul Islam, Sahar Bayat, Matthew A. Wright, Subrata Chandra Roy, Conrad Sawicki, Carrie L. Donley, Amar S. Kumbhar, Roman Chernikov, Misganaw Adigo Weret, Kamila M. Wiaderek, Chad Risko, Ruhul Amin, Saiful M. Islam","doi":"10.1021/jacs.4c15552","DOIUrl":"https://doi.org/10.1021/jacs.4c15552","url":null,"abstract":"While Li-ion batteries (LIBs) are a leading energy storage technology, their energy densities are limited by the low capacity of conventional intercalation cathodes, driving interest in high energy-density Li–S batteries that make use of conversion chemistry. Achieving high capacity, reversibility, and cycle stability, and controlling volume changes in conversion batteries during the charge–discharge process, however, remains challenging. Here, we present a porous, amorphous, sulfide-based Mn_<i>x</i>Mo₃S₁₃ chalcogel, which concurrently offers high capacity and cycle stability. The solution-processable room temperature synthesized Mn_<i>x</i>Mo₃S₁₃ (<i>x</i> = 0.25) chalcogel exhibits a local structure that resembles the Mo₃S₁₃ cluster with Mn²⁺ distributed across the Mo₃S₁₃ matrix, as determined by synchrotron X-ray pair distribution function (PDF) and extended X-ray absorption fine structure (EXAFS). Ab initio molecular dynamics (AIMD) simulations reveal that Mn²⁺ incorporation shortens the polysulfide chain in the gel matrix compared to the Mo₃S₁₃ chalcogel, while forming a coordination environment with disulfide groups, analogous to the experimental findings. A Li/Mn_0.25Mo₃S₁₃ half-cell delivers 897 mAh g^–1 capacity during the first discharge and retains 571 mAh g^–1 capacity after 100 cycles at a C/3 rate. Distribution of relaxation time (DRT) unveils a stable solid–electrolyte interphase (SEI) formation upon cycling that enables charge–discharge reversibility. Here, the enhanced capacity retention and cycle stability compared to those of the Li/Mo₃S₁₃ cell are attributed to the reduced dissolution of active mass into the electrolyte, facilitated by the formation of shorter polysulfide chains within the Mn_0.25Mo₃S₁₃ structure and the strong affinity of Lewis-acidic Mn²⁺ for polysulfide anions generated during the charge–discharge process of the Li/Mn_0.25Mo₃S₁₃ cell. Thus, this work illustrates a design principle of material for high-capacity and cycle-stable Li-metal sulfide batteries.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"81 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462774","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":"Manipulating Hydrogen-Bonding Donor/Acceptor in Ultra-Robust Isoreticular Zr(IV) Metal–Organic Frameworks for Efficient Regulation of Water Sorption Inflection Point and Steepness","authors":"Yuan Geng, Yifei Gao, Pengfu Gao, Jingjing Zhang, Xianhui Tang, Jinqiao Dong, Jingjing Jiao, Helin Niu, Wei Gong, Yong Cui","doi":"10.1021/jacs.4c17145","DOIUrl":"https://doi.org/10.1021/jacs.4c17145","url":null,"abstract":"The development of porous materials exhibiting steep and stepwise adsorption of water vapor at desired humidity is crucial for implementing diverse applications such as humidity control, heat allocation, and atmospheric water harvesting. The precise molecular-level elucidation of structural characteristics and chemical components that dictate the water sorption behaviors in confined nanospaces, metal–organic frameworks (MOFs) in particular, is fundamentally important, but this has yet to be largely explored. In this work, by leveraging the isoreticular principle, we crafted two pairs of isostructural Zr-MOFs with linker backbones of benzene and pyrazine acting as hydrogen-bonding donor and acceptor, respectively. The outstanding water sorption cyclic durability of the four Zr-MOFs permits persuasive investigation of the correlation of the water sorption inflection point and steepness (the two central figures-of-merit for water sorption) with the linker functionality. The two pyrazine-carrying Zr-MOFs both show steep water uptake at lower relative pressure and slightly decreased steepness, which are quantitatively described by the Dubinin-Astakhov relation. We deciphered the privileged water clusters through single-crystal X-ray diffraction studies in which the pyrazine moiety formed stronger hydrogen-bonding interactions with guest water molecules and favored the formation of water pentamers instead of hexamers that are observed in the benzene analog. The hydrogen-bonding donor/acceptor manipulation approach presented in this work may facilitate future research endeavors focusing on molecular attribute engineering in predeterminedly ultrawater-resistant MOF platforms for efficient regulation of water sorption behaviors toward customized applications.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"25 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462779","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":"Asymmetric Radical Cyclopropanation of α,β-Unsaturated Amides with α-Boryl and α-Silyl Dibromomethanes via Cr(II)-Based Metalloradical Catalysis.","authors":"Xinyu Wang, Zhaoxin Shi, Mingrui Xu, Xiaoyu Lin, Zhaobin Wang","doi":"10.1021/jacs.4c13269","DOIUrl":"https://doi.org/10.1021/jacs.4c13269","url":null,"abstract":"<p><p>Transition-metal-catalyzed asymmetric carbene-transfer reactions represent a powerful strategy for synthesizing chiral cyclopropanes. However, current methods predominantly rely on stabilized carbene-bearing <i>α</i>-π-conjugated groups, restricting access to less stabilized carbenes, such as <i>α</i>-silyl and <i>α</i>-boryl carbenes. Herein, we present an unprecedented Cr(II)-based metalloradical system for the asymmetric cyclopropanation of <i>α</i>,<i>β</i>-unsaturated amides with <i>α</i>-boryl and <i>α</i>-silyl dibromomethanes in the presence of Mn as the reducing agent. Employing a chiral chromium complex, the reaction proceeds under mild conditions, yielding cyclopropanes with three contiguous stereocenters in high diastereo- and enantioselectivities. This method features a Cr-catalyzed radical-based stepwise cyclopropanation mechanism. The broad substrate scope, encompassing various <i>α</i>,<i>β</i>-unsaturated amides, demonstrates the protocol's versatility and robustness. Mechanistic insights, supported by experimental and computational studies, suggest the formation of <i>α</i>-Cr(III)-alkyl radical intermediates, delineating a pathway distinct from that of classical concerted cyclopropanations. This approach provides a powerful tool for synthesizing highly functionalized cyclopropanes, offering high potential for applications in drug discovery and development.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143456255","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":"Interfacial Hydrogen-Bond Network Regulation Tuned Water Dissociation Enables Selective Chlorination of Alkenes.","authors":"Junwei Yao, Chuanqi Cheng, Yongmeng Wu, Cuibo Liu, Shuoshuo Guo, Ying Gao, Bin Zhang","doi":"10.1021/jacs.5c00818","DOIUrl":"https://doi.org/10.1021/jacs.5c00818","url":null,"abstract":"<p><p>Electrocatalytically selective chlorination of olefins in Cl^--containing solutions is a sustainable method for synthesizing chlorohydrin/vicinal dichloride; however, controlling the selectivity is challenging. Here, aqueous/dimethyl carbonate (DMC) hybrid electrolytes with different H₂O/DMC ratios are designed to modulate the ·OH formation to increase the corresponding selectivities. The combined results of in/ex situ spectroscopies and molecular dynamics simulations reveal the origin of high selectivity. TFSI^- shields the transportation of free H₂O to provide moderate ·OH formation for the synthesis of chlorohydrin. DMC reconstructs hydrogen bonds with free H₂O to minimize the interaction between them and the anode, matching the requirements of vicinal dichloride production. Thus, these hybrid electrolytes not only achieve high selectivities of 80% and 76% for chlorohydrin and vicinal dichloride, respectively, but also enable the selective chlorination of other olefins with high isolated yields of up to 74%. This work provides a facile strategy to regulate the selectivity of anodic chlorination via a rational electrolyte design.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143456259","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":"DNA Framework-Enabled Ocular Barrier Penetration for Microinvasive Antiangiogenic Therapy","authors":"Ruobing Wang, Yanhan Liu, Yuelu Zhang, Qiuxue Yi, Wenjuan Xiao, Tianqin Wang, Qi Chen, Jiayang Xiang, Lu Song, Chunhong Li, Fan Li, Lin Liu, Qian Li, Chunhai Fan, Xiuhai Mao, Xiaolei Zuo","doi":"10.1021/jacs.4c16529","DOIUrl":"https://doi.org/10.1021/jacs.4c16529","url":null,"abstract":"Therapeutic aptamers targeting vascular endothelial growth factor A (VEGFA) have advanced the development of antiangiogenic drugs for treating choroidal neovascularization (CNV) diseases. However, despite FDA approval for use in neovascular age-related macular degeneration (nAMD), the effective <i>in vivo</i> delivery of therapeutic aptamers is hindered by ocular barriers and rapid degradation in biofluids. Here, we demonstrated a microinvasive delivery of VEGFA-targeted aptamers to the ocular fundus using tetrahedral framework nucleic acids (tFNAs). Upon incorporating anti-VEGFA aptamers to the tFNAs (apt-tFNA), we interrogated their penetration across the outer blood–retinal barrier (oBRB) to the innermost retinal in the eyeball, while maintaining their structural integrity. In addition, the apt-tFNA showed superior efficacy in inhibiting vascular proliferation and migration by neutralizing VEGFA. Furthermore, in a laser-induced CNV mouse model, subconjunctival injection of apt-tFNA exhibited comparable antiangiogenic efficacy to intravitreal ranibizumab, a monoclonal antibody fragment. These findings suggest that FNAs can effectively deliver therapeutic aptamers to the ocular fundus without compromising their antiangiogenic properties, highlighting their potential for microinvasive and feasible periocular administration in treating neovascular ophthalmic diseases.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"20 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462776","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":"Manipulating a Thermosalient Crystal Using Selective Deuteration","authors":"Alexander Angeloski, Pablo Galaviz, Richard A. Mole, Ross O. Piltz, Andrew M. McDonagh, Courtney Ennis, Dominique Appadoo","doi":"10.1021/jacs.5c01140","DOIUrl":"https://doi.org/10.1021/jacs.5c01140","url":null,"abstract":"The thermosalient transformation in nickel(II) bis(diisopropyl)dithiocarbamate has been investigated using selective deuteration. The deuterated crystals undergo a reversible displacive phase transition that is ∼4 K higher in temperature compared to the protonated analogue. Neutron, synchrotron, density-functional theory, and calorimetric techniques were utilized to demonstrate the substantial effect of deuterium. All techniques demonstrated the equivalence of the mechanism on an atomic scale between the protonated and deuterated complexes. The data collected in this study reveal details of the changes of atomic motion that underpin the thermosalience inherent in this system. Deuterium decreased the frequency of atomic vibrations thus increasing the temperature of the observed transformation. This study represents a key advancement in the field of thermosalient molecular systems and provides insights into the control and manipulation of thermosalient materials.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"50 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462782","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":"High-Spin Manganese(V) in an Active Center Analogue of the Oxygen-Evolving Complex.","authors":"Olesya S Ablyasova, Mihkel Ugandi, Esma B Boydas, Mayara da Silva Santos, Max Flach, Vicente Zamudio-Bayer, Michael Roemelt, J Tobias Lau, Konstantin Hirsch","doi":"10.1021/jacs.4c14543","DOIUrl":"https://doi.org/10.1021/jacs.4c14543","url":null,"abstract":"<p><p>In a comprehensive investigation of the dinuclear [Mn₂O₃]⁺ cluster, the smallest dimanganese entity with two μ-oxo bridges and a terminal oxo ligand, and a simplified structural model of the active center in the oxygen-evolving complex, we identify antiferromagnetically coupled high-spin manganese centers in very different oxidation states of +2 and +5, but rule out the presence of a manganese(IV)-oxyl species by experimental X-ray absorption and X-ray magnetic circular dichroism spectroscopy combined with multireference calculations. This first identification of a high-spin manganese(V) center in any polynuclear oxidomanganese complex underscores the need for multireference computational methods to describe high-valent oxidomanganese species.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447296","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":"Molecular Photoelectrodes with Enhanced Photogenerated Charge Transport for Efficient Solar Hydrogen Evolution.","authors":"Yifan Gao, Feiqing Sun, Yanjie Fang, Yingke Wen, Feiyang Hong, Bing Shan","doi":"10.1021/jacs.4c17133","DOIUrl":"https://doi.org/10.1021/jacs.4c17133","url":null,"abstract":"<p><p>Photoelectrocatalytic cells for seawater splitting have shown promise toward large-scale deployment; however, challenges remain in operation performances, which outline clear research needs to scale up photoelectrodes with small loss of efficiency. Here, we report an approach for scalable and robust solar H₂ evolution by enhancing photogenerated charge transport in a H₂-evolving molecular photoelectrode. The photoelectrode is based on p-type conjugated polymers that are homogeneously distributed in a polycarbazole network. With a self-assembled NiS₂ catalyst, the photoelectrode under solar irradiation (100 mW cm^-2, AM 1.5 G) is capable of evolving H₂ from seawater at an external quantum efficiency (EQE) of 34.4% under an applied bias of -0.06 V vs RHE. When scaling up from 1 cm² to 25 cm², the photoelectrode generates photocurrents stabilized at 0.4 A and maintains the high EQE at an efficiency loss of less than 1%. Investigation of the photogenerated charge-transport dynamics reveals that the kinetic basis for scaling up lies in the desirable hole diffusion length that far exceeds the spacing between adjacent conjugated-polymer chains due to interchain π-π interactions.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447309","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":"Multimodal Precise Control Over Multiselective Carbonylation of 1,3-Enynes.","authors":"Chang-Sheng Kuai, Yuanrui Wang, Ting Yang, Xiao-Feng Wu","doi":"10.1021/jacs.5c00032","DOIUrl":"https://doi.org/10.1021/jacs.5c00032","url":null,"abstract":"<p><p>Efficiently constructing structurally diverse and complex organic molecules through selective catalytic functionalization is a central goal in synthetic chemistry, yet achieving precise control over multiple reactive centers in multisite substrates remains a formidable challenge. Building on foundational advances in single- and dual-selective transformations, we report a multimodal strategy for the selective carbonylation of 1,3-enynes, a versatile class of multisite substrates. Through meticulous fine-tuning of the catalytic conditions, our approach enables five distinct regio- and stereoselective carbonylative transformations, including direct functionalization (1,2- and 2,1-hydroaminocarbonylation) and tandem cyclization pathways (2,4-, 1,3-, and 2,3-carbonylation). Furthermore, mechanistic studies suggested that multidimensional precise regulation enables the seamless relay of up to three tandem reactions (hydroaminocarbonylation-hydroamination-transamination) with exceptional accuracy. This unified platform not only establishes a robust framework for tackling the enduring challenges of selectivity control in multisite substrates but also broadens the chemical space accessible through 1,3-enyne transformations, exemplifying atom- and step-economic principles and paving the way for transformative advancements in drug discovery, materials science, and beyond.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447311","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}