Journal of the American Chemical Society最新文献_第8页

Zeotype-Confined Frustrated Lewis Pair and Its Role in Catalyzing Hydrogenation

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-04-22 DOI: 10.1021/jacs.5c03123

Mengyuan Li, Yihan Ye, Bing Bai, Cheng Liu, Hanlixin Wang, Zhaochao Xu, Jianping Xiao, Feng Jiao, Xiulian Pan, Xinhe Bao

{"title":"Zeotype-Confined Frustrated Lewis Pair and Its Role in Catalyzing Hydrogenation","authors":"Mengyuan Li, Yihan Ye, Bing Bai, Cheng Liu, Hanlixin Wang, Zhaochao Xu, Jianping Xiao, Feng Jiao, Xiulian Pan, Xinhe Bao","doi":"10.1021/jacs.5c03123","DOIUrl":"https://doi.org/10.1021/jacs.5c03123","url":null,"abstract":"Recent theoretical studies predicted that the frustrated Lewis pair (FLP) formed by carbonaceous species confined in zeolites/zeotypes can activate H–H and C–H bonds. However, there still lacks experimental evidence and understanding on the role of FLP in the hydrogenation reaction. Herein, we combined experiments and density functional theory (DFT) calculations to demonstrate that the Brønsted acid sites with weak acid strength can transfer H+ to the confined carbonaceous species to form Si–O––Al as a Lewis base and carbocation as a Lewis acid. They are electrostatically attracted and sterically repelled, thus, forming FLP sites. We present for the first time experimental evidence and a general principle about the formation of FLP sites inside zeotypes and investigated the effect of the topology and the acid strength on the FLP formation. FLP sites are active in ethylene hydrogenation, and their activity is inversely correlated with their parent Brønsted acid strength. FLP derived from weaker Brønsted acid sites promotes C2H4 adsorption and H2 activation, thus enhancing hydrogenation. This work not only provides mechanistic insights into the origin of olefin hydrogenation over metal-free zeolites/zeotypes but also offers guidance for further development of high-performance zeolite/zeotype-based catalysts and heterogeneous FLP catalysts.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"39 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862540","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Nanopores with an Engineered Selective Entropic Gate Detect Proteins at Nanomolar Concentration in Complex Biological Sample

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-04-22 DOI: 10.1021/jacs.4c17147

Sabine Straathof, Giovanni Di Muccio, Giovanni Maglia

引用次数: 0

Photocatalyst-Dependent Enantioselectivity in the Light-Driven Deracemization of Cyclic α-Aryl Ketones

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-04-22 DOI: 10.1021/jacs.5c00847

Justin Y. Wang, Eris Villalona, Robert R. Knowles

{"title":"Photocatalyst-Dependent Enantioselectivity in the Light-Driven Deracemization of Cyclic α-Aryl Ketones","authors":"Justin Y. Wang, Eris Villalona, Robert R. Knowles","doi":"10.1021/jacs.5c00847","DOIUrl":"https://doi.org/10.1021/jacs.5c00847","url":null,"abstract":"We report a photoredox-enabled deracemization of cyclic α-aryl ketones that occurs with high stereoselectivity and yield and proceeds by mechanistically distinct proton transfer reactions. This reaction is jointly mediated by a visible-light photocatalyst and a chiral phosphate base cocatalyst under blue light irradiation. Notably, the extent of deracemization for this reaction exhibits an unexpected dependence on the identity of the photocatalyst and the concentration of a chiral base cocatalyst, wherein the extent of deracemization can be increased by employing photocatalysts with more positive ground-state reduction potentials, raising the concentration of the chiral base cocatalyst, or by a combination of these factors. This effect is attributed to two competing processes, back-electron transfer and deprotonation, which consume the same reaction intermediate, and we propose a kinetic model that rationalizes this behavior. We also demonstrate that the redox properties of the photocatalyst impact the stereoselectivity of the product-forming step, which is the dominant stereoselective step in this transformation. Together, these mechanistic insights facilitate a deeper understanding of the complexity of light-driven deracemization reactions involving reversible electron transfer and suggest approaches by which the stereoselectivity of these processes may be increased.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"32 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862534","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Magnetic Properties Tuning via Broad Range Site Deficiency in Square Net Material UCuxBi2

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-04-22 DOI: 10.1021/jacs.4c18438

Hope A. Long, Daniel Duong, Joanna Blawat, Gregory Morrison, Yan Wu, Huibo Cao, Nabaraj Pokhrel, David S. Parker, John Singleton, Rongying Jin, Vladislav V. Klepov

{"title":"Magnetic Properties Tuning via Broad Range Site Deficiency in Square Net Material UCuxBi2","authors":"Hope A. Long, Daniel Duong, Joanna Blawat, Gregory Morrison, Yan Wu, Huibo Cao, Nabaraj Pokhrel, David S. Parker, John Singleton, Rongying Jin, Vladislav V. Klepov","doi":"10.1021/jacs.4c18438","DOIUrl":"https://doi.org/10.1021/jacs.4c18438","url":null,"abstract":"HfCuSi2-type pnictogen compounds have recently been shown to be a versatile platform for designing materials with topologically nontrivial band structures. However, these phases require strict control over the electron count to tune the Fermi level, which can only be achieved in compositions with A2+M2+Pn2 and A3+M+Pn2 (A = lanthanides, M = transition metals, Pn = pnictogens P–Bi) charge distribution. While such lanthanide compounds have been thoroughly studied as candidate magnetic topological materials, their heavy element analogs with uranium and bismuth remain largely underexplored. In this report, we present the synthesis of UCuxBi2 single crystals and study their magnetic properties. Detailed structural analysis revealed that flux-grown crystals always form as a site-deficient UCuxBi2 composition, where x varies between 0.20 and 0.64. Magnetic property measurements revealed a dependence of the magnetic coupling on the Cu site deficiency, linearly changing the Néel temperature from 51 K for UCu0.60Bi2 to 118 K for UCu0.30Bi2. Moreover, higher Cu concentration promotes a metamagnetic transition in highly magnetically anisotropic UCu0.60Bi2 single crystals. We show that DFT calculations can successfully model site deficiency in the UCuxSb2 and UCuxBi2 systems. This work paves the way toward using the site deficiency to tune the Fermi level in more ubiquitous A3+M2+xPn2 phases, which previously have not been considered topological candidate materials due to unfavorable electron count.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"33 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858128","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Light- and Heat-Responsive Frustrated Lewis Pair Enables On-Demand Fixation of Ethylene

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-04-22 DOI: 10.1021/jacs.5c03130

Taiki Yanagi, Jun Takaya

{"title":"Light- and Heat-Responsive Frustrated Lewis Pair Enables On-Demand Fixation of Ethylene","authors":"Taiki Yanagi, Jun Takaya","doi":"10.1021/jacs.5c03130","DOIUrl":"https://doi.org/10.1021/jacs.5c03130","url":null,"abstract":"Frustrated Lewis pairs (FLPs) have been widely utilized as useful reagents and catalysts for activation of small molecules (SMs) through thermally controlled equilibrium formation of FLP–SM adducts. Herein, we report a light- and heat-responsive FLP system for on-demand fixation of ethylene. The system realizes capture and release of ethylene orthogonally triggered by visible light and heat, demonstrating potential utility as a nonmetallic and environmentally benign method for separation and storage of ethylene. The applicability to other alkenes is also demonstrated. Mechanistic investigations clarify that the photoexcited FLP enables stepwise radical addition to ethylene, followed by skeletal rearrangement to afford the FLP–ethylene adduct, which undergoes thermally promoted, concerted retro-cycloaddition to release ethylene and the free FLP. As a synthetic application, nonequilibrium, selective cis-to-trans isomerization of cyclooctene is achieved through the capture and release of cyclooctene with the FLP. This work discloses unique photochemical reactivity and application of FLPs, leading to further expansion of FLP chemistry into chemical science.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"17 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858156","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Unlocking Phase Purity of Sodium Iron Sulfate for Low-Cost and High-Performance Sodium-Ion Batteries

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-04-21 DOI: 10.1021/jacs.5c02485

Changyu Liu, Kean Chen, Fumin Li, Along Zhao, Ping Liu, Zhongxue Chen, Yongjin Fang, Yuliang Cao

{"title":"Unlocking Phase Purity of Sodium Iron Sulfate for Low-Cost and High-Performance Sodium-Ion Batteries","authors":"Changyu Liu, Kean Chen, Fumin Li, Along Zhao, Ping Liu, Zhongxue Chen, Yongjin Fang, Yuliang Cao","doi":"10.1021/jacs.5c02485","DOIUrl":"https://doi.org/10.1021/jacs.5c02485","url":null,"abstract":"The alluaudite-type sulfate Na2Fe2(SO4)3 has gained significant attention as a promising cathode material for sodium-ion batteries (SIBs). However, the inevitable formation of impurities during synthesis and the irreversible structural distortion caused by Fe–Na exchange during electrochemical reactions severely hinder its electrochemical performance. Herein, we tackle these challenges by engineering an enlarged Fe–Fe distance in the lattice through partial PO43– substitution. This strategic modification significantly alleviates the Coulombic repulsion between Fe ions and effectively prevents Fe-migration during the electrochemical reaction. Moreover, the unique ion state within the structure ensures enhanced ion/electron transport kinetics, minimal volume change, and a stable framework conducive to long cycling life. Notably, the novel Fe-fully occupied phase-pure Na2.5Fe2(SO4)2.5(PO4)0.5 [also denoted as Na5Fe4(SO4)5(PO4)] electrode delivers a record-high discharge capacity of 112 mA h g–1 at 0.2C, coupled with exceptional cycling stability with 88.8% capacity retention over 10,000 cycles at 10C. Additionally, the enhanced adsorption energy of Na2.5Fe2(SO4)2.5(PO4)0.5 cathode toward H2O contributes to its outstanding air stability in humid atmosphere. This finding offers valuable insights for the development of advanced, low-cost materials for SIBs.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"91 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858159","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Ordered Graphane Nanoribbons Synthesized via High-Pressure Diels–Alder Polymerization of 2,2′-Bipyrazine

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-04-21 DOI: 10.1021/jacs.5c03116

Fang Li, Xingyu Tang, Yunfan Fei, Jie Zhang, Jie Liu, Puyi Lang, Guangwei Che, Zilin Zhao, Yuqing Zheng, Yuan Fang, Chen Li, Dexiang Gao, Xiao Dong, Takanori Hattori, Jun Abe, Ho-kwang Mao, Haiyan Zheng, Kuo Li

{"title":"Ordered Graphane Nanoribbons Synthesized via High-Pressure Diels–Alder Polymerization of 2,2′-Bipyrazine","authors":"Fang Li, Xingyu Tang, Yunfan Fei, Jie Zhang, Jie Liu, Puyi Lang, Guangwei Che, Zilin Zhao, Yuqing Zheng, Yuan Fang, Chen Li, Dexiang Gao, Xiao Dong, Takanori Hattori, Jun Abe, Ho-kwang Mao, Haiyan Zheng, Kuo Li","doi":"10.1021/jacs.5c03116","DOIUrl":"https://doi.org/10.1021/jacs.5c03116","url":null,"abstract":"Graphane shares the same two-dimensional honeycomb structure of graphene, but its saturated carbon skeleton gives rise to a bandgap and therefore provides more possibilities for the development of novel carbon-based semiconductors. However, the hydrogenation of graphene usually leads to disordered and incompletely hydrogenated graphane, and the precise synthesis of graphane with a specific configuration is still very challenging. Here, we synthesized a crystalline graphane nanoribbon (GANR) via pressure-induced polymerization of 2,2′-bipyrazine (BPZ). By performing Rietveld refinement of in situ neutron diffraction data, nuclear magnetic resonance spectroscopy, infrared spectra, and theoretical calculation, we found that BPZ experienced Diels–Alder polymerization between the π···π stacked aromatic rings and formed extended boat-GANR structures with exceptional long-range order. The unreacted −C═N– groups bridge the two ends of the boat and are ready for further functionalization. The GANR has a bandgap of 2.25 eV, with booming photoelectric response (ION/IOFF = 18.8). Our work highlights that high-pressure topochemical polymerization is a promising method for the precise synthesis of graphane with specific structure and desired properties.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"128 8 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853845","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Making Cells as a “Nirvana Phoenix”: Precise Coupling of Precursors Prior to ROS Bursts for Intracellular Synthesis of Quantum Dots

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-04-21 DOI: 10.1021/jacs.5c02861

Juan Kong, An-An Liu, Xia Xu, Bo Tang, Yan-Yan Chen, Wei Zhao, Jianhong Jia, Ling-Ling Yang, Gongyu Li, Dai-Wen Pang

{"title":"Making Cells as a “Nirvana Phoenix”: Precise Coupling of Precursors Prior to ROS Bursts for Intracellular Synthesis of Quantum Dots","authors":"Juan Kong, An-An Liu, Xia Xu, Bo Tang, Yan-Yan Chen, Wei Zhao, Jianhong Jia, Ling-Ling Yang, Gongyu Li, Dai-Wen Pang","doi":"10.1021/jacs.5c02861","DOIUrl":"https://doi.org/10.1021/jacs.5c02861","url":null,"abstract":"Rationally coupling natural biochemical reactions for live-cell synthesis of inorganic nanocrystals with fluorescence, such as quantum dots (QDs) especially near-infrared (NIR), holds significant potential for in situ labeling and bioimaging. However, the introduced exogenous reactants and intracellularly produced species, e.g., reactive oxygen species (ROS), often cause cell damage, decreasing the fluorescence of the QDs. Herein, we have found that cell-adaptable selenocystine ((Cys-Se)2) can be reduced to biocompatible low-valence Se precursors, which could be subsequently hijacked by timely added Ag-glutathione (AgSG) to be transformed into NIR Ag2Se QDs. Such a comprehensive control strategy can inhibit the production of cytotoxic Se species and ROS bursts, significantly increasing the cell viability from 4 to 80% and enhancing the fluorescence of intracellularly synthesized Ag2Se QDs by over 8.7 times. Notably, the proliferative and in vivo tumorigenic capacities of the cells with strong NIR fluorescence-emitting functions could be maintained, enabling long-term tracking of cell division and disease progression. This work has provided new insights into fully excavating the potential of cells for the synthesis of inorganic nanocrystals by designing biocompatible precursors and also opened a new window for conventional synthetic biology from organic to inorganic.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"62 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858155","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Proton-Modulated Nickel Hydride Electrocatalysis for the Hydrogenation of Unsaturated Bonds and Olefin Isomerization

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-04-21 DOI: 10.1021/jacs.5c03821

Xue Song, Yuan-Qiong Huang, Bodi Zhao, Hanshuo Wu, Xiaotian Qi, Jianchun Wang

{"title":"Proton-Modulated Nickel Hydride Electrocatalysis for the Hydrogenation of Unsaturated Bonds and Olefin Isomerization","authors":"Xue Song, Yuan-Qiong Huang, Bodi Zhao, Hanshuo Wu, Xiaotian Qi, Jianchun Wang","doi":"10.1021/jacs.5c03821","DOIUrl":"https://doi.org/10.1021/jacs.5c03821","url":null,"abstract":"Transition-metal hydrides stand as indispensable intermediates in both energy conversion and organic synthesis. Their electrochemical generation represents a compelling sustainable approach, enabling precise control over the reactivity and expanding the scope of electrocatalytic hydrogenation and isomerization. However, a major challenge in Ni-catalyzed electrochemical hydrogenation is the competing hydrogen evolution reaction (HER), which has led to various innovative strategies aimed at circumventing Ni–H formation. Here, we pursued an alternative approach by designing a bifunctional ligand with a pendant amine moiety to promote Ni–H formation. This design enabled selective (semi)hydrogenation of a diverse range of substrates, including terminal and internal alkynes, alkenes, and aldehydes, achieving an unprecedented substrate scope. Remarkably, we also demonstrated tunable positional selectivity for olefin isomerization by employing different types of proton sources. Our hydrogenation and isomerization method also exhibits excellent functional group tolerance, streamlining access to pharmaceuticals and their derivatives. Computational studies revealed the crucial, noninnocent role of the proton source in modulating metal hydride selectivity, either through hydrogen bonding, direct protonation of the pendant amine, or facilitation of protodemetalation.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"7 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858160","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Singlet Carbenes Are Stereoinductive Main Group Ambiphiles

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-04-21 DOI: 10.1021/jacs.5c03845

Jan Lorkowski, Patrick Yorkgitis, Fanny Morvan, Jennifer Morvan, Nicolas Vanthuyne, Thierry Roisnel, Milan Gembicky, Guy Bertrand, Marc Mauduit, Rodolphe Jazzar

引用次数: 0