Journal of the American Chemical Society最新文献

{"title":"Correction to \"Determination of Uranium Central-Field Covalency with 3<i>d</i>4<i>f</i> Resonant Inelastic X-ray Scattering\".","authors":"Timothy G Burrow, Nathan M Alcock, Myron S Huzan, Maja A Dunstan, John A Seed, Blanka Detlefs, Pieter Glatzel, Myrtille O J Y Hunault, Jesper Bendix, Kasper S Pedersen, Michael L Baker","doi":"10.1021/jacs.5c14044","DOIUrl":"https://doi.org/10.1021/jacs.5c14044","url":null,"abstract":"","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145205075","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":"Transitory Topochemical Tailoring of a van der Waals Superconductor.","authors":"Xiaoyu Song,Ziyu Liu,Eric F Seewald,Asish K Kundu,Daniel Muñoz-Segovia,Myung-Geun Han,Scott R Docherty,Daniel G Chica,Julian P Ingham,Jiayi Li,Junsik Mun,Madisen Holbrook,Qifeng Jiang,Jordan Cox,Jeffrey McNeill,Yimei Zhu,Colin Nuckolls,Andrew J Millis,Elio Vescovo,Raquel Queiroz,Cory R Dean,Abhay N Pasupathy,Xavier Roy","doi":"10.1021/jacs.5c14254","DOIUrl":"https://doi.org/10.1021/jacs.5c14254","url":null,"abstract":"Topochemical intercalation is widely used to access metastable phases with novel electronic properties, but the reverse reaction (deintercalation) typically restores the original state, limiting practical use. Here, we present a topochemical approach that employs a sacrificial intercalant that thermally decomposes to irreversibly lock in the new electronic state. Using 2-aminobutane as the sacrificial intercalant, we convert the van der Waals (vdW) material 1T-TiSe2 into a superconductor and the vdW superconductor 2H-NbSe2 into a nonsuperconducting metal, while preserving the ability to exfoliate the resulting crystals. We find that this transitory intercalation increases the electron density in both materials and partially suppresses the CDW in TiSe2. By tuning the thermolysis temperature, we can systematically vary the carrier density in TiSe2, enabling us to map its phase diagram. The superconductivity in TiSe2 is retained in exfoliated flakes, although with a lower critical temperature. This transitory topochemical strategy enables access to new electronic states with precisely tuned carrier densities that are otherwise inaccessible through direct solid-state synthesis.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"255 7 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194693","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 β-C-H Arylation of α-Fluoroalkyl Cyclopropane and Cyclobutane Carboxylic Acids.","authors":"D Quang Phan, Jin-Quan Yu","doi":"10.1021/jacs.5c13423","DOIUrl":"https://doi.org/10.1021/jacs.5c13423","url":null,"abstract":"<p><p>Fluoroalkyl-substituted small-membered rings are highly valuable scaffolds in drug discovery; nevertheless, there exists no general method to prepare them enantioselectively. Herein, we report a highly enantioselective β-C-H arylation of simple and readily available α-fluoroalkyl cyclopropane and cyclobutane carboxylic acids via C-H activation. This transformation enabled by chiral monoprotected-<i>N</i>-amino sulfonamide (MPASA) ligand is compatible with a broad range of aryl iodides, affording an efficient route to diverse small-membered rings with all-carbon quaternary centers bearing fluoroalkyls, which have been difficult to access to date. The synthetic utility of the arylation product was demonstrated by converting the carboxylic acid into alcohol and amine, which may be used to prepare new analogues of bioactive compounds. Preliminary mechanistic studies were also conducted, giving initial insights into catalyst speciation and the stability of this reaction.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145205045","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 Condensation-Inspired Assembly of DNA Nanotubes into Reversible Superstructures: A Base Pairing-Orthogonal Way to Create Rings, Bundles, or Vast Networks.","authors":"Laura Bourdon, Xiang Zhen Xu, Laurent J Michot, Mathieu Morel, Sergii Rudiuk, Ayako Yamada, Damien Baigl","doi":"10.1021/jacs.5c10921","DOIUrl":"https://doi.org/10.1021/jacs.5c10921","url":null,"abstract":"<p><p>By offering exquisite programmability, sequence-specific DNA self-assembly is the foundation of structural DNA nanotechnology but necessitates custom-designed DNA strands. Finding assembly principles orthogonal to base pairing is thus desirable not only to organize DNA in a sequence-independent manner but also to bring additional levels of control over preformed DNA self-assembled structures. Here, we report that self-assembled DNA nanotubes, upon the addition of DNA-condensing multivalent cations, including the naturally occurring polyamines spermidine and spermine, spontaneously condense to form higher-order structures including well-defined micrometer-sized rings and 30 to 60 nm wide bundles, in which DNA strands are parallelly packed with an interspacing ranging from 2.5 to 3 nm. In the semidilute regime, a new organization into vast tridimensional networks is observed for a specific range of charge ratios, prior to the formation of highly clustered bundles. We demonstrate that the process is electrostatically driven, conferring a ubiquitous character to this assembly principle. We report in particular a pivotal role of the counterion valency (the higher it is, the lower the charge ratio required), emphasizing the role of DNA neutralization through the entropically driven exchange between DNA counterions and the condensing agents. We also show an important role of DNA concentration for controlling the individual or interconnected nature of the formed structures as well as favoring the nanotube assembly. We finally devise methods for additional control, such as superstructure disassembly upon monovalent ion addition or photocontrol using a photosensitive DNA-condensing agent.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145205060","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":"Chemically Induced Ferroic-like Phase and Collective Chemotaxis in an Active Swarm.","authors":"Changjin Wu,Yaxin Huang,Binglin Zeng,Jingyuan Chen,Chun Hung Chu,Mingcheng Yang,Ho Cheung Shum,Jinyao Tang","doi":"10.1021/jacs.5c10021","DOIUrl":"https://doi.org/10.1021/jacs.5c10021","url":null,"abstract":"Amplification of weak chemical signals through intracellular cascade networks is crucial for long-range cohesive migration in biological processes, such as embryogenesis and cancer metastasis. While this capability has transformative potential for synthetic systems in precision medicine and adaptive materials, the lack of cascade communication in artificial matter has been a significant barrier. This study demonstrates that a binary active colloid mixture, mediated by a chemical reaction, forms a simple chemical reaction network capable of self-organizing into polarized dynamic swarms, dramatically enhancing chemical amplification. By applying the classical Ising model, we rationalize the self-polarization with increasing chemical activity, drawing an analogy to ferroic materials in the chemically polarized active phase. Under optimal conditions, these \"ferrochemical\" swarms can amplify weak chemical gradients by over 104 times, resulting in exceptional chemical sensitivity and remarkable long-range collective chemotaxis. As a proof of concept, we demonstrate the application of silver-doped active swarms to enhance antibacterial efficacy, showcasing a chemotactic swarm that effectively combats dental biofilm growth on human teeth.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"6 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194745","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":"Unravelling the Influence of the Local Structure on the Ultralow Thermal Conductivity of the Bismuthinite-Aikinite Series, Cu_1-<i>x</i>□_<i>x</i>Pb_1-<i>x</i>Bi_1+<i>x</i>S₃.","authors":"Paz Vaqueiro, Anna Herlihy, Mahmoud Elgaml, Shriparna Mukherjee, David A Keen, David J Voneshen, Anthony V Powell","doi":"10.1021/jacs.5c12526","DOIUrl":"https://doi.org/10.1021/jacs.5c12526","url":null,"abstract":"<p><p>Understanding the relationship between crystal structure, bonding and thermal transport is critical for the discovery of materials with ultralow thermal conductivities. Materials in the bismuthinite-aikinite series, Cu_1-<i>x</i>□_<i>x</i>Pb_1-<i>x</i>Bi_1+<i>x</i>S₃ (0 ≤ <i>x</i> ≤ 1), in which a Bi³⁺ cation and a vacancy (□) are progressively substituted by a Pb²⁺ and a Cu⁺ cation, exhibit ultralow thermal conductivities (∼0.5 W m^-1K^-1 for <i>x</i> < 1). Here, we investigate the effect of decreasing the Pb²⁺ and Cu⁺ content on the crystal structure and properties of Cu_1-<i>x</i>□_<i>x</i>Pb_1-<i>x</i>Bi_1+<i>x</i>S₃ (<i>x</i> = 0, 0.33, 0.6 and 0.83). These materials exhibit two-channel thermal transport, with non-propagating phonons being the dominant contribution. Neutron diffraction data reveal that intermediate compositions crystallize in the krupkaite structure (<i>x</i> = 0.5, <i>P</i>2₁<i>ma</i>), instead of the end-member aikinite structure (<i>x</i> = 0, <i>Pnma</i>). Pair distribution function (PDF) analysis reveals that the disordering of vacancies and cations deviates significantly from that expected for a statistical distribution and that, at a local level, copper-rich and copper-poor regions occur. Reducing the Pb²⁺ and Cu⁺ content results in lattice softening, which may be attributed to the increased concentration of vacancies in copper-poor regions. Moreover, the persistence of short Pb²⁺-Cu⁺ distances in the copper-rich regions is likely to facilitate the cooperative interaction between lone pairs and rattling Cu⁺ cations that leads to phonon scattering. These findings provide crucial insights into the effect of the local structure on the phonon transport and highlight the potential of local-structure design to achieve high thermoelectric performance in crystalline solids.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145205083","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":"Dual Proton-Electron Conductivity in 2D Azaborine Metal-Organic Frameworks.","authors":"Alice Y Su,Julius J Oppenheim,Mircea Dincă","doi":"10.1021/jacs.5c13331","DOIUrl":"https://doi.org/10.1021/jacs.5c13331","url":null,"abstract":"Dual proton-electron conductors are highly sought after for applications in electronics and energy storage. Whereas two-dimensional metal-organic frameworks (MOFs) (2D MOFs) with high electrical conductivity are now numerous, introducing conduits for ion transport in these is challenging. Herein, we report the synthesis of two new mixed electron-proton conductors, M3TABC2 (M = Cu, Zn; TABC = hexahydroxy-1,5,9-triaza-2,6,10-trihydroxyboracoronene), made from a new conjugated azaborine ligand with mobile protons. Cu3TABC2 and Zn3TABC2 show high electronic conductivities of 6.0 × 10-2 S/cm and 2.2 × 10-4 S/cm, and ionic conductivities of 1.6 ± 0.1 × 10-5 S/cm and 1.9 ± 0.4 × 10-5 S/cm, respectively. Overall, this work demonstrates the incorporation of mobile protons into aromatic ligands as a strategy for enabling mixed conductivity in 2D MOFs.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"16 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189358","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":"Overriding Norrish Type II to Access Cyclopropanols.","authors":"James W Pearson, Samantha L Dudra, Anthony F Palermo, Benjamin S Y Chiu, Julie Dang, Alexis L Gabbey, Bridget A B Henson, Teh Ren Hou, Negin Nabavi, Sophie A L Rousseaux","doi":"10.1021/jacs.5c13001","DOIUrl":"https://doi.org/10.1021/jacs.5c13001","url":null,"abstract":"<p><p>The propensity for photoexcited aryl ketones to undergo 1,5-hydrogen atom transfer (HAT) reactions is a fundamental process in organic synthesis and polymer degradation. Since its discovery in 1958, Norrish-Yang photocyclization has become a prominent method to access cyclobutanols under mild photoirradiative conditions. Despite its successful extension to larger ring systems, access to medicinally relevant 3-membered rings remains limited due to the strong kinetic preference for 1,5-HAT over 1,4-HAT. In this work, we demonstrate the first photocyclization of β-boryl aryl ketones to cyclopropanols. Our strategy relies on solvent-controlled selective population of the π,π* triplet state over the n,π* triplet state, with the former preferentially undergoing 1,4-boryl group transfer over 1,5-HAT. This protocol proceeds under mild irradiative conditions with excellent functional group tolerance, providing access to a broad range of highly valuable cyclopropanol scaffolds.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145190406","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":"Dipole-Induced Inversion of Spin-Dependent Charge Transport through α-Helical Peptide-Based Single-Molecule Junctions.","authors":"Albert C Aragonès,Monica Varese,Kavita Garg,Wenzhu Kuang,Qiankun Wang,Ernest Giralt,Vladimiro Mujica,Rafael Gutierrez,Gianaurelio Cuniberti,Luis Puerta,Ismael Díez-Pérez","doi":"10.1021/jacs.5c10892","DOIUrl":"https://doi.org/10.1021/jacs.5c10892","url":null,"abstract":"We report on a remarkable phenomenon of interfacial electric dipole inversion coupled to changes in atomic spin densities that translates into the enantiomeric inversion of electron spin-dependent conductance in a 2-terminal single-molecule junction, consisting of a 22 amino acid chiral α-helical peptide sequence connecting two metal electrodes. This phenomenon is conventionally associated with the Chirality-Induced Spin Selectivity (CISS) effect and how it induces spin polarization and spin filtering of the electron transport along the main peptide axis. Here, the inversion of the spin-dependent charge transport behavior is achieved by keeping constant the chiral symmetry of the junction while inverting the direction of the internal electrical dipole moment running along the main helical peptide axis. Using a spinterface model, in which the electrode-molecule injection barriers are dependent both on the electric dipole and magnetic spin moment, we have been able to rationalize the current pattern as arising from a surface dipole inversion and changes in the atomic spin densities in atoms located within the peptide backbone. Both experimental and computational results show that the observed electric dipole-induced spin-dependent transport inversion in the chiral peptide junction links to an inversion in the spin-dependent resistance due to the combined effect of the helical-based CISS effect and the electrode/molecule spinterface.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"6 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189359","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":"Postsynthetic Triazolate Functionalization of Ni₂Cl₂BTDD: Creation of Supplementary CO₂ Adsorption Sites and Exceptional CO₂ Selectivity.","authors":"Ju Hyoung Kim, Hongryeol Yun, Chan Gu Kim, Namju Kim, Yurim Yang, Saeeun Yoo, Dohyun Moon, Dongwon Kim, Chang Seop Hong","doi":"10.1021/jacs.5c13450","DOIUrl":"https://doi.org/10.1021/jacs.5c13450","url":null,"abstract":"<p><p>Postsynthetic modification (PSM) offers a versatile approach to tune metal-organic frameworks (MOFs) by introducing functional groups or exchanging bridging ligands while preserving open metal sites (OMSs). Nevertheless, generating additional adsorption sites via PSM remains challenging. Herein, we report a new PSM strategy that creates supplementary sorption sites within a robust MOF framework. We synthesized triazolate-exchanged Ni₂(triazolates)<i>_x</i>Cl_2-<i>x</i>BTDD (BTDD = bis(1H-1,2,3-triazolo[4,5-<i>b</i>],[4',5'-i])dibenzo[1,4]dioxin), where bridging chlorides in the parent Ni₂Cl₂BTDD were successfully replaced with triazolate ligands. Rietveld refinement of synchrotron X-ray diffraction confirmed that triazolates bridge adjacent Ni(II) centers through 1,2-nitrogen atoms without obstructing the OMSs. This structural modification substantially enhanced CO₂ adsorption owing to newly formed binding sites and cooperative interactions between triazolate moieties and BTDDs. Among the modified frameworks, Ni_dmtz incorporating 3,5-dimethyl-1,2,4-triazolate (dmtz) showed a remarkable improvement: CO₂ uptake increased 5.2-fold at 0.15 bar and 2.6-fold at 1 bar compared to the parent framework, while also displaying enhanced stability under humid conditions. Notably, the Ideal Adsorbed Solution Theory (IAST) selectivity for CO₂/N₂ (15/85 v/v) reached 456,000, significantly surpassing most reported MOFs. Grand Canonical Monte Carlo simulations revealed the presence of a third adsorption site in Ni_dmtz, where CO₂ interacts with the methyl-substituted triazolate in addition to conventional ligand pocket sites. This study highlights a simple yet effective PSM approach to design multifunctional sorbents and provides valuable insights into the rational development of MOFs for efficient CO₂ capture.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145197509","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}