Chemical Science最新文献

{"title":"A chemo-selective deprotection–cyclization strategy enables fluorescent imaging of hydroxylamine and reveals its pathologic role in Parkinson’s disease","authors":"Shunping Zang, Jia Ke, Hanbing Zheng, Qing Liu, Yang Liu, Chaoyi Yao, Benhua Wang, Minhuan Lan, Xiangzhi Song","doi":"10.1039/d6sc01655c","DOIUrl":"https://doi.org/10.1039/d6sc01655c","url":null,"abstract":"Hydroxylamine (HA), a reactive nitrogen species generated by neuronal nitric oxide synthase (nNOS), has been largely overlooked in neurodegenerative disorders. Herein, we report the first identification of HA overexpression in Parkinson’s disease (PD) and elucidate its pathological role using chemo-selective fluorescence imaging combined with proteomic analysis. A general HA-responsive probe platform was developed by introducing a 1-(4,4-dimethyl-2,6-dioxacyclohexylidene)ethyl (Dde) unit as a highly specific HA-recognition motif. Among the resulting probes, DCI-HA-2 exhibited remarkable sensitivity, fast response, and excellent selectivity toward HA. Using DCI-HA-2, elevated HA levels were visualized in PD cells, PD model mice, and brain tissues for the first time. Mechanistically, nNOS-derived HA suppresses cystathionine β-synthase (CBS) expression, leading to impaired hydrogen sulfide (H2S) biosynthesis, and simultaneously induces adenosine-5’-triphosphate (ATP) depletion, thereby disrupting adenosine 5′-monophosphate-activated protein kinase (AMPK) signaling in PD pathology. This work identifies HA as a previously unrecognized pathological regulator in PD, and establishes a powerful chemical strategy for probing HA-associated pathological processes in complex biological systems.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"6 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147753514","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":"NH₄ ⁺-mediated interfacial chemistry for collaborative dual-pathway high-mass-loading energy storage.","authors":"Jinxin Wang, Wei Guo, Mingming Sun, Geng Zhang, Mengting Cheng, Wenbin Xie, Na Hu, Yuehan Yang, Qiuyu Zhang","doi":"10.1039/d6sc02038k","DOIUrl":"https://doi.org/10.1039/d6sc02038k","url":null,"abstract":"<p><p>The deposition/dissolution mechanism of MnO₂ with two-electron transfer is promising for high-energy aqueous energy storage. However, this reaction is severely limited by the kinetically unfavorable dissolution step, a challenge that is greatly exacerbated as the deposit thickens. Herein, by refining NH₄ ⁺-mediated interface chemistry, we achieve the precise configuration of MnO₂ with controlled hydroxylation, which guides the reversible MnO₂/Mn²⁺ conversion under high-mass-loading conditions. The partially hydroxylated surface further creates a kinetically favorable microenvironment for NH₄ ⁺ storage, ultimately leading to energetic dual-pathway storage behaviors. This enables a remarkable areal capacitance of 13.8 F cm^-2 and sound cycling stability over 6000 cycles under high-mass-loading conditions (27.1 mg cm^-2). Theoretical calculations reveal that the controlled partial hydroxylation of MnO₂ promotes electronic conduction and lowers the adsorption energy of NH₄ ⁺, outperforming both highly hydroxylated and pure MnO₂. The adsorbed NH₄ ⁺ delivers intimate interfacial electronic interaction with partially hydroxylated MnO₂ to trigger local charge redistribution, substantially lowering the MnO₂/Mn²⁺ conversion energy barrier of the nonspontaneous rate-determining step at the NH₄ ⁺-proximal site. Our findings highlight the significance of the interfacial microenvironment governing the collaborative dual-pathway storage chemistry, which provides guidance for boosting high-mass-loading energy storage.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13123726/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147763918","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis, Characterization, and Imidogen Photochemistry of a Hydrazoic Acid Adduct of Rh2","authors":"Arpan Paikar, Phong Thai, Matthew T Figgins, Bodhisattwa Mandal, Matthew Lekas, Joseph Reibenspies, Gerard Van Trieste, David Charles Powers","doi":"10.1039/d6sc02258h","DOIUrl":"https://doi.org/10.1039/d6sc02258h","url":null,"abstract":"Metal-imidogen (i.e., M-NH) intermediates are proposed in metal-catalyzed NH-transfer reactions. Transition metal complexes of hydrazoic acid (HN3) could serve as precursors to these transient intermediates; however, the coordination chemistry of HN3 is essentially unknown. Here, we report the synthesis and characterization of Rh2(esp)2(HN3)2, the first crystalline transition metal complex of HN3 (esp = α,α,αʹ,αʹ-tetramethyl-1,3-benzenedipropionate). Temperature-dependent multi-nuclear NMR, UV-vis, and IR spectroscopies demonstrate that HN3 is a weakly coordinating ligand (Keq = 1100 ± 100 M - 2 at 243 K). Cryogenic photolysis (77 K) enabled observation of a non-steady state intermediate, which we assign to be a triplet Rh2-NH complex, that engages in olefin aziridination chemistry. The nitrene photochemistry of Rh2(esp)2(HN3)2 was corroborated by in crystallo synthesis and cryogenic spectroscopic characterization of a family of N-aryl nitrene complexes. Together, these results establish the coordination chemistry of HN3, confirm the triplet ground state of the Rh2-NH intermediate responsible for catalytic NH transfer, and demonstrate a photochemical platform to observe intermediates in NH-transfer catalysis.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"427 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147755279","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 the Radical Polarity Matching Principle: Selective Chlorohydroxylation of Electron-Deficient Alkenes Enabled by Ce Photocatalysis","authors":"Luchuan Ou, Yihang Bai, Shanshuo Liu, Zongling Kan, Yu Lan, Jiali Zhu, Shihan Liu, Zhigang Ren, Shi-Jun Li, Linbin Niu","doi":"10.1039/d6sc00166a","DOIUrl":"https://doi.org/10.1039/d6sc00166a","url":null,"abstract":"Radical addition to alkenes generally follows the polarity matching principle; for instance, the electrophilic chlorine radical favors electron-rich double bonds over electron-deficient ones in alkenes. Herein, we achieve a one-step selective aerobic chlorohydroxylation of alkenes via Ce-LMCT-generated chlorine radicals. The protocol exhibits a broad substrate scope, notably extending to electron-deficient, amide-containing alkenes—a class of substrates historically challenging for the addition of electrophilic radicals due to the polarity matching principle. Theoretical calculations reveal that the radical adduct generated from the chlorine radical and amide-containing alkene is stabilized by the amide group, which helps the system to override the radical polarity matching principle.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"29 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147753512","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":"Excimer-mediated multiexciton generation in covalently linked cross foldamers of thiophene-fused perylene bisimides","authors":"Weicong Li, Wei Zhang, Jiadong Zhou, Linlin Liu, Hongwei Song, Zengqi Xie","doi":"10.1039/d6sc00414h","DOIUrl":"https://doi.org/10.1039/d6sc00414h","url":null,"abstract":"Singlet fission (SF) is a promising strategy to surpass the Shockley–Queisser limit in organic photovoltaics, but the structural and electronic determinants controlling excimer-mediated multiexciton (ME) generation remain insufficiently understood. Herein, we designed two covalently linked cross foldamers, <strong>CF(4)</strong> and <strong>CF(7)</strong>, based on thiophene-fused perylene bisimide units, with controlled intramolecular chromophore rotational angles (88° and 55°) <em>via</em> alkyl chain engineering, while maintaining a constant π–π stacking distance. Steady-state and ultrafast spectroscopy studies revealed that both foldamers undergo excimer-mediated ME generation but with distinct dynamics: weakly coupled <strong>CF(4)</strong> (88°) achieves rapid ME formation in 27 ps, whereas strongly coupled <strong>CF(7)</strong> (55°) stabilizes the excimer, slowing ME formation to 114 ps. These results establish a clear structure–dynamics relationship, demonstrating that rotational angle modulation enables tuning of excimer energetics and SF efficiency, providing a general design strategy for π-conjugated assemblies.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147753518","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":"Traceless protein semisynthesis in cells using the promiscuous ultra-fast split intein NrdJ-1.","authors":"Xuanjia Ye, Joshua Sokol, Christian Kofoed, Anushka Dheer, Juner Zhang, Tom W Muir","doi":"10.1039/d6sc01808d","DOIUrl":"10.1039/d6sc01808d","url":null,"abstract":"<p><p>Chemistry-driven approaches that allow proteins to be manipulated in ways not permitted by standard genetics are indispensable in the basic and applied biomedical sciences. Of the various platform technologies in common use, those that exploit intein-mediated protein splicing have proven especially powerful owing to compatibility with both <i>in vitro</i> and <i>in vivo</i> applications. Here, we provide detailed biochemical characterization of the split intein, NrdJ-1. We demonstrate that the rapid splicing kinetics associated with this system are largely independent of splice junction primary sequence context. The promiscuity and high efficiency of this split intein makes it well suited to the generation of chemically modified proteins <i>in vitro</i> and in living cells, as demonstrated by the traceless generation of semisynthetic chromatin harboring various post-translational modifications. These studies highlight the utility of NrdJ-1 for traceless protein editing and suggest it is a superior choice for many intracellular biochemical applications.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13123727/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147763899","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Organic Small Molecule Catalyzed Carbonylation Reactions","authors":"Mao-Lin Yang, Le-Cheng Wang, hefei yang, Jiajun Zhang, Xiao-Feng Wu","doi":"10.1039/d6sc02732f","DOIUrl":"https://doi.org/10.1039/d6sc02732f","url":null,"abstract":"C1 chemistry is important from both academia research and industrial application which are extensively studied with metal catalysts. Considering the advantages of organic small molecule catalysts, it's super attractive to explore them as catalyst in carbonylation chemistry. This Review examines organic small molecule catalyzed carbonylation from advanced catalysis perspective, with particular emphasis on N-heterocyclic carbene (NHC) catalysis, oxygen, sulfur, selenium, nitrogen and phosphines main-group species-based catalysts further expand the conceptual and synthetic landscape of sustainable carbonylation. These advances define carbonylation as a catalyst designed reaction class and highlight opportunities for future organic small molecule driven development.Carbonylation reactions constitute a powerful toolbox in modern synthetic chemistry because they provide a direct and atom-economic entry to carbonyl functionalities that permeate pharmaceuticals, natural products, agrochemicals and functional materials 1 . According to FDA statistics from 2015 to 2020, approximately 80% of approved drugs contain carbonyl functional groups (Fig 1 .1a) 2 . For example, the widely prescribed anticoagulant Eliquis (ranked second in 2024 retail drug sales for thrombosis prevention) and the anti-myeloma agent Revlimid (ranked 28th) each contain three or more carbonyl groups and achieved market values of $20.699 billion and $5.809 billion, respectively 3 . In synthetic chemistry, carbonylation technologies are among the most efficient and atom-economical methods for constructing carbonyl compounds 4-8 : these processes convert carbon monoxide (CO)-derived from coal, natural gas or biomass-into value-added carbonylated products with essentially 100% atom utilization 9 . CO is thus recognized as an abundant, cost-effective and versatile C1 feedstock in carbonylation chemistry. A canonical industrial example is the methanol carbonylation to acetic acid embodied by the Monsanto and Cativa processes, which together underpin the production of a substantial fraction of the world's acetic acid 10,11 .1) Advanced Carbonylation Process and the Value of Carbonyl-Containing Motifs80% 20%","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"27 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147753517","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":"Regioselective synthesis of aza-saccharins via anionic [1,4] Fries-type rearrangement of aryl sulfonimidoyl fluorides","authors":"Mario Leypold, Lorenzo Poli, Max Earl, Okky D. Putra, Karolina Kwapien, Richard J. Lewis, John J. Murphy, Marta Passamonti, Lena M. von Sydow, Victor Spelling, Ioannis Asproudis, Malvika Sardana, Claudia Gatti, Hikaru Seki, Thomas Lemaitre, Radvile Juskaite, Ranganath Gopalakrishnan, Stuart J. Francis, Cristina Gardelli, Per-Ola Norrby, Werngard Czechtizky","doi":"10.1039/d6sc00432f","DOIUrl":"https://doi.org/10.1039/d6sc00432f","url":null,"abstract":"A regioselective synthesis of aromatic and aliphatic aza-saccharins as cyclic sulfonimidamide derivatives is reported, starting from easily accessible aryl sulfonimidoyl fluorides and primary or secondary amines with broad functional group tolerance. The transformation is enabled by electron-withdrawing substituents and proceeds through an anionic [1,4] Fries-type rearrangement at cryogenic temperature, initiated by KHMDS-mediated <em>ortho</em>-deprotonation and rapid carbonyl migration. Mechanistic investigations indicate the formation of aryl sulfonimidoyl fluoridate anions, a distinct and previously unexplored motif in S(<small>VI</small>) and SuFEx chemistry. The involvement of these low-temperature-persistent intermediates is supported by cryogenic <small>¹⁹</small>F/<small>¹⁵</small>N NMR studies of a <small>¹⁵</small><em>N</em>-labeled substrate, interception by acylation to give a stable adduct whose structure was confirmed by X-ray diffraction, and complementary DFT calculations indicating that the fluoridate anion is a viable low-energy intermediate. Regioselectivity follows predictable electronics-driven trends governed by <em>meta</em>-substituents, while selective aza-saccharin formation can be modulated by base choice and reagent addition order. Notably, the fluoridate anions are configurationally stable at sulfur, as demonstrated in a representative example, and subsequent amination <em>via in situ</em> SuFEx capture proceeds stereospecifically with inversion at sulfur. This synthetic method provides a mechanistically defined and stereocontrolled entry to chiral aza-saccharins with potential relevance to medicinal chemistry, agrochemical discovery and related disciplines.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"153 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147753511","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":"Layered oxide cathodes for sodium-ion batteries: origins of microcracks and countermeasures","authors":"Qiang Ma, Ling-Yi Kong, Bang-Yuan Guo, Qi-Lin Ran, Ya-Fang Wang, Yan-Fang Zhu, Yao Xiao","doi":"10.1039/d6sc02126c","DOIUrl":"https://doi.org/10.1039/d6sc02126c","url":null,"abstract":"Layered transition metal oxide cathodes (Na<small>_<em>x</em></small>TMO<small>₂</small>) for sodium ion batteries have stood out among various cathode materials owing to their advantages in cost and electrochemical performance. However, their further practical application is hindered by deep-seated structural degradation, interfacial instability, and poor air stability. Among these issues, microcracks serving as a critical bridge between intrinsic defects in Na<small>_<em>x</em></small>TMO<small>₂</small> and macroscopic performance decay have emerged as a central focus of current research. Accordingly, this review systematically summarizes the origins of microcrack formation in Na<small>_<em>x</em></small>TMO<small>₂</small> and the corresponding mitigation strategies. The influence of primary structural defects introduced during material synthesis is first examined. Subsequently, the structural and chemical roots of microcrack formation during electrochemical processes are elucidated. Finally, crack formation pathways induced by environmental factors and interfacial evolution, particularly those associated with air exposure and cathode–electrolyte interfaces, are discussed. Building on these mechanistic insights, we critically compare current suppression strategies, including electronic structure regulation, lattice strain engineering, and interfacial engineering. The failure mechanisms and mitigation approaches related to microcracks summarized in this review are expected to contribute to the overall performance enhancement of Na<small>_<em>x</em></small>TMO<small>₂</small> and to provide important guidance for their industrial application in sodium-ion batteries.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"54 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147753515","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":"Anion-sublattice engineering of Li3PS4:Br and I incorporation enhances ionic conductivity and Li-metal compatibility","authors":"Tej P. Poudel, Michael J. Deck, Ifeoluwa P. Oyekunle, Pawan K. Ojha, Bright O. Ogbolu, Islamiyat Ojelade, Thilina N. D. D. Gamaralagale, Erica Truong, Yongkang Jin, Amirhossein Zareihassangheshlaghi, Yan-Yan Hu","doi":"10.1039/d6sc00740f","DOIUrl":"https://doi.org/10.1039/d6sc00740f","url":null,"abstract":"All-solid-state batteries (ASSBs) are promising to enhance the safety and energy density of rechargeable batteries. Li<small>₃</small>PS<small>₄</small> remains one of the most viable solid electrolytes (SEs) for all-solid-state lithium batteries. However, its low ionic conductivity and poor stability limit its commercial use. In this work, we introduce lithium bromide (LiBr) and lithium iodide (LiI) into the anionic sublattice of Li<small>₃</small>PS<small>₄</small> to induce local disorder. An eightfold increase in ionic conductivity to 4.36 mS cm<small>⁻¹</small> at 25 °C is achieved with the 2Li<small>₃</small>PS<small>₄</small>:LiBr:LiI composition. 2Li<small>₃</small>PS<small>₄</small>:LiBr:LiI also exhibits a high room temperature critical current density of 0.92 mA cm<small>⁻²</small> and improved electrochemical stability against lithium metal. The half-cell fabricated with 2Li<small>₃</small>PS<small>₄</small>:LiBr:LiI as the separator and TiS<small>₂</small> as the active cathode material shows significantly better rate and long-term cycling performance compared to cells based on Li<small>₃</small>PS<small>₄</small>. Solid-state NMR and Raman spectroscopy indicate the formation of bridging PS<small>₄</small><small>³⁻</small> tetrahedra facilitated by the incorporation of I<small>⁻</small> and Br<small>⁻</small>. This study further highlights the advantages of strategic halide incorporation in thiophosphate electrolytes to enhance the performance of Li<small>₃</small>PS<small>₄</small>-based SEs and, in turn, ASSBs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"26 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147751611","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}