Chemical Science最新文献

{"title":"Identification of a Photoredox-Active Pt(IV) Complex that Induces Light-Mediated Cell Death","authors":"Jevon Marsh, Lina Hacker, Sophie Alice Twigger, Jake Vickery, Shitong Huang, Claudia Almuzara Romero, Aaron Langston, Ismael Perez, Rebecca A Musgrave, Ester M Hammond, Adam Charles Sedgwick","doi":"10.1039/d5sc02879e","DOIUrl":"https://doi.org/10.1039/d5sc02879e","url":null,"abstract":"We report the synthesis and characterisation of a series of fluorogenic Pt(IV) complexes - CarboBlue, OxaliBlue and CisBlue. These Pt(IV) complexes were identified as photoactive, oxidising biomolecules under light irradation to then undergo rapid intramolecular photoreduction to release the fluorescent reporter, Nap-OH and corresponding Pt(II) species. OxaliBlue and CisBlue displayed cytotoxicity regardless of light irradiation. In contrast, HCT116 cells treated with CarboBlue displayed a light-dependent increase in fluorescence emission along with selective light-induced toxicity.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"56 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144924164","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":"Prediction of Enzyme function using interpretable optimized Ensemble learning framework","authors":"Saikat Dhibar, Sumon Basak, Biman Jana","doi":"10.1039/d5sc04513d","DOIUrl":"https://doi.org/10.1039/d5sc04513d","url":null,"abstract":"Accurate prediction of enzyme function, particularly for newly discovered uncharacterized sequences, is immensely important for modern biology research. Recently machine learning (ML) based methods have shown promises. However, such tools often suffer from complexity in feature extraction, interpretability, and generalization ability. In this study, we construct the dataset for enzyme functions and present an interpretable ML method, SOLVE (Soft-Voting Optimized Learning for Versatile Enzymes) that addresses these issues by using only combination of tokenized subsequences from the protein's primary sequence for classification. SOLVE utilizes an ensemble learning framework integrating random forest (RF), light gradient boosting machine (LightGBM) and decision tree (DT) models with an optimized weighted strategy which enhances prediction accuracy, distinguishes enzymes from non-enzymes, and predicts enzyme commission (EC) numbers for mono- and multi-functional enzymes. The focal loss penalty in SOLVE effectively mitigates class imbalance, refining functional annotation accuracy. Additionally, SOLVE provides interpretability through Shapley analyses, identifying functional motifs at catalytic and allosteric sites of enzymes. By leveraging only primary sequence data, SOLVE streamlines high-throughput enzyme function prediction for functionally uncharacterized sequences and outperforms existing tools across all evaluation metrics on independent datasets. With high prediction accuracy and its identification ability of functional regions, SOLVE can become a promising tool in different fields of biology and therapeutic drug design.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"141 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144924165","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":"Engineering Ultrapotent Trivalent Anticoagulants Through Hybridisation of Salivary Peptides from Multiple Haematophagous Organisms","authors":"Joshua W C Maxwell, Jorge Ripoll-Rozada, Angus S Mackay, Imala Alwis, Daniel J. Ford, Cameron B. J. Trought, Joana A. Santos, Rhyll E. Smythe, Joanna S.T. Liu, Zack Zuccolotto, Simone M. Schoenwaelder, Shaun P. Jackson, Pedro José Barbosa Pereira, Richard James Payne","doi":"10.1039/d5sc04734j","DOIUrl":"https://doi.org/10.1039/d5sc04734j","url":null,"abstract":"Haematophagous organisms are a rich source of salivary anticoagulant polypeptides that exert their activity by blocking the catalytic site and one of two positively charged exosites on the host protease thrombin. Here, we describe a molecular engineering approach to hybridise post-translationally sulfated polypeptides from different blood-feeding organisms to enhance anticoagulant activity. This led to the discovery of a triply sulfated hybrid anticoagulant, XChimera, possessing fragments from flea, leech, and fly salivary polypeptides that exhibits femtomolar inhibitory activity against thrombin. The crystallographic structure of a complex of XChimera with thrombin shows that it displays a trivalent binding mode in which it simultaneously blocks three functional sites of the protease, the active site and exosites I and II. This trivalent chimera exhibited ultrapotent anticoagulant activity in a suite of in vitro clotting assays and was also shown to possess potent in vivo antithrombotic activity in a murine model of thrombosis.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"59 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144928287","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":"From the Laboratory to Space: Unveiling Isomeric Diversity of C5H2 in the Reaction of Tricarbon (C3, X1Σg+) with the Vinyl Radical (C2H3, X2A')","authors":"Iakov Medevedkov, Anatoliy A Nikolayev, Shane Joseph Goettl, Zhenghai Yang, Alexander Mebel, Ralf I. Kaiser","doi":"10.1039/d5sc04699h","DOIUrl":"https://doi.org/10.1039/d5sc04699h","url":null,"abstract":"By connecting laboratory kinetics with cosmic observables, this work highlights the critical role of reactions between highly reactive species in shaping the molecular inventory of the interstellar medium and opens new windows into the spectroscopically elusive corners of astrochemical complexity. The gas phase formation of distinct C<small>₅</small>H<small>₂</small> isomers is explored through the bimolecular reaction of tricarbon (C<small>₃</small>, X<small>¹</small>Σ<small>_g</small><small>⁺</small>) with the vinyl radical (C<small>₂</small>H<small>₃</small>, X<small>²</small>A′) at a collision energy of 44 ± 1 kJ mol<small>^–1</small> employing the crossed molecular beam technique augmented by electronic structure and Rice–Ramsperger–Kassel–Marcus (RRKM) calculations. This barrierless and exoergic reaction follows indirect dynamics and is initiated by the addition of tricarbon to the radical center of the vinyl radical forming a C<small>_s</small> symmetric doublet collisional complex (CCCCHCH<small>₂</small>). Subsequent low-barrier isomerization steps culminate in the resonantly stabilized 2,4-pentadiynyl-1 radical (CHCCCCH<small>₂</small>), which decomposes via atomic hydrogen loss. Statistical calculations identify linear, triplet pentadiynylidene (<strong>p2</strong>, X<small>³</small>Σ<small>_g</small><small>⁻</small>) as the dominant product, while singlet carbenes ethynyl­cyclo­propenylidene (<strong>p1</strong>, X<small>¹</small>A′), pentatetraenylidene (<strong>p3</strong>, X<small>¹</small>A<small>₁</small>), and ethynylpropadienylidene (<strong>p4</strong>, X<small>¹</small>A′) are formed with lower branching ratios. The least stable isomer, 2-cyclopropen-1-ylidenethenylidene (‘eiffelene’; <strong>p5</strong>, X<small>¹</small>A<small>₁</small>), remains thermodynamically feasible, but exhibits negligible branching ratios. Two isomers detected in TMC-1 to date (<strong>p1</strong> and <strong>p3</strong>) possess significant dipole moments making them amenable to radio telescopic observations, whereas linear pentadiynylidene (<strong>p2</strong>; D<small>_∞h</small>) is only traceable via infrared spectroscopy or through its cyanopentadiynylidene derivative (HCCCCCCN). This study highlights the isomer diversity accessed in the low temperature hydrocarbon chemistry of barrierless and exoergic bimolecular reactions involving two unstable, reactants in cold molecular clouds.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"24 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144924167","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":"Noncovalent Immobilization of Chiral Lewis Acids on Single-Walled Carbon Nanotubes as a Tool for Synthetic Organic Aquachemistry","authors":"Taku Kitanosono, Satoshi Tanaka, Dongxin Zhang, Tomoya Hisada, Yasuhiro Yamashita, Shu Kobayashi","doi":"10.1039/d5sc05390k","DOIUrl":"https://doi.org/10.1039/d5sc05390k","url":null,"abstract":"Polycyclic aromatic hydrocarbons (PAHs) were employed as anchoring tags to noncovalently immobilize Lewis acids onto single-walled carbon nanotubes (SWNTs). This heterogeneous system demonstrated remarkable performance in asymmetric catalysis, particularly in water devoid of organic solvents or surfactants, outperforming other carbonaceous π-materials in activity, stereoselectivity, and reusability. The use of large-diameter SWNTs modified with 4-fluorophenyl groups further enhanced catalytic activity. Notably, Sc(PyS)3-SWNT combined with a chiral modifier retained high performance without the covalent anchorage, even after multiple reuse cycles. No leaching of scandium or the chiral modifier was observed, consistent with TGA results, despite washing with solvents where the chiral modifier is highly soluble. XPS analysis demonstrated that among the supports examined, SWNTs exhibited the most significant electron donation to the Sc and S centers, underscoring the exceptional electronic interaction responsible for the stable immobilization. Despite its high surface area and adsorption capacity, activated carbon showed poor performance and significant leaching, suggesting that electron donation from SWNTs stabilizes flexible, solution-like conformations of the Lewis acid complex, mitigating the unavoidable attenuation of Lewis acidity more effectively than other supports. This strategy also mitigates deactivation risks posed by nucleophiles such as amines, thiols, and free N–H indoles, which typically displace chiral ligands. Thus, a robust, non-covalent immobilization platform has been established, capable of delivering high activity, selectivity, and durability even in water, which is traditionally challenging for Lewis acid catalysis. This approach offers a promising pathway toward more sustainable and environmentally conscious asymmetric synthesis.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144924160","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":"Sulfenate Anion Catalyzed Enantio- and Diastereoselective Aziridination","authors":"Youge Pu, Anthony M. Smaldone, Javier Adrio, Patrick J. Walsh","doi":"10.1039/d5sc05077d","DOIUrl":"https://doi.org/10.1039/d5sc05077d","url":null,"abstract":"The synthesis of enantioenriched aziridines is important for drug development due to their prevalence in bioactive molecules. Previous methods often use expensive catalysts, activated substrates, or show poor stereoselectivity. Herein, we report a novel organocatalytic approach using enantioenriched [2.2]paracyclophane (PCP)-based sulfenate anion catalysts, enabling the synthesis of 18 cyclopropanated aziridines from unactivated imines and commercially available benzyl chlorides in 50%–99% yields with 73%–99% ee and &gt;20:1 dr. This approach fills a gap in the existing methods for aziridine synthesis, facilitating the generation of cyclopropyl-substituted aziridines with high stereoselectivity under mild and transition metal-free reaction conditions.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"26 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144924163","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-entropy metal phosphide nanoparticles for accelerated lithium polysulfide conversion","authors":"Manchuan Guo, Jin Guo, Tao Ren, Haici Deng, Yanqiu Zhu, Jinliang Zhu","doi":"10.1039/d5sc04604a","DOIUrl":"https://doi.org/10.1039/d5sc04604a","url":null,"abstract":"To overcome the persistent challenges of sluggish lithium polysulfide (LiPS) conversion kinetics and the shuttle effect in Li–S batteries, this work introduces a novel, cost-effective thermal treatment strategy for synthesizing high-entropy metal phosphide catalysts using cation-bonded phosphate resins. For the first time, we successfully fabricated single-phase high-entropy Fe0.20Co0.62Ni0.14Cu0.23Mn0.38P nanoparticles anchored on a porous carbon network (HEP/C). The HEP/C demonstrates enhanced electronic conductivity and superior LiPS adsorption capability, substantially accelerating their redox kinetics. These catalytic improvements arise from (1) synergistic electronic modulation by the five constituent metals, which elevates d-band electron energy levels, and (2) lattice distortion induced by atomic radius mismatches, collectively generating a dense array of highly active catalytic sites. The HEP/C@S cathode delivers an ultrahigh initial specific capacity of 1402.18 mAh g−1 at 0.2C, outstanding cycling stability with merely 0.05% capacity decay per cycleover 1000 cycles at 5C, and a remarkable initial energy density of 455 Wh kg−1 in practical pouch cells. This work not only presents an efficient synthesis strategy for high-entropy materials but also provides fundamental insights into the design principles of advanced LiPS conversion catalysts for high-performance Li–S batteries.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"120 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144924166","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":"Light Them Up: Photoresponsive Imine-Containing Systems","authors":"Jiarong Wu, Jake L. Greenfield","doi":"10.1039/d5sc05210f","DOIUrl":"https://doi.org/10.1039/d5sc05210f","url":null,"abstract":"The reversible covalent bond formation that underpins dynamic covalent chemistry (DCC) enables the construction of stimuli-responsive systems and the efficient assembly of complex architectures. While most DCC studies have focused on systems at thermodynamic equilibrium, there is growing interest in systems that operate away from equilibrium—either by shifting to a new free-energy landscape in response to a stimulus, or by accessing an out-of-equilibrium state following an energy input. Imine-based systems are especially attractive due to the accessibility of their building blocks and their dynamic behaviour in both condensation and transimination reactions. These equilibria can be perturbed by chemical stimuli or light. While many modular systems combining imines with separate photoswitches have been studied in the context of light-responsive DCC, only recently have imine-based photoswitches—where light responsiveness is built directly into the dynamic covalent bond—emerged as a distinct strategy. In this Perspective, we compare representative examples of both approaches, outline their respective strengths, and discuss key challenges and opportunities for advancing light-driven, out-of-equilibrium imine systems.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"12 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144924168","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":"Single-Atom Catalysts Meet Electrospinning: A Blissful Marriage for Energy Catalysis","authors":"Bingyan Shi, Xiaofeng Lu","doi":"10.1039/d5sc03248b","DOIUrl":"https://doi.org/10.1039/d5sc03248b","url":null,"abstract":"Since the introduction of the concept of single-atom (SA) catalysis, numerous SA catalysts (SACs) with exceptional catalytic performance have been developed. Electrospinning represents a powerful technique for fabricating nanofibrous materials, characterized by high porosity, distinct electron/mass transfer property, self-supporting capability, and low density. Consequently, integrating SACs with electrospun nanofibers (ENFs) harnesses their structural advantages, thereby augmenting catalytic efficacy. This review examines the concept of SA-ENFs, underscoring the synergy between the nano-sized support architecture and atomic-level catalysts, which collectively offer abundant catalytic active sites. Furthermore, the well-defined spatial arrangement of nanofibers combined with highly efficient SAs imparts unique electron transfer and electrolyte transport capabilities, thereby promoting the catalytic performance. Herein, a detailed understanding of the influence of the coordination environment, and the interactions between multiple active sites within ENFs on the electrocatalytic performance is highlighted. This review also identifies potential challenges facing this novel class of SA-ENFs in electrocatalytic applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"13 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144928289","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":"Regiodivergent Lewis Acid Catalysis of Bicyclo[1.1.0]butanes with 2-Naphthols","authors":"Guofu Zhong, Lin Fan, Pengyang Wang, Chang He, Xiaoyu Chen, Linlong Dai, Daokai Xiong","doi":"10.1039/d5sc05468k","DOIUrl":"https://doi.org/10.1039/d5sc05468k","url":null,"abstract":"Enhancing drug efficacy often involves increasing the proportion of sp³-hybridized carbons. Three-dimensional polycyclic frameworks, such as bicyclo[1.1.1]pentanes (BCPs) and bicyclo[2.1.1]hexanes (BCHs), serve as excellent benzene bioisosteres, improving bioavailability and reducing toxicity while retaining biological activity. However, synthetic routes to 2D/3D-ring-fused BCHs via dearomatization are scarce, previously limited to cycloadditions of bicyclobutanes (BCBs) with indoles, bicyclic aza-arenes, or naphthalenes. Herein, we achieve Lewis acid-catalyzed dearomatization of BCBs with 2-naphthol. Eu(OTf)<small>₃</small> catalysis provides dearomatized tertiary alcohols, while AgBF<small>₄</small> promotes dearomatization/aromatization to directly access naphthalene-fused BCHs, showcasing remarkable reaction selectivity. Mechanistic studies definitively identify cyclobutyl carbocations as key intermediates. This strategy is anticipated to accelerate the exploration of fused BCH scaffolds in medicinal and synthetic chemistry.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"89 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144924169","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}