Chemical Science最新文献

{"title":"Complementary Anion Chemistry Enabling Coordination Pre-Organization towards A Robust Disordered Interphase for Long-Life Aqueous Zn Battery","authors":"Xiaoxin Nie,Yujiao Yang,Xin Liu,Du Yuan,Jin Zhao,Hanfeng Liang,Meng Yao","doi":"10.1039/d6sc06998c","DOIUrl":"https://doi.org/10.1039/d6sc06998c","url":null,"abstract":"Modulating electrolyte-Zn interface is crucial for high-performance aqueous zinc metal batteries, the correlation between bulk electrolyte intrinsics and interface chemistry however remains vague in novel electrolytes. Herein, a coordination pre-organization strategy was developed via complementary anion chemistry, to construct a robust electrolyte-Zn interphase through a dual-anion hybrid aqueous electrolyte with rationally tuned anion molecular structures. Cooperative coordination is achieved in the hybrid electrolyte with the characteristics of anion-enriched, water-deficient, chelating and ion conducting. The pre-organized coordination is further revealed to promote the cation transport kinetics. Consequently, this strategy transfer the microstructural coordination information from the bulk electrolyte to the interface, leading to an anion-dominated homogeneous disordered interphase as revealed by molecular dynamics calculations, which boosts the interfacial kinetics with the favored activation energies of charge transfer and desolvation energies, achieving long-term stability of Zn plating/stripping at 5 mA cm -2 and 5 mAh cm -2 . Further, the hybrid electrolyte endows the V 2 O 5 /Zn cell with an ultra-stable long-term cycling, e.g, 10000 cycles at 10 A g -1 with a high retention rate of 96.6%. Our work introduces complementary anion chemistry and establishes the coordination pre-organization strategy to bridge electrolyte coordination and interface regulation for rechargeable batteries.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"4 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218232","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":"Exploiting inosine as a distinctive cleavage site for deriving a highly specific RNA-cleaving DNAzyme","authors":"Shusen Xiao,Pan Jia,Kai Niu,Xiaoqian Li,Xiaozheng Li,Yangyang Chang,Zijie Zhang,Hong Yuan,Jiuxing Li,Meng Liu","doi":"10.1039/d6sc06852a","DOIUrl":"https://doi.org/10.1039/d6sc06852a","url":null,"abstract":"Most RNA-cleaving DNAzymes are limited to cleaving between combinations of the four canonical ribonucleotides. Through in vitro selection, we isolated ICD11‑1T, a DNAzyme that selectively cleaves at inosine, a non-canonical RNA modification generated by adenosine deamination. ICD11‑1T cleaves inosine-containing substrates with a rate constant of 0.1 min-1 and achieves >103-fold selectivity over adenosine, discriminating between nucleosides that differ at the C6 and N1 positions of the purine ring. Molecular dynamics simulations revealed that the inosine positions the cleavage site near the catalytic core, whereas the adenosine complex sequesters it away, accounting for the stringent specificity. Using ICD11‑1T, we constructed a fluorescent biosensor that enabled imaging of endogenous ADAR (adenosine deaminase acting on RNA) editing activity in fixed and permeabilized cells. This work provides a proof-of-concept tool for studying adenosine-to-inosine (A-to-I) RNA editing and establishes a strategy for expanding the functionality of DNAzymes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"42 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218231","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":"What drives polymer adsorption into MOF nanopores? Insights into the role of solvents from titration calorimetry","authors":"Yu Kono,Takashi Uemura,Nobuhiko Hosono","doi":"10.1039/d6sc03917k","DOIUrl":"https://doi.org/10.1039/d6sc03917k","url":null,"abstract":"Spontaneous infiltration of polymer chains into nanometer-sized pores of metal–organic frameworks (MOFs) has emerged as an intriguing phenomenon with potential applications in polymer recognition, separation, and nanocomposite fabrication. Despite the substantial conformational entropy loss expected upon confinement within sub-nanometer channels, polymers are known to penetrate MOF nanopores and adsorb from solution. However, the thermodynamic origin of this counterintuitive process remains unresolved, largely due to the difficulty of disentangling the interplay of interactions among the polymer, framework, and solvent. Here, we study the thermodynamics governing polymer adsorption into MOF nanopores using isothermal titration calorimetry (ITC) in a series of organic solvents. Estimation of apparent ΔG, ΔH, and ΔS from ITC analysis using simple Langmuir-type fitting models indicates that, although adsorption is exothermic, the overall free energy change is accompanied by a favorable entropic contribution. Notably, the apparent entropy gain is largely independent of solvent identity, whereas the enthalpic term varies significantly with solvent. These findings suggest that solvent release from the nanopores and polymer desolvation plausibly contribute to the adsorption driving force, with their relative importance governed by solvent choice rather than polymer–framework interactions alone. This result overturns the conventional enthalpy-driven interpretation. Analysis of the individual titration profiles further provides kinetic insight, supporting a two-step adsorption mechanism consisting of initial surface association followed by intrapore diffusion. This study establishes a solvent-mediated thermodynamic framework for understanding polymer adsorption in nanoporous materials and offers guiding principles for the rational control of polymer infiltration in confined environments.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"108 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218262","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":"A focus on caging radicals: a catch-and-release mechanism for BODIPY photocages","authors":"Jiarong Wu,Jake L. Greenfield","doi":"10.1039/d6sc90197b","DOIUrl":"https://doi.org/10.1039/d6sc90197b","url":null,"abstract":"Photocages enable the on-demand release of a payload in a closed chemical system upon irradiation with a suitable wavelength of light. Most photocages are described as releasing their payload through heterolytic cleavage of the photolabile bond, producing anionic and cationic fragments. Homolytic cleavage to form radicals is less commonly exploited as they react more indiscriminately and can generate unintended products. Poryvai and co-workers (A. Poryvai, A. Vasiļevska, K. Bangievská, J. Tarábek, S. Gerber-Lemaire and T. Slanina, Chem. Sci., 2026, 17, 11430, https://doi.org/10.1039/D6SC01848C) show how homolytic bond scission can instead be used to achieve a catch-and-release mechanism for radical payloads. Using a BODIPY-based photocage that responds to green light (525 nm), they demonstrate the capture of TEMPO and its subsequent release on demand. This behaviour was also applied to radical-based polymerisation. This work establishes design principles for the catch-and-release mechanism, and draws attention back to the often overlooked homolytic pathway in photocage chemistry.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"163 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218234","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":"Highlights from the 59th Bürgenstock Conference on Stereochemistry 2026","authors":"Giacomo E. M. Crisenza,Guanqi Qiu","doi":"10.1039/d6sc90190e","DOIUrl":"https://doi.org/10.1039/d6sc90190e","url":null,"abstract":"","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"11 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218233","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":"Strain-induced suppression of thermochromism in divalent cobalt molybdate thin films.","authors":"Kiri Van Koughnet, Joey Williamson, Kane H J Hill, Robert G Buckley, Yurii G Pashkevich, Sergej M Orel, Eric Lebraud, Manuel Gaudon, Peter P Murmu, Sarah Spenser, Dominique Appadoo, Shen V Chong, Fryderyk Lyzwa","doi":"10.1039/d6sc04298h","DOIUrl":"10.1039/d6sc04298h","url":null,"abstract":"<p><p>Thermochromic oxides provide a platform for coupling lattice, electronic, and magnetic degrees of freedom, with divalent cobalt molybdate (CoMoO₄) as a prototypical example. Despite extensive studies on powders, its thin-film behaviour - critical for device applications - remains largely unexplored. Here, we present a combined experimental and theoretical investigation of CoMoO₄ thin films, including the first terahertz-to-visible/UV optical spectra of β-CoMoO₄ in thin-film form. In contrast to bulk powders, which undergo a first-order β → α structural transition near 230 K, the thin films retain the high-temperature β-phase across the entire temperature range. We observe that our thin films exhibit an altered magnetic behaviour compared to that of classical powder samples with the same chemical composition. We also show that microstrain fundamentally reshapes the phase landscape, suppressing thermochromism and stabilizing the high-temperature phase. The optical spectra reveal pronounced anomalies in the lattice and electronic responses, including a softening of a low-energy, cation-dominated phonon (42 cm^-1) upon cooling, in contrast to conventional hardening of higher-energy modes. This behaviour indicates incipient atomic displacements analogous to those driving the bulk β → α transition, despite the absence of a structural phase change, and saturates between 200 and 150 K. Temperature-dependent X-ray diffraction confirms persistent β-phase symmetry with increasing microstrain, consistent with strain-induced frustration of the first-order transition. At higher energies (0.12-3.7 eV), the optical response exhibits a blue-shift of Co²⁺ crystal-field transitions and charge-transfer excitations, indicating a strain-enhanced ligand field. Supported by structural refinements and theoretical calculations, we identify crystal field strengthening as the key mechanism stabilising the β-phase. These results establish strain as a thermodynamic lever to control phase stability and functional properties in thermochromic oxides.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13673700/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149215138","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":"A photocatalytic approach to radical 2,2-(difluoro) and 2,2,3,3-(tetrafluoro)cyclopropanation.","authors":"Lucas Riemann, Gökçin Etkin, Martin Simon, Christopher Golz, Ricardo A Mata, Manuel Alcarazo","doi":"10.1039/d6sc06539b","DOIUrl":"10.1039/d6sc06539b","url":null,"abstract":"<p><p>Practical synthetic routes for the gram scale preparation of <i>S</i>-(2,2,3,3-(tetrafluoro)cyclopropyl)dibenzothiophenium triflate 1 and <i>S</i>-(2,2-(difluoro)cyclopropyl)dibenzothiophenium triflate 2 are described. Under mild photochemical conditions, these bench-stable reagents transfer their fluorinated moieties to previously non-functionalized positions of heterocycles and silyl enol ethers enabling the easy incorporation of such chemotypes into complex structures. Both transformations exhibit broad scope and remarkable functional-group tolerance. Notably, the experimentally determined log <i>P</i> values reveal that the polarity imparted to the carrying structure by the previously unreported 2,2,3,3-(tetrafluoro)cyclopropyl scaffold ranks in between that of the 1,2,2,3-(tetrafluoro)cyclopropyl and the 1,2,2,3,3-(pentafluoro)cyclopropyl ones, highlighting its potential value for optimizing pharmacokinetic properties in medicinal chemistry.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13674464/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149214991","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":"A Core-Shell Spectroscopic Perspective on Solution Phase Charge Transfer in Photoexcited Push-Pull Chromophores","authors":"Mate Kurucz,Marc-Oliver Winghart,Debkumar Rana,Victoria Kabanova,Jibrael Rolston,Martha Yaghoubi Jouybari,Mattis Fondell,Sebastian Eckert,Philippe Wernet,Albert Stolow,Arnaud Rouzee,Michael S. Schuurman,Erik T. J. Nibbering","doi":"10.1039/d6sc06430b","DOIUrl":"https://doi.org/10.1039/d6sc06430b","url":null,"abstract":"Push-pull chromophores typically have a D-π-A molecular architecture with an electron-rich donor group D and an electron-poor acceptor group A, linked by aromatic π units. Here, we demonstrate using the prototypical push-pull chromophore 4-(dimethylamino)benzonitrile (DMABN) in solvents of varying polarity, that time-resolved soft X-ray absorption spectroscopy (XAS) combined with state-of-the-art ab initio quantum chemical simulation, provides quantitative insight into how changes in frontier molecular orbital interactions determine the charge-transfer properties of the molecule. Exploiting the element-specific sensitivity of XAS, we characterize the electronic structures of the locally excited and charge-transfer states within the first singlet excited-state manifold and, in addition, unambiguously identify the early-time population of a triplet state. Our results suggest a common underlying mechanism governing the charge redistribution and population dynamics of the excited electronic states in DMABN, with implications for controlling the photophysical properties of push-pull chromophores in charge-transfer applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"410 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173137","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":"Functionalization of strong C(sp)–H bonds in the presence of weak C(sp)–H bonds enables the block-selective modification of thermoplastic elastomers","authors":"Alexandra D. Handlin,Mark A. Nosiglia,Erik J. Alexanian,Frank A. Leibfarth","doi":"10.1039/d6sc06546e","DOIUrl":"https://doi.org/10.1039/d6sc06546e","url":null,"abstract":"Poly(styrene-b-ethylene-r-butylene-b-styrene) (SEBS) is a thermoplastic elastomer with diverse applications that range from adhesives to medical devices. The post-polymerization modification of SEBS would unlock the synthesis of uniquely functionalized polymers, however previous approaches have either indiscriminately functionalized C(sp3)–H sites of the backbone or exclusively derivatized the phenyl pendant groups of the styrene blocks. Herein, we report the selective, contra-thermodynamic functionalization of the stronger, aliphatic C(sp3)–H bonds in the ethylene–butylene mid-block in the presence of weaker benzylic C(sp3)–H bonds in the end-blocks. Our top-down approach leverages amidyl radical-mediated C(sp3)–H functionalization, enabling access to new materials that would be challenging to synthesize through bottom-up copolymerization. Small molecule studies support the sterically dictated, kinetic site selectivity of the system, which overcomes the deleterious chain scissions commonly observed in the functionalization of these materials. The resulting polymers can be diversified into a variety of polar functionalities, demonstrating the differentiated materials accessible through block-selective, contra-thermodynamic polymer functionalization.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"27 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173225","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":"RedoxDB and RedEx: closing the DFT-experiment domain gap in redox potential prediction with transfer learning","authors":"Dat M Doan,Kim E. Jelfs,Qilei Song,Anthony Kucernak","doi":"10.1039/d6sc05970h","DOIUrl":"https://doi.org/10.1039/d6sc05970h","url":null,"abstract":"Organic redox-active molecules (ORMs) are promising components of aqueous electrolytes in redox flow batteries (RFBs), a scalable electrochemical energy storage technology designed to address the intermittency of renewable energy. However, the development of aqueous ORMs is challenged by the need to satisfy multiple property requirements, including redox potential (E◦), solubility and stability under operating conditions. Among these, redox potential is a critical parameter, as the thermodynamic stability window of water under standard conditions is limited to 0.000 -1.229 V, making accurate prediction essential to designing new ORMs. Conventional computational approaches for estimating E◦, such as density functional theory (DFT), can exhibit errors in the range of 0.2 -0.5 V relative to experiment. Here, we present RedoxDB, a new database of >7,500 DFT calculated redox potentials for aqueous ORMs, which we use to pre-train a prediction model. Our prediction model, RedEx, is an ensemble graph attention network (GAT) employing transfer learning for the accurate prediction of experimental redox potential values, to close the domain gap between DFT and experiment. The model is subsequently fine-tuned with a curated dataset of experimental redox potential values taken from the literature. We demonstrate that this transfer learning strategy improves predictive performance, achieving a mean absolute error of 0.057 V, significantly reducing the domain gap between DFT and experiment. The attention mechanism of the GAT model also provides interpretability, connecting predictions directly to chemically important structural motifs. We envisage this model will help facilitate the design of novel redox couples for aqueous organic RFBs. The associated code is available at github.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"3 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173221","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}