Chemical Science最新文献

{"title":"Atomically thin vanadium oxide nanosheets via top-down exfoliation for ultrafast-charging zinc-ion batteries","authors":"Weikang Jiang,Xiling Niu,Kaiyue Zhu,Weili Xie,Zhengsen Wang,Weishen Yang","doi":"10.1039/d6sc05963e","DOIUrl":"https://doi.org/10.1039/d6sc05963e","url":null,"abstract":"Aqueous zinc-ion battery (ZIB) is a promising energy storage solution due to the high safety, environmental friendliness and low cost. Although high ionic conductivity of aqueous electrolyte and fast kinetic of zinc plating/stripping hold a promise for fast discharge/charge, the rate capability of AZIB remains limited by the poor ion and electron transport in cathode materials.This study addresses this challenge by developing atomically thin vanadium oxide nanosheets (∼2 nm thickness) through a top-down exfoliation strategy of bulk ZnV6O16•nH2O. Driven by small-molecule-assisted interlayer interactions, a mild wet ball-milling and ultrasonication process effectively disrupts interlayer hydrogen bonding and enables efficient layer separation. Benefiting from the reduced thickness (layers) and weakened interlayer interactions, the exfoliated ZnV6O16•nH2O nanosheets deliver a solid-state ion diffusion coefficient nearly eight times higher than bulk, together with a decreased diffusion barrier (84.6 meV versus 187.5 meV), promoting rapid charge storage. Finally, a high capacity of 346 mAh g-1 (4.5 times that of bulk) at 50 A g-1 and excellent cycling stability (77% capacity retention after 30,000 cycles at 100 A g-1 ) are achieved in coin-type cells based on ultrathin ZVO nanosheets. Moreover, a 45 cm2 pouch cell maintains 98% capacity retention over 550 cycles, highlighting the strong potential of scalable preparation and practical application. These findings demonstrate a promising strategy for designing high-performance, fast-charging batteries, advancing grid-scale energy storage solutions.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"14 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148899305","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":"Strategies toward efficient tin-based perovskite solar cells","authors":"Tomoya Nakamura,Chien-Yu Chen,Atsushi Wakamiya","doi":"10.1039/d6sc06089g","DOIUrl":"https://doi.org/10.1039/d6sc06089g","url":null,"abstract":"Tin halide perovskite solar cells are considered one of the most promising alternatives to conventional lead-based perovskite photovoltaics due to their structural and electronic similarities, along with their lower toxicity. However, the chemistry of tin halide perovskites is distinct from that of their lead counterparts. As a result, tin halide perovskite solar cells still lag behind lead-based devices in both performance and long-term stability. This review summarizes recent progress in strategies to address these challenges, focusing on controlling key issues such as Sn2+ oxidation, rapid crystallization, and high defect densities. Specific approaches discussed include precursor purification, the use of chemical additives, compositional engineering, surface modifications, interlayers, and the design of charge-transporting materials. Future advances will require the development of thicker high-quality absorber layers, robust electron- and hole-selective contacts, improved operational durability, and scalable fabrication methods. These integrated strategies will be essential for realizing efficient, stable, and large-area lead-free perovskite photovoltaics.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"30 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148899308","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 periodic system of polycyclic aromatic hydrocarbons for predictive molecular growth processes","authors":"Wang Li,Hu Ju,Ming-Gao Xu,Shane J. Goettl,Jiu-Zhong Yang,Long Zhao,Ralf I. Kaiser","doi":"10.1039/d6sc05859k","DOIUrl":"https://doi.org/10.1039/d6sc05859k","url":null,"abstract":"Radical–radical reactions of resonantly stabilized species such as propargyl (C3H3˙) and benzyl (C7H7˙) efficiently generate polycyclic aromatic hydrocarbons (PAHs). Key mechanisms—propargyl addition–benzannulation (PABA), methyl addition–ring expansion (MARE), and cyclopentadienyl addition–naphthylization (CPAN)—govern early-stage aromatic growth, but transforming these mechanisms to larger PAHs is computationally challenging due to combinatorial intermediates and reactions on excited state triplet surfaces. Here, we introduce a “periodic system” of PAHs that organizes aromatic growth according to transferable radical–radical motifs, enabling prediction of molecular evolution across the size regime. Using (2-naphthyl)-methyl (2-C11H9˙) and benzyl (C7H7˙) radicals as benchmarks, we experimentally demonstrate the predicted gas-phase formation of four- and five-ring PAHs, including (1) C18H12 isomers: tetracene, benz[a]anthracene, and [4]helicene; (2) C22H14 isomers: benzo[a]tetracene, benzo[a]tetraphene, and [5]helicene. Secondary hydrogen-loss and successive reactions produce even larger 2D and 3D aromatics, such as nanobowls and fullerenes, and their building blocks (corannulene and coronene). This framework provides a unifying and predictive description of PAH growth across combustion and circumstellar environments such as carbon-rich envelopes of late-type Asymptotic Giant Branch (AGB) stars and planetary nebulae.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"28 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148899307","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":"Azulene as an Anomaly in Triplet-State Engineering Via Bromination and/or Carbonylation: Internal Conversion Overrides Intersystem Crossing","authors":"Kavya Vinod,Claire Tonnelé,Anup Rana,Amalnadh T.,P. E. Swathi Krishna,Juan Carlos Roldao,Henrik Ottosson,David Casanova,Mahesh Hariharan","doi":"10.1039/d6sc00694a","DOIUrl":"https://doi.org/10.1039/d6sc00694a","url":null,"abstract":"Azulene, a non-benzenoid aromatic system, exhibits a unique electronic structure that gives rise to unconventional excited-state dynamics. Here, we investigate a series of halogenated and carbonylated azulenes using ultrafast spectroscopy and quantum chemical calculations. Despite incorporating substituents that are known to enhance intersystem crossing (ISC), halogenated/carbonylated azulenes exclusively display singlet excited-state dynamics. Femtosecond and nanosecond transient absorption measurements reveal rapid internal conversion without any detectable triplet population. Computational analysis using the Marcus formalism confirms that, although spin–orbit coupling increases upon bromination/carbonylation, ISC remains orders of magnitude too slow to compete with fast internal conversion. These findings highlight the intrinsic resistance of azulene derivatives to triplet-state formation, challenging established strategies for promoting ISC and offering new insights into substitution-dependent excited-state pathways in non-benzenoid aromatics.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"37 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148899306","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":"Universal Charge-Tag Labelling of Undetectable Polymers and Greases for Mass Spectrometric Characterization","authors":"Charles Killeen,Liliia Pestereva,Maxine Turner,Luca Swainson,Jeremy E Wulff,J. Scott McIndoe","doi":"10.1039/d6sc05830b","DOIUrl":"https://doi.org/10.1039/d6sc05830b","url":null,"abstract":"Despite massive advances in mass spectrometric technologies, there remains a class of materials largely impervious to analysis: high molecular weight aliphatic hydrocarbons. Electrospray ionization mass spectrometry (ESI-MS) is used extensively as a tool in petroleomics to identify and fingerprint the polar constituents of oil, but the non-polar constituents remain challenging to analyze with ESI-MS due to poor ionization efficiency. Derivatization methods which bond electrospray-active tags to analytes impart charge and increase analyte response, and have been developed for many different classes of petrochemicals, but not hydrocarbons. In this work, a method is described which renders aliphatic hydrocarbons amenable to ESI-MS analysis through the C-H insertion into a substrate molecule of a diazirine-derived carbene, which is bound to a pendant alkyne. Subsequent electrospray-tagging occurs through copper-catalyzed azide alkyne cycloaddition, appending a triphenylphosphonium cation to the derivatized compound. The process was developed and benchmarked with cyclododecane as a model substrate to evaluate tagging efficiency and product distribution, then applied to characterize the composition of several commercial product samples. While derivatization efficiency and ionization response may vary across substrates, the method provides a complementary route to established ionization techniques by enabling hydrocarbon analysis within ESI-based high-resolution mass spectrometric workflows. Its primary utility lies in enabling ESI-compatible fingerprinting of unfunctionalized compounds (heteroatom-containing species may react preferentially).","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"14 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148893373","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":"On the multiple solutions of the complex absorbing potential method for resonances","authors":"Fábris Kossoski","doi":"10.1039/d6sc03887e","DOIUrl":"https://doi.org/10.1039/d6sc03887e","url":null,"abstract":"The complex absorbing potential (CAP) method is an effective approach to model anionic resonances. However, the existing optimization criteria for the CAP strength give rise to multiple solutions, and the common practice has been to pick a single one as describing the resonant state and to discard the rest as unphysical. Here, we challenge this view by demonstrating that several solutions can be acceptable approximations for the resonance. This ambiguity introduces an important source of uncertainty in CAP calculations that we show to be generally larger than the errors stemming from the basis set incompleteness and the approximate electronic structure method, affecting energies and properties alike. Moreover, various strategies that have been proposed to mitigate the appearance of multiple solutions are shown to be ineffective, like enlarging the basis set, subtracting the energy contribution from the CAP, and introducing a real perturbative potential. Although the CAP method has proven merits in the description of anionic resonances, the existence of multiple solutions emerges as a critical and unsolved problem.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"30 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148893370","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":"Inhibitor fluorination pattern modulates protein surface dynamics and chemically induced dimerization","authors":"Eric Schwegler,Jean-Martin Harder,Marco D. Preuss,Charlotte Guhl,Shuaibing Zhang,Annika Wagner,Nicole Bader,Pierre Stallforth,Hermann Schindelin,Till Opatz,Markus Lakemeyer,Ute Hellmich","doi":"10.1039/d6sc05625c","DOIUrl":"https://doi.org/10.1039/d6sc05625c","url":null,"abstract":"Chemically induced proximity of biomacromolecules is a powerful strategy to regulate cellular processes using small molecule ligands that act as “molecular glues” to influence complex lifetime, localization and function. However, the structure-activity relationships governing such inducible interactions remain elusive. Here, using a series of self-assembling homodimerizers that target an essential parasitic redox enzyme, we present a systematic, fluorination-guided strategy to tune induced protein homodimer affinity by two orders of magnitude. Combining NMR spectroscopy, MD simulations, chromatography, multi-angle light scattering, mass spectrometry, calorimetry, and functional assays, we demonstrate that the fluorination pattern of the dimerizer tunes homodimer affinity by modulating the conformational dynamics of both the bound ligand and the protein residues constituting the dimer interface. These findings establish a generalizable framework for understanding how ligand fluorination shapes protein surface dynamics and protein interactions. They further reveal how the fluorination pattern of molecular glues modulates inducible protein assembly across biologically relevant affinity ranges, providing mechanistic principles for the rational design of proximity-inducing molecules.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"70 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148893402","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":"Hierarchical Crystal Structure Prediction of Zeolitic Imidazolate Frameworks Using DFT and Machine-Learned Interatomic Potentials","authors":"Yizhi Xu,Jordan Dorrell,Katarina Lisac,Ivana Brekalo,James Darby,Andrew J. Morris,Mihails Arhangelskis","doi":"10.1039/d6sc04307k","DOIUrl":"https://doi.org/10.1039/d6sc04307k","url":null,"abstract":"Crystal structure prediction (CSP) is emerging as a powerful method for the computational design of metal-organic frameworks (MOFs). In this article we employ CSP to perform high-throughput exploration of the crystal energy landscape of zinc imidazolate (ZnIm2). As the most polymorphic member of the zeolitic imidazolate framework (ZIF) family, ZnIm2 has at least 24 reported structural and topological forms, and new polymorphs still being regularly discovered. With the aid of custom-trained machine-learned interatomic potentials (MLIPs) we have performed a high-throughput sampling of over 3 million randomly-generated crystal packing arrangements and identified 9609 energy minima characterized by 1484 network topologies, including 855 topologies that have not been reported before. All but one experimentally-reported structures of ZnIm2, falling within the search boundaries, were ultimately matched with the predicted structures, demonstrating the power of the CSP method in sampling experimentally-relevant ZIF structures. Finally, through a combination of topological analysis, density and porosity considerations, we have identified a set of structures representing promising targets for future experimental screening, as well as demonstrated how structures of mechanochemically synthesized MOFs could be identified via matching experimental powder diffraction patterns with simulated patterns from the predicted structures.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"33 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148893369","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":"Bismuth-Guided Cavity Confinement Breaks the Stability-Utilization Trade-off in Zinc Powder Anodes","authors":"Yunxuan Jiang,Ziyuan Lan,Can Li,Xiaoning Li,Botian Liu","doi":"10.1039/d6sc05962g","DOIUrl":"https://doi.org/10.1039/d6sc05962g","url":null,"abstract":"The practical application of aqueous zinc-ion batteries (AZIBs) is severely hindered by the poor reversibility of Zn anode, which stems from a self-amplifying cycle involving dendrite growth, interfacial side reactions, and electrically isolated “dead Zn” formation. Here, we report a spray-assembled three-dimensional copper mesh supported particulate Zn anode, in which Zn particles are encapsulated by an inner bismuth interlayer and an outer carbon confinement shell (3D-C/Bi@Zn-p). Unlike conventional surface stabilization strategies, this surface-engineered architecture enables a unique interface-guided cavity-confined inward deposition mechanism. During stripping, Zn is selectively extracted from the particle core, leaving behind a robust bismuth-carbon composite shell embedded with isolated internal cavities. In the subsequent plating step, the passivated carbon outer layer effectively suppresses parasitic reactions and prevents Zn nucleation on the external surface, while the inner bismuth layer provides a highly zincophilic interface that kinetically directs Zn2+ exclusively plating into the cavity interior. Consequently, Zn plating is spatially confined within isolated cavities, effectively suppressing outward dendrite propagation and eliminating the risk of short circuits. Benefiting from this cavity-confined inward deposition behavior, the 3D-C/Bi@Zn-p anode delivers a Coulombic efficiency approaching 100% and enables record-high stable cycling for over 10,000 h at 1 mA cm-2 under high zinc utilization of 10.8%. Notably, stable Zn plating/stripping can still be maintained at an ultrahigh Zn utilization of 108%, far beyond the <1% Zn utilization commonly employed in most laboratory-scale studies. Furthermore, when paired with an oxygen-deficient V2O5-x cathode, the full cell delivers 211.6 Wh kg-1 and 81.2 % capacity retention after 1,000 cycles under lean-anode conditions (N/P=2.4, ~30.3% Zn utilization), outperforming most reported AZIBs. This interface-guided cavity-confined inward deposition strategy establishes new spatial confinement paradigm for reversible metal anodes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"43 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148893372","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 Rh-catalyzed addition of indoles to enones and the key role of the free N ̶ H group with acyclic enones","authors":"Mark Power,Geoffrey Stosse,Ching Ching Lam,Katrina Mackey,Mark E. Light,Douglas Kjell,Kendall N. Houk,Gerard P. McGlacken","doi":"10.1039/d6sc05410b","DOIUrl":"https://doi.org/10.1039/d6sc05410b","url":null,"abstract":"The protection of N ̶ H groups is often essential to harness highly valuable metal-catalyzed C ̶ C coupling protocols. However, the avoidance of protecting groups has enormous advantages in terms of atom- and step-economy, and can, on occasion, be required. Herein, we report a Rh-catalyzed asymmetric conjugate addition using free N ̶ H indole boronic acids and esters with enones. Excellent yields (up to 96%) and e.r. values (up to >99:1) were obtained. Each position on the carbocyclic backbone of the indole is accessible. Two sets of conditions involving two sets of chiral ligands (a chiral sulfinamide (S-ligand) and BINAP) were optimized for cyclic and acyclic enones respectively. The origin of success and failure for each ligand family was investigated using DFT calculations. For example, the calculations suggested that using the chiral S-ligand and an acyclic enone allows for ligation of two enone units, which scuppers catalytic activity. Secondly, using the BINAP ligand with acyclic enones, specifically at the C7 position of indole, allows for an H ̶ bond between the indole (N ̶ H) and the enone, which is critical for high yields and enantioselectivities. In certain cases, a subsequent one-pot process ensues where the indole product undergoes an intramolecular addition (:NH) to the newly tethered ketone (C=O), to form unusual tetracyclic hemiaminals, with two chiral centers. As expected, in cyclic enone systems, the cyclization in step 2 occurs with an excellent d.r. However remarkably, when flexible acyclic enones are used, excellent d.r. values are retained. DFT calculations were again employed which suggest that both product diastereoisomers are of similar thermodynamic energy values, so a high kinetic barrier is expected. Finally, the methodology was also extended to 1,2-addition reactions to form quaternary centers with excellent e.r.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"27 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148893371","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}