Chemical Science最新文献

{"title":"Correction: Advanced fabrication techniques for polymer–metal nanocomposite films: state-of-the-art innovations in energy and electronic applications","authors":"Muhammad Tayyab, Liu Zizhe, Sajid Rauf, Zixuan Xu, R. U. R. Sagar, Faisal Faiz, Zuhra Tayyab, Rashid Ur Rehman, Muhammad Imran, Anjam Waheed, Rida Javed, A. Surulinathan, Zulakha Zafar, Xian-Zhu Fu, Jing-Li Luo","doi":"10.1039/d5sc90087e","DOIUrl":"https://doi.org/10.1039/d5sc90087e","url":null,"abstract":"Correction for ‘Advanced fabrication techniques for polymer–metal nanocomposite films: state-of-the-art innovations in energy and electronic applications’ by Muhammad Tayyab <em>et al.</em>, <em>Chem. Sci.</em>, 2025, <strong>16</strong>, 3362–3407, https://doi.org/10.1039/D4SC04600E.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"97 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872434","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":"Alkali metal salts of 1,2,3-benzodiazaborines: Platforms for late-stage N-functionalization and metal complexation","authors":"Leonie Wüst, Lea Scheuring, Tim Wellnitz, Krzysztof Radacki, Holger Braunschweig","doi":"10.1039/d5sc01395j","DOIUrl":"https://doi.org/10.1039/d5sc01395j","url":null,"abstract":"The standard procedure for the preparation of benzoid 1,2,3-diazaborines (DABs) is the condensation of 2-formylphenyl boronic acid with a hydrazine. The choice of hydrazine derivative irreversibly predetermines the N-substituent in most cases and is additionally limited by the availability and hazardous nature of the respective hydrazines. Options to subsequently modify the N-substituent are scarce. Herein, we explore an approach to postsynthetic N-functionalization via isolable, nucleophilic DAB alkali metal amides. The structures of these metalated DABs were extensively studied, utilizing <small>¹</small>H DOSY NMR spectroscopy and XRD analysis. Subsequent reactivity studies of these unusual amides revealed an intricate, dualistic reactivity pattern. Upon treatment with mild electrophiles, the DAB amides react as N-nucleophiles, facilitating the straightforward introduction of functional groups at the N<small>_α</small> position. Due to the incorporation of the second N<small>_β</small> atom, they can moreover serve as anionic diazo ligands for the formation of <em>µ</em>-DAB-bridging coinage metal complexes, which bear a striking resemblance to well-studied complexes with pyrazolato (pz<small>⁻</small>) ligands. Overall, this work demonstrates how BN incorporation opens new avenues in ligand design and provides a valuable tool for post-synthetic modification of aryl DABs with organic and inorganic substrates.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"14 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872440","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-Molecule Nanopore Sensing of Proline cis/trans Amide Isomers","authors":"Luca Iesu, Mariam Sai, Vladimir Torbeev, Bruno Kieffer, Juan Pelta, Benjamin Cressiot","doi":"10.1039/d5sc01156f","DOIUrl":"https://doi.org/10.1039/d5sc01156f","url":null,"abstract":"Molecules known as stereoisomers possess identical numbers and types of atoms, which are oriented differently in space. Cis-trans isomerization of proline, a distinctive case of stereoisomerism in peptides and proteins, includes the rearrangement of chemical groups around an acyl-proline amide bond that bears the partial double bond character. Many cellular processes are affected by cis-trans proline isomerization and associated conformational protein interconversions. This work explored the conformer ratio of natural and chemically modified prolines using the aerolysin pore as a nanosensor. Despite the well-known involvement of proline in protein folding, stability, and aggregation, the highly demanding discrimination of cis and trans isomers of the Xaa-Pro peptide bond has not so far been reported at a single-molecular level using an electrical detection with a nanopore. For a proline-rich 19 amino acid fragment of the Dynamin 2 protein, one of the subfamilies of GTP-binding proteins, the third proline in the sequence was substituted by two stereoisomeric 4-fluoroprolines. The nanopore experiments were able to sense the influence of fluorination in shifting the cis/trans conformers’ equilibrium compared to the natural proline: for 4-(R)-fluoroproline, the trans amide isomer is more favored, while the opposite shift was observed for 4-(S)-fluoroproline. NMR spectroscopy was used to validate the nanopore results. Overall, our findings demonstrate the high sensitivity of single-molecule nanopore sensing as an analytical tool for stereoisomer identification within peptides.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"132 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872483","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":"Icosahedron kernel defect in Pt1Agx series of bimetallic nanoclusters enhances photocatalytic hydrogen evolution","authors":"Dong Tan, Tengfei Ding, Kaidong Shen, Chang Xu, Shan Jin, Daqiao Hu, Song Sun, Manzhou Zhu","doi":"10.1039/d5sc01735a","DOIUrl":"https://doi.org/10.1039/d5sc01735a","url":null,"abstract":"Developing high-efficiency photocatalysts for photocatalytic hydrogen production and understanding the structure–property relationships is much desired. In this study, a family of Pt<small>₁</small>Ag<small>_<em>x</em></small> (<em>x</em> = 9, 11, 13 and 14) nanoclusters (NCs), including a new Pt<small>₁</small>Ag<small>₁₁</small>(SR)<small>₅</small>(P(Ph-OMe)<small>₃</small>)<small>₇</small> NC, were designed and synthesized <em>via</em> ligand engineering (SR = 2,3,5,6-tetrafluorothiophenol, P(Ph-OMe)<small>₃</small> = tris(4-methylphenyl)phosphine). The positive effect of the kernel structural defect on photocatalytic activity was investigated using the photocatalytic water-splitting reaction as a model, and the mechanistic relationship between the defect structure and catalytic activity was clarified. In this series of Pt<small>₁</small>Ag<small>_<em>x</em></small> bimetallic NCs, the Pt<small>₁</small>Ag<small>₁₁</small> NC, which exhibits a distinctive defect-containing icosahedral kernel structure, displayed excellent catalytic performance for photocatalytic hydrogen evolution, with the hydrogen production rate reaching 1780 μmol g<small>⁻¹</small> h<small>⁻¹</small>. The experimental results revealed that the superior catalytic activity of Pt<small>₁</small>Ag<small>₁₁</small>/g-C<small>₃</small>N<small>₄</small> may originate from the formation of Z-scheme heterojunction between Pt<small>₁</small>Ag<small>₁₁</small> and the g-C<small>₃</small>N<small>₄</small>, facilitating efficient electron–hole separation and charge transfer. Furthermore, density-functional theory (DFT) calculations reveal the critical role of the defect-containing icosahedron-kernel on photocatalytic activity, which is favourable for the formation of the most stable nanocomposites and the easy absorption of H* intermediates on the Ag sites in Pt<small>₁</small>Ag<small>₁₁</small>/g-C<small>₃</small>N<small>₄</small>. This paper provides insights into the effect that the defects have on the mechanism of the photocatalytic hydrogen evolution reaction at the atomic level and promotes the rational design of high-efficiency photocatalysts.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"5 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143876170","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":"α-N-Phthalimido-Oxy Isobutyrate-Mediated Deoxygenative Arylation: Total Synthesis of Alanenses A and B","authors":"Young Eum Hyun, Jeonguk Kweon, Thi Hieu Linh Phan, Dongwook Kim, Sunkyu Han","doi":"10.1039/d5sc00341e","DOIUrl":"https://doi.org/10.1039/d5sc00341e","url":null,"abstract":"Inspired by our biosynthetic hypothesis for alanense A, we developed two distinct methods for the deoxygenative arylation of α-<em>N</em>-phthalimido-oxy isobutyrate (NPIB), derived from hydroxyl groups adjacent to or conjugated with a carbonyl moiety. One approach utilizes photoredox catalysis to achieve a radical-mediated arylation reaction. Alternatively, we designed an acid-mediated arylation method that proceeds through a cationic intermediate. The acid-mediated approach was successfully applied to the total syntheses of alanenses A and B, as well as O7′-methyllacinilene E.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"14 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872435","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":"Affinity peptide ligands: new tools for chasing non-canonical N-phosphoproteome","authors":"He Wang, Xiaoyu Zhang, Dongdong Wang, Qianqian Jiang, Yue Sun, Baofeng Zhao, Zhen Liang, Guangyan Qing, Bo Jiang, Lihua Zhang, Yukui Zhang","doi":"10.1039/d5sc01557j","DOIUrl":"https://doi.org/10.1039/d5sc01557j","url":null,"abstract":"The enrichment of protein <em>N</em>-phosphorylation encounters substantial challenges due to the inherent instability of the N–P bond, severely impeding the manifestation of its biological functions. Traditional enrichment methods often rely on antibodies, organic solvents and metal ion interactions, which are limited by lack of universality, potential degradation of sample integrity, or reduced selectivity for <em>N</em>-phosphorylation. To overcome these challenges, we innovatively capitalized phage display technology to identify affinity peptides that specifically bind to the N–PO<small>₃</small> group. By functionalizing magnetic nanoparticles with the affinity peptide, we developed a novel, organic solvent- and metal-free enrichment strategy that enhanced both the selectivity and efficiency for all three types of <em>N</em>-phosphopeptide capture under neutral conditions, ensuring superior preservation of sample integrity and allowing more accurate proteomic analysis. This strategy has demonstrated robust enrichment capabilities for both prokaryotic and eukaryotic samples. In HeLa cells, 1995 novel <em>N</em>-phosphorylation sites were identified, representing a substantial increase of 2- to 5-fold in detection depth over previous approaches and significantly expanding the scale of the <em>N</em>-phosphoproteome database. Additionally, it was discovered that <em>N</em>-phosphorylation modification was highly concentrated in the nucleus. By integrating the nuclear isolation technique, 1296 <em>N</em>-phosphorylation sites were identified for the first time, offering new leads for uncovering the functions of <em>N</em>-phosphorylation in nuclear proteins. Finally, in conjunction with the quantitative proteomics method, the dynamic changes in <em>N</em>-phosphorylation modification during the progression of Alzheimer's disease were investigated, providing fresh perspectives on the research of AD pathogenesis. Overall, this work not only presents a new approach for efficient enrichment of <em>N</em>-phosphopeptides but also advances the functional study of <em>N</em>-phosphorylated proteins in physiological and pathological processes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872437","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":"Enabling uniform lithiation in solid-state synthesis by preventing pre-matured surface grain coarsening through grain boundary engineering","authors":"Yifan Wu, Xincan Cai, Weiyi Lin, Yingdong Deng, Qing Zhang, Haoyuan Li, Pu Yan, Guohui Zhong, Jin Xie","doi":"10.1039/d5sc00271k","DOIUrl":"https://doi.org/10.1039/d5sc00271k","url":null,"abstract":"Solid-state calcination profoundly influences the structural integrity and electrochemical performance of polycrystalline layered oxide cathode materials in lithium-ion batteries. As temperatures rise, heterogeneous phase transitions driven by solid-state diffusion can result in structural non-uniformity. In this study, we employ operando characterization techniques and high-resolution electron microscopy to scrutinize the inherent heterogeneity observed in the early-stage of the solid-state lithiation process and its subsequent influence on the formation and merging of resultant LiNi0.9Co0.05Mn0.05 (NCM90) grains on the surface of the secondary particle. We found a conformal atomic layer deposited WO3 layer on the hydroxide precursor could be in-situ lithiated to form LixWOy compounds, which are stable and none-dissolvable at the grain boundaries, further acting as segregation layer to prevent the merging of grains during the formation of layered phase on the surface of secondary particles, which preserves the route for the uniform lithiation for the inner part of the secondary particles. These investigations shed light on the effect of solid-state reaction heterogeneity and present a novel methodology for mitigating the persistent challenge by grain boundary engineering.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"73 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872439","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":"An overlooked cyclase plays a central role in the biosynthesis of indole diterpenes","authors":"Rosannah Cameron, Daniel Berry, Alistair T. Richardson, Luke J. Stevenson, Yonathan Lukito, Kelly Styles, Natasha S. L. Nipper, Rose May McLellan, Emily Parker","doi":"10.1039/d5sc02009c","DOIUrl":"https://doi.org/10.1039/d5sc02009c","url":null,"abstract":"Indole diterpenes (IDTs) are a large class of highly complex fungal natural products that possess a wide array of intriguing bioactivities. While IDTs are structurally diverse, the first four steps of IDT biosynthesis are highly conserved and result typically in the formation of a tetrahydropyran (THP)-ring containing structure, most commonly paspaline. The biosynthetic genes responsible for these steps are the most extensively studied of all IDT genes and collectively define the core biosynthetic pathway. Here we show that the fourth fundamental step, formation of the THP ring, is catalysed by a terpene cyclase encoded by an overlooked and uncharacterised fifth gene, idtA. All previously delineated biosynthetic routes have incorrectly attributed this step to the terpene cyclase IdtB, leading to imprecise pathway reconstructions and ignoring the fully evolved biosynthetic solution for core IDT generation. Moreover, while IdtA terpene cyclases are found in Eurotiomycete fungi, in Sordariomycete fungi this step is catalysed by the unrelated protein IdtS, demonstrating that two distinct solutions to this chemistry exist. All biosynthetic gene clusters known to specify production of THP-containing IDTs include an idtA or idtS gene. These findings reset the paradigm for core IDT biosynthesis and support accurate heterologous biosynthesis of these complex natural products.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"37 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143876169","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":"Critical issues and optimization strategies of vanadium dioxide-based cathodes towards high-performance aqueous Zn-ion batteries","authors":"Botao Wan, Yajiang Wang, Xiudong Chen, Changchao Zhan, Huixiong Jiang, Jin-Hang Liu, Yun Gao, Xiaoduo Jiang, Xiaohua Cao, Hang Zhang, Shi-Xue Dou, Yao Xiao","doi":"10.1039/d5sc01889g","DOIUrl":"https://doi.org/10.1039/d5sc01889g","url":null,"abstract":"Aqueous zinc-ion batteries (AZIBs) are gaining significant attention due to their excellent safety, cost-effectiveness, and environmental friendliness, making them highly competitive energy storage solutions. Despite these advantages, the commercial application of AZIBs faces substantial challenges, particularly those related to performance limitations of cathode materials. Among potential candidates, vanadium dioxide (VO<small>₂</small>) stands out due to its exceptional electrochemical properties and unique crystal structure, rendering it a promising cathode material for AZIB applications. The review summarizes the recent research progress on VO<small>₂</small> in AZIBs, analyzes its crystal structures (tetragonal VO<small>₂</small>(A), monoclinic VO<small>₂</small>(B, D, M), and rutile VO<small>₂</small>(R)), morphology and energy storage mechanisms (Zn<small>²⁺</small> insertion/extraction, H<small>⁺</small>/Zn<small>²⁺</small> co-insertion/extraction, and chemical reaction mechanism), and discusses the relationship between the structure and performance. The review also addresses key challenges associated with VO<small>₂</small> as a cathode material, including dissolution, by-product formation, and limited ion diffusion kinetics. To overcome these issues, various optimization strategies are systematically discussed, such as ion/molecule pre-intercalation, composite material fabrication, defect engineering, and elemental doping. Finally, potential research directions and strategies to further enhance the performance and commercial viability of VO<small>₂</small>-based cathodes are proposed.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"33 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872436","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":"Photoinduced carbonylative annulation access to β-lactams","authors":"Yuanrui Wang, Xin Qi, Zhipeng Bao, Xiao-Feng Wu","doi":"10.1039/d5sc02418h","DOIUrl":"https://doi.org/10.1039/d5sc02418h","url":null,"abstract":"In radical carbonylation chemistry, orderly and sequential construction of C-C and C-N bonds with CO can effectively approach amide units and quickly incorporate a wide range of functional groups. However, this procedure remains underdeveloped for the synthesis of β-lactams. In general, especially for four-membered rings, end-to-end annulation is a thermodynamically unfavorable process compared to [2+2] cycloaddition. Here we developed a photoinduced radical relay carbonylative annulation (RRCA) strategy in which the key β-amino acyl radical intermediates exhibit superior capability of cyclization. This unique and underrated property is crucial in the process of successfully overcoming the tension of four-membered annulation for the synthesis of β-lactams. Mild conditions and widely substrate compatibility indicate the value of this method in the field of new drug discovery with special therapeutic effects. Particularly, embedding the amine group of the amino acid into the β-lactam skeleton further illustrate the utility of this methodology enabling late-stage modification of bioactive molecules.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"26 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872438","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}