Chemical Science最新文献

{"title":"Ligand-induced Changes in the Electrocatalytic Activity of Atomically Precise Au₂₅ Nanoclusters","authors":"Lipan Luo, Xia Zhou, Yuping Chen, Fang Sun, Likai Wang, Qing Tang","doi":"10.1039/d4sc07181f","DOIUrl":"https://doi.org/10.1039/d4sc07181f","url":null,"abstract":"Atomically precise gold nanoclusters have shown great promise as model elctrocatalysts in pivotal electrocatalytic processes such as hydrogen evolution reaction (HER) and carbon dioxide reduction reaction (CO2RR). Although the influence of ligands on the electronic properties of these nanoclusters are well acknowledged, the ligand effects on their electrocatalytic performances have been rarely explored. Herein, using [Au25(SR)18]- nanocluster as the prototype model, we demonstrated the importance of ligand hydrophilicity versus hydrophobicity in modulating the interface dynamics and electrocatalytic performance. Our first-principle computations revealed that Au25 protected by hydrophilic -SCH2COOH ligands dictates faster kinetics in stripping the thiolate ligand and exhibits better HER activity due to enhanced proton transfer facilitated by boosted interface hydrogen bonding. Conversely, Au25 protected by hydrophobic -SCH2CH3 ligands demonstrates enhanced CO2RR performance by minimizing water interference to stabilize the key *COOH intermediate and lower the barrier for CO formation. Experimental validation using synthesized hydrophilic and hydrophobic ligand-protected Au25 nanoclusters (NCs), such as [Au25(MPA)18]- (MPA = Mercaptopropionic acid), [Au25(MHA)18]- (MHA = 6-Mercaptohexanoic acid), and [Au25(SC6H13)18]-, confirms these findings, where the hydrophilic ligand-protected Au25 NCs exhibit better activity and stability in HER, while the hydrophobic ligand-protected Au25 NCs achieve higher Faradaic efficiency and current density in CO2RR. The mechanistic insights in this study provide valuable guidance for the rational design of surface microenvironment in efficient nanocatalysts for sustainable energy applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"18 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990196","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":"Dynamics and Kinetic Exploration of Oxygen Reduction Reaction at Fe-N4/C-water Interface Accelerated by Machine Learning Force Field","authors":"Qinghan Yu, Pai Li, Xing Ni, Youyong Li, Lu Wang","doi":"10.1039/d4sc06422d","DOIUrl":"https://doi.org/10.1039/d4sc06422d","url":null,"abstract":"Understanding the oxygen reduction reaction (ORR) mechanism and accurately characterizing the reaction interface are essential for improving fuel cell efficiency. We developed an active learning framework combining utilized machine learning force fields and enhanced sampling to explore dynamics and kinetics of ORR on Fe-N4/C under a fully explicit solvent model. Different possible reaction paths have been explored and the O2 adsorption process is confirmed as the rate-determining step of ORR at the Fe-N4/C-water interface, which needs to overcome a free energy barrier of 0.39 eV. By statistical analysis of solvent configurations for proton-coupled electron transfer (PCET) processes, it is revealed that the configurations of interface water remarkably influence the reaction efficiency. More hydrogen bonds and longer lifetime facilitates the PCET reactions and even make them barrierless. Our theoretical framework highlights the significance of solvent configurations in determining free energy barriers, and offers new insights into the reaction mechanism of ORR on Fe-N4/C catalysts.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"74 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990157","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":"Recent advances in synthesis and application of Magnéli phase titanium oxides for energy storage and environmental remediation","authors":"S. Amanda Ekanayake, Haoxin Mai, Dehong Chen, Rachel A. Caruso","doi":"10.1039/d4sc04477k","DOIUrl":"https://doi.org/10.1039/d4sc04477k","url":null,"abstract":"High-temperature reduction of TiO<small>₂</small> causes the gradual formation of structural defects, leading to oxygen vacancy planar defects and giving rise to Magnéli phases, which are substoichiometric titanium oxides that follow the formula Ti<small>_<em>n</em></small>O<small>_{2<em>n</em>−1}</small>, with 4 ≤ <em>n</em> ≤ 9. A high concentration of defects provides several possible configurations for Ti<small>⁴⁺</small> and Ti<small>³⁺</small> within the crystal, with the variation in charge ordered states changing the electronic structure of the material. The changes in crystal and electronic structures of Magnéli phases introduce unique properties absent in TiO<small>₂</small>, facilitating their diverse applications. Their exceptional electrical conductivity, stability in harsh chemical environments and capability to generate hydroxyl radicals make them highly valuable in electrochemical applications. Additionally, their high specific capacity and corrosion resistance make them ideal for energy storage facilities. These properties, combined with excellent solar light absorption, have led to their widespread use in electrochemical, photochemical, photothermal, catalytic and energy storage applications. To provide a complete overview of the formation, properties, and environmental- and energy-related applications of Magnéli phase titanium suboxides, this review initially highlights the crystal structure and the physical, thermoelectrical and optical properties of these materials. The conventional and novel strategies developed to synthesise these materials are then discussed, along with potential approaches to overcome challenges associated with current issues and future low-energy fabrication methods. Finally, we provide a comprehensive overview of their applications across various fields, including environmental remediation, energy storage, and thermoelectric and optoelectronic technologies. We also discuss promising new directions for the use of Magnéli phase titanium suboxides and solutions to challenges in energy and environment-related applications, and provide guidance on how these materials can be developed and utilised to meet diverse research application needs. By making use of control measures to mitigate the potential hazards associated with their nanoparticles, Magnéli phases can be considered as versatile materials with potential for next generation energy needs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"31 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990195","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":"Potent inhibitors of the human RNA ligase Rlig1 highlights its role in RNA integrity maintenance under oxidative cellular stress","authors":"Lisa A. Schlor, Maya Peußner, Silke Müller, Andreas Marx","doi":"10.1039/d4sc06542e","DOIUrl":"https://doi.org/10.1039/d4sc06542e","url":null,"abstract":"Human RNA ligase 1 (Rlig1) calalyzes the ligation of 5’-phosphate to 3’-hydroxyl ends via a conserved three-step mechanism. Rlig1-deficient HEK293 cells exhibit reduced cell viability and RNA integrity under oxidative stress, suggesting Rlig1’s role in RNA repair maintenance. Reactive oxygen species (ROS) are linked to various diseases, including neurodegenerative disorders and cancers, where RNA damage has significant effects. This study identifies and characterizes Rlig1 inhibitors to elucidate its role in RNA metabolism. We developed a fluorescence resonance energy transfer (FRET)-based assay to monitor RNA ligation and screened a library of 13,026 bioactive small molecules. SGI-1027 emerged as a promising lead compound, and structure-activity relationship (SAR) studies revealed that the terminal residues play a key role in its inhibitory effect. In total 22 SGI-1027 derivatives were synthesized and tested, providing insights into the structural requirements for effective Rlig1 inhibition. Three derivatives showed low micromolar IC50 values and minimal cytotoxicity in HEK293 cells under physiological conditions. The combination of Rlig1 inhibition and oxidative stress led to reduced cell viability and compromised RNA integrity, reinforcing Rlig1's role in RNA maintenance. These findings provide a foundation for developing novel therapeutics aimed at targeting RNA maintenance pathways in conditions of dysregulated ROS levels.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"26 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142989468","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":"Thiosemicarbazones as versatile photoswitches with light-controllable supramolecular activity","authors":"Bengi Sentürk, Burkhard Butschke, Fabian Eisenreich","doi":"10.1039/d4sc08530b","DOIUrl":"https://doi.org/10.1039/d4sc08530b","url":null,"abstract":"Using photoswitchable molecules to manipulate supramolecular interactions under light illumination has driven advancements in numerous fields, allowing for the strategic alteration of molecular systems. However, integrating the moiety responsible for these interactions into the photochromic scaffold can be complex and may hamper the switching efficiency. We thus explored a simple class of organic molecules, namely thiosemicarbazones, featuring both a photoisomerizable C<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/>N double bond and a thiourea moiety capable of hydrogen bonding. The scalable two-step synthesis allowed us to prepare 23 thiosemicarbazones to systematically elucidate their optical properties. Attaching various functional groups, extended π-systems, and heterocycles enabled fine-tuning of their absorption profiles. UV light illumination converts thiosemicarbazones from the stable <em>E</em>-isomer to the metastable <em>Z</em>-isomer, exhibiting both negative and positive T-type photochromism, a wide range of thermal half-lives, PSS values up to 92%, and high fatigue resistance. Substituting the C<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/>N moiety with a pyridinyl group stabilizes the <em>Z</em>-isomer <em>via</em> intramolecular hydrogen bonding, confirmed by single-crystal X-ray analysis, and transforms thiosemicarbazones into bistable P-type photoswitches. Additionally, thiosemicarbazones dimerize or form aggregates through hydrogen bonding—a process that can be turned off or on with light. Overall, thiosemicarbazones offer tunable photochromic and supramolecular properties, rendering them a promising photoswitch for creating stimuli-responsive systems.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988377","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":"In Silico Screening of P,N-Ligands Facilitates Optimization of Au(III)-Mediated S-Arylation","authors":"Joseph Treacy, James A. R. Tilden, Elaine Y. Chao, Zihuan Fu, Alex Spokoyny, K. N. Houk, Heather Maynard","doi":"10.1039/d4sc05920d","DOIUrl":"https://doi.org/10.1039/d4sc05920d","url":null,"abstract":"Metal-mediated cysteine <em>S</em>-arylation is an emerging bioconjugation technique due to its high chemoselectivity, rapid kinetics, and aqueous compatibility. We have previously demonstrated that by altering the sterics of the ligand and aryl groups of an Au(III) oxidative addition complex, one can modulate the kinetics of the bimolecular coordination and induce rate constants up to 16,600 m<small>⁻</small><small>¹</small>s<small>⁻</small><small>¹</small>. To further enhance the rate of coordination, density functional theory (DFT) calculations were performed to investigate the steric properties of the <em>P</em>,<em>N</em>-ligated Au(III) oxidative addition complex as well as the thermodynamics of the <em>S</em>-arylation reaction. This allowed for the accelerated screening of 13 new Au(III) oxidative addition complexes. Three of these more sterically promising, synthetically available <em>P</em>,<em>N</em>-ligands were synthesized, incorporated into Au(I) and Au(III) complexes, and the rates studied experimentally. The comprehensive mechanistic insights from the DFT calculations led to the development of new reagents with bimolecular coordination rate constants as fast as 20,200 m<small>⁻</small><small>¹</small>s<small>⁻</small><small>¹</small>. Further experimental characterization of these reagents’ efficacy as <em>S</em>-arylation reagents led to a proposed switch in selectivity-determining step for the fastest reagent, which was further confirmed by profiling the reductive elimination kinetics. This work provides a concise workflow for the screening of metal-mediated cysteine <em>S</em>-arylation reagents and new fundamental insights into the coordination chemistry behavior of Au(III) systems.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"54 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986624","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":"Inhibiting Homogeneous Catalysis of Cobalt Ions towards Stable Battery Cycling of LiCoO2 at 4.6 V","authors":"Chao Sun, Bing Zhao, Qing Wen, Xiang-tao Chen, Ningyun Hong, Jinbo Zeng, Jiafeng Zhang, Lingjun Li, Jiexi Wang, Xiahui Zhang, Junchao Zheng","doi":"10.1039/d4sc07831d","DOIUrl":"https://doi.org/10.1039/d4sc07831d","url":null,"abstract":"Raising cut-off voltage increases the energy density of LiCoO2 for lithium-ion batteries, but it exacerbates the decomposition of the electrolyte and the capacity decay of LiCoO2. To address such issues, many artificial cathode-electrolyte-interphase (CEI) are constructed to stabilize the cathode interface by additive. However, it is rarely explored for the electrolyte degradation by catalytic oxidation of Co ions dissolved in the electrolytes. Herein, we report a new strategy of additive engineering towards the enhanced cycling stability of LiCoO2 at 4.6 V. We found that the Co4+ ions dissolved in the electrolyte due to interfacial failure degrades the electrolyte rapidly by homogeneous catalysis, which can be deactivated by chelation reaction of nitrilotri(methylphosphonic acid) (ATMP) additive with Co4+. Benefiting from the deactivated Co ions by ATMP, the catalytic oxidation of the electrolyte is suppressed, which is more stable to the LiCoO2 interface than the artificially constructed CEI, and thus the LiCoO2 cathode delivers a high capacity of 197.7 mAh g-1 after 200 cycles at 4.6 V with a retention rate of 91.4%. This work provides new insights into additive engineering towards stable cathode/electrolyte interfaces for next-generation batteries.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"54 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986848","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 the Solid Electrolyte Interphase for Enhancing High-Rate Cycling and Temperature Adaptability of Lithium-Ion Batteries","authors":"Zhongming Wang, Zhiyuan He, Zhongsheng Wang, Kecheng Long, Jixu Yang, Shaozhen Huang, Zhibin Wu, Lin Mei, Libao Chen","doi":"10.1039/d4sc07916g","DOIUrl":"https://doi.org/10.1039/d4sc07916g","url":null,"abstract":"In overcoming the barrier of rapid Li+ transfer in lithium-ion batteries under extreme temperatures, the desolvation process and interfacial charge transport play critical roles. However, tunning the solvation structure and designing kinetically-stable electrode-electrolyte interface to achieve high-rate charging and discharging remains challenges. Here, a lithium nonafluoro-1-butanesulfonate (NFSALi) additive is introduced to optimize a stability and robust solid electrolyte interface film (SEI), realizing the rapid Li+ transfer process and the structural integrity of electrode materials. The NFSALi-derived thinner, fluorine-rich, and sulfur-containing SEI in nitrile-assistant carbonate electrolytes effectively suppresses decomposition of valeronitrile solvent during high-rate cycling and wide-temperature operation (−40~55 ℃). More importantly, the graphiteǁLiNi0.5Co0.2Mn0.3O2 pouch cell demonstrates a capacity retention of 66.88% after 200 high-rate cycles with 3 C charging and 5 C discharging at a high-temperature condition of 55 °C. This work provides significant guidance to develop inorganic-rich interfacial chemistry for lithium-ion batteries under extreme operating conditions.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"96 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986622","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":"Ruthenium-catalyzed C–H bond activation and annulation of phenothiazine-3-carbaldehydes: facile access to dual-emission materials","authors":"Junxiang Liu, Kangmin Wang, Liqiu Wan, Xianhui Yang, Bijin Li","doi":"10.1039/d4sc07825j","DOIUrl":"https://doi.org/10.1039/d4sc07825j","url":null,"abstract":"Reported herein is the first example of a ruthenium-catalyzed C–H activation/annulation of phenothiazine-3-carbaldehydes to construct structurally diverse pyrido[3,4-<em>c</em>]phenothiazin-3-iums with dual-emission characteristics. Novel organic single-molecule white-light materials based on pyrido[3,4-<em>c</em>]phenothiazin-3-iums with dual-emission and thermally activated delayed fluorescence (TADF) characteristics have been developed for the first time herein. Furthermore, the dual-emission molecule could be fabricated as water-dispersed NPs, which could be applied in two-channel emission intensity ratio imaging to observe the intercellular structure and can specifically target the cell membrane.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"42 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986623","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 0D to 2D: Microwave-assisted Synthesis of Electrically Conductive Metal-Organic Frameworks with Controlled Morphologies","authors":"Xiaoyu Fang, Ji Yong Choi, Chenwei Lu, Elizabeth Reichert, Hoai T. B. Pham, Jihye Park","doi":"10.1039/d4sc07025a","DOIUrl":"https://doi.org/10.1039/d4sc07025a","url":null,"abstract":"Morphology control of electrically conductive metal-organic frameworks (EC-MOFs) can be a powerful means to tune their surface area and carrier transport pathways, particularly beneficial for energy conversion and storage. However, controlling EC-MOFs’ morphology is underexplored due to the uncontrollable crystal nucleation and rapid growth kinetics. This work introduces a microwave-assisted strategy to readily synthesize Cu-HHTP (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) with controlled morphologies. We employed modulators to facilitate particles’ directional growth to 1D and 2D crystals. Meanwhile, we found that ultrasonication can manipulate crystal seeding, yielding 0D spherical Cu-HHTP crystals. Electronic conductivity measurements suggest that the isotropic nature of the 0D crystals allows a conductivity of 7.34 × 10<small>^-1</small> S cm<small>^-1</small>, much higher than <strong>1D and 2D counterparts’</strong>. Additionally, the controlled 0D morphology enhanced the material’s capacitance and effective surface area and significantly improved its photocurrent response. These findings underscore the pivotal impact of controlled morphology in optimizing EC-MOFs’ physicochemical properties.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"96 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986851","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}