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Probing the Freezing Chemistry of Singly Levitated Aqueous Trifluoroacetic Acid Droplets in a Cryogenically Cooled Simulation Chamber Relevant to Earth’s Upper Troposphere 在与地球对流层上层相关的低温冷却模拟室内探测单悬浮三氟乙酸液滴的冻结化学
IF 8.4 1区 化学
Chemical Science Pub Date : 2025-05-10 DOI: 10.1039/d5sc01698c
Koushik Mondal, Souvick Biswas, Nils Wrangell Melbourne, Rui Sun, Ralf I. Kaiser
{"title":"Probing the Freezing Chemistry of Singly Levitated Aqueous Trifluoroacetic Acid Droplets in a Cryogenically Cooled Simulation Chamber Relevant to Earth’s Upper Troposphere","authors":"Koushik Mondal, Souvick Biswas, Nils Wrangell Melbourne, Rui Sun, Ralf I. Kaiser","doi":"10.1039/d5sc01698c","DOIUrl":"https://doi.org/10.1039/d5sc01698c","url":null,"abstract":"Trifluoroacetic acid (CF<small><sub>3</sub></small>COOH, TFA), the primary upper terrestrial atmosphere degradation product of several fluorinated hydrocarbons primarily used as refrigerants, poses a significant environmental challenge due to its growing atmospheric accumulation and extremely low reactivity. This combined experimental and theoretical study of TFA-doped water droplets, conducted inside a cryogenically cooled ultrasonic levitator simulation chamber utilizing time-dependent Raman spectroscopy and optical visualization techniques, addresses the dynamic chemical changes during the freezing event for the first time. The low-temperature experimental approach mimics TFA's interactions within water droplets in the upper troposphere and arctic regions, particularly at subzero temperatures. Key findings reveal structural transformation towards the formation of undissociated neutral TFA in hexagonal ice environments compared to the anionic form, providing fundamental insight into the role of TFA in ice nucleation. Furthermore, state-of-the-art electronic structure calculations provide insights into the stability of this undissociated TFA within the hexagonal ice-encapsulated environment, wherein structural distortions of the regular hexagonal ice crystal and secondary F—H interactions mostly between anionic TFA forms and the ice lattice are evidenced at the molecular level. This research untangles the chemical insight to the TFA on ice nucleation leading to cloud glaciation, hence providing a plausible reason behind its presence in remote arctic regions through long-range transport.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"7 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143930838","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}
引用次数: 0
Multifunctional Cytochrome P450 Orchestrates Radical Cleavage and Non-radical Cyclization in 5-Oxaindolizidine Biosynthesis 多功能细胞色素P450在5-氧苯多利嗪生物合成中协调自由基切割和非自由基环化
IF 8.4 1区 化学
Chemical Science Pub Date : 2025-05-10 DOI: 10.1039/d4sc07174c
Kaijin Zhang, Jingxian Sun, Wencai Song, Junyu Liu, Chuanteng Ma, Ying-Han Chen, Yan Guan, Yuting Liu, Zilin Ren, Qian Che, Guojian Zhang, Yankai Liu, Tianjiao Zhu, Dehai Li
{"title":"Multifunctional Cytochrome P450 Orchestrates Radical Cleavage and Non-radical Cyclization in 5-Oxaindolizidine Biosynthesis","authors":"Kaijin Zhang, Jingxian Sun, Wencai Song, Junyu Liu, Chuanteng Ma, Ying-Han Chen, Yan Guan, Yuting Liu, Zilin Ren, Qian Che, Guojian Zhang, Yankai Liu, Tianjiao Zhu, Dehai Li","doi":"10.1039/d4sc07174c","DOIUrl":"https://doi.org/10.1039/d4sc07174c","url":null,"abstract":"Penicilactam A (1), a fungal alkaloid featuring a rare 5-oxaindolizidine scaffold, has long eluded biosynthetic characterization despite recent advances in microbial genomics. Through retro-biosynthetic analysis of Penicillium citrinum HDN11-186, we identified the pnlt gene cluster governing its production. This pathway ultilizes a hybrid polyketide synthase-nonribosomal peptide synthetase (PKS-NRPS) system to assemble the prolinol-containing precursor scalusamide A (2). The multifunctional cytochrome P450 enzyme PnltC then orchestrates two mechanistically distinct reactions: radical-mediated C–C bond cleavage followed by iminium-driven cyclization. Combined structural and computational analyses unveil PnltC’s unprecedented catalytic logic, merging radical oxidation with non-radical cyclization within a single active site, which challenges existing paradigms of P450 enzymology. Our findings expand the functional repertore of oxygenases in natural products (NPs) biosynthesis, revealing nature’s sophisticated strategies for constructing complex nitrogen heterocycles.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"42 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143930845","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}
引用次数: 0
Widespread False Negatives in DNA-Encoded Library Data: How Linker Effects Impair Machine Learning-Based Lead Prediction dna编码文库数据中普遍存在的假阴性:链接器效应如何损害基于机器学习的先导预测
IF 8.4 1区 化学
Chemical Science Pub Date : 2025-05-09 DOI: 10.1039/d5sc00844a
Alba Lucia Montoya Arias, Adam Hogendorf, Steven Tingey, Aadarsh Kuberan, Lik Hang Yuen, Herwig Schüler, Raphael Franzini
{"title":"Widespread False Negatives in DNA-Encoded Library Data: How Linker Effects Impair Machine Learning-Based Lead Prediction","authors":"Alba Lucia Montoya Arias, Adam Hogendorf, Steven Tingey, Aadarsh Kuberan, Lik Hang Yuen, Herwig Schüler, Raphael Franzini","doi":"10.1039/d5sc00844a","DOIUrl":"https://doi.org/10.1039/d5sc00844a","url":null,"abstract":"DNA-encoded chemical libraries (DECLs) have become integral to early-stage drug discovery, yielding active compounds and extensive labeled datasets for machine learning (ML)-based prediction of bioactive molecules. However, the information content of DECL selection data remains scarcely explored. This study systematically investigates for the first time the prevalence of false negatives and the influence of the linker in DECL data. Using a focused DECL targeting the poly-(ADP-ribose) polymerases PARP1/2 and TNKS1/2 as a model system, we found that our DECL selections frequently miss active compounds, with numerous false negatives for each identified hit. The presence of the DNA-conjugation linker emerged as a factor contributing to the underdetection of active molecules. This bias toward false negatives compromises the predictive power of DECL data for prioritizing hits, anticipating target selectivity, and training ML models, as determined by analyzing the effects of undersampling and oversampling techniques in learning the PARP2 data. Conversely, the linker’s presence in DECLs offers advantages, such as enabling the identification of target-selective protein engagers, even when the underlying molecules themselves may not be selective. These findings highlight the challenges and opportunities of DECL data, emphasizing the need for best practices in data handling and ML model development in drug discovery.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"10 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143930843","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}
引用次数: 0
Precise construction of spiro stereocenters via enantioselective radical addition through modulating photocatalysis from redox to energy transfer 通过调节光催化从氧化还原到能量转移,通过对映选择性自由基加成精确构建螺旋立体中心
IF 8.4 1区 化学
Chemical Science Pub Date : 2025-05-09 DOI: 10.1039/d5sc01583a
Fayu Liu, Yanqi Guo, Weidong Lu, Xiaowei Zhao, Yanli Yin, Zhiyong Jiang
{"title":"Precise construction of spiro stereocenters via enantioselective radical addition through modulating photocatalysis from redox to energy transfer","authors":"Fayu Liu, Yanqi Guo, Weidong Lu, Xiaowei Zhao, Yanli Yin, Zhiyong Jiang","doi":"10.1039/d5sc01583a","DOIUrl":"https://doi.org/10.1039/d5sc01583a","url":null,"abstract":"Chiral hydrogen-bonding catalysis has been successfully applied in a wide range of asymmetric photocatalytic radical-based reactions. However, it faces intrinsic challenges in the reactions that rely on oxidative quenching to initiate transformations. A critical issue arises from the formation of anionic side intermediates, which preferentially interact with protons from chiral catalysts, undermining the essential enantiocontrol required for effective product formation. In this study, we demonstrate that creating energy transfer instead of single-electron transfer to trigger these transformations presents a promising solution. As a proof-of-concept, we report the first photocatalytic spirocyclization of olefinic sulfonyl oximes with vinyl azides, furnishing a diverse array of spiroaminals with high yields (up to 94%) and enantioselectivities (up to 99% ee). The success of this method hinges on employing a sulfonyl group as an <em>N</em>-protective group for oximes, which facilitates energy transfer as an alternative mechanism to initiate the transformation. This approach not only enhances reactivity and chemoselectivity but also creates an optimal environment for enantiocontrol. The synthetic significance of this work is underscored by the establishment of these products as a novel class of chiral ligands, with preliminary studies indicating their effectiveness in asymmetric alkynylation reactions.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"148 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143946070","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}
引用次数: 0
Correlative analysis of Ni(ii) coordination states in molten salts using a combination of X-ray and optical spectroscopies and simulations. 熔盐中Ni(ii)配位态的x射线、光谱及模拟分析
IF 7.6 1区 化学
Chemical Science Pub Date : 2025-05-09 DOI: 10.1039/d5sc01059d
Yang Liu, Mehmet Topsakal, Kaifeng Zheng, Luis E Betancourt, Michael Woods, Santanu Roy, Nirmalendu Patra, Denis Leshchev, Phillip Halstenberg, Dmitry S Maltsev, Sheng Dai, Alexander S Ivanov, Vyacheslav S Bryantsev, James F Wishart, Ruchi Gakhar, Anatoly I Frenkel, Simerjeet K Gill
{"title":"Correlative analysis of Ni(ii) coordination states in molten salts using a combination of X-ray and optical spectroscopies and simulations.","authors":"Yang Liu, Mehmet Topsakal, Kaifeng Zheng, Luis E Betancourt, Michael Woods, Santanu Roy, Nirmalendu Patra, Denis Leshchev, Phillip Halstenberg, Dmitry S Maltsev, Sheng Dai, Alexander S Ivanov, Vyacheslav S Bryantsev, James F Wishart, Ruchi Gakhar, Anatoly I Frenkel, Simerjeet K Gill","doi":"10.1039/d5sc01059d","DOIUrl":"https://doi.org/10.1039/d5sc01059d","url":null,"abstract":"<p><p>Understanding the factors that control the speciation of metal ions in molten salts is crucial for the successful deployment of molten salts in both concentrated solar power and nuclear energy applications. The speciation of the Ni(ii) ion is of interest because it is a common corrosion product, and the distribution of coordination states it occupies is highly sensitive to the molten salt matrix. We employ <i>in situ</i> X-ray absorption spectroscopy (XAS), optical spectroscopy, and <i>ab initio</i> molecular dynamics (AIMD) simulations to investigate and understand the heterogeneities of Ni(ii) coordination in LiCl-KCl, NaCl-MgCl<sub>2,</sub> and LiCl-ZnCl<sub>2</sub> molten salt systems. The main challenge lies in identifying the population distribution of Ni(ii) coordination states as a function of temperature and melt composition. We combined the multivariate curve resolution - alternating least squares (MCR-ALS) analysis of the XAS data and principal component analysis (PCA) of the optical spectra to determine the number of unique coordination states coexisting in the molten state, extract X-ray spectra for each state, and obtain their mixing fractions at different temperatures and for different salt mixtures. AIMD simulations were essential in identifying the coordination states corresponding to the deconvoluted spectra. The differences in the coordination states of Ni(ii) in different salt systems are discussed in terms of the effects of the varying polarizing powers of the cations in the host salt matrix on chloride ion coordination to Ni(ii). Such elucidation of the local structure adopted by metal ions enables a better understanding of the factors controlling the speciation of ions and their effect on molten salt properties.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12063551/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143981640","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}
引用次数: 0
3MMLCT excited states of luminescent binuclear PdII complexes: excited state inner-sphere electron-transfer reactions and application 发光双核PdII配合物的3MMLCT激发态:激发态内球电子转移反应及其应用
IF 8.4 1区 化学
Chemical Science Pub Date : 2025-05-08 DOI: 10.1039/d4sc08612k
Chi-Ming Che, Minying Xue, Wai-Pong To, Gang Cheng, Yuzhen Zhang, Zhou Tang, Lili Du, Kam-Hung Low, Qingyun Wan
{"title":"3MMLCT excited states of luminescent binuclear PdII complexes: excited state inner-sphere electron-transfer reactions and application","authors":"Chi-Ming Che, Minying Xue, Wai-Pong To, Gang Cheng, Yuzhen Zhang, Zhou Tang, Lili Du, Kam-Hung Low, Qingyun Wan","doi":"10.1039/d4sc08612k","DOIUrl":"https://doi.org/10.1039/d4sc08612k","url":null,"abstract":"Compared with PtII analogues that exhibit unique stimulus-induced switching luminescence properties and novel material applications, the properties and reactivity of the 3MMLCT excited state of PdII complexes in solutions are under-developed. Here, we prepared a series of binuclear cyclometalated PdII complexes with short intramolecular Pd-Pd distances of 2.79–2.89 Å and luminescent 3MMLCT excited states in solutions at 298 K (emission quantum yield and radiative decay rate constant up to 0.70 and 2×105 s-1, respectively). Their photo-physical properties have been examined by femtosecond time-resolved absorption spectroscopy, and the 1e oxidation products of binuclear PdII complexes have been studied by electron paramagnetic resonance spectroscopy and computational studies. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations show that changing the C-deprotonated aryl pyridine (C^N) ligand to the strong σ-donor aryl N-heterocyclic carbene (C^C*) ligand significantly increases the energy level of the metal centered (3dd) excited state. The binuclear PdII complex with a redox-active formamidinate bridging ligand reacts with benzyl bromide to immediately generate PdII-PdIII-Br species upon light irradiation. Quenching and time-resolved absorption experiments show that the PdII-3MMLCT excited state reacts with alkyl bromides via an inner-sphere electron transfer pathway. These binuclear PdII complexes were examined as organic light-emitting diode (OLED) emitters and photocatalysts for C-C bond formation reactions.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"286 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143920236","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}
引用次数: 0
Multinitrogen π-Conjugated Conductive Polymer Stabilizing Ultra-Large Interlayer Spacing in Vanadium Oxides for High-Performance Aqueous Zinc-Ion Batteries 多氮π共轭导电聚合物稳定高性能水锌离子电池中钒氧化物的超大层间距
IF 8.4 1区 化学
Chemical Science Pub Date : 2025-05-08 DOI: 10.1039/d5sc01545f
Weijian Li, Kaiyue Zhu, Weikang Jiang, Hanmiao Yang, Weili Xie, Zhengsen Wang, Weishen Yang
{"title":"Multinitrogen π-Conjugated Conductive Polymer Stabilizing Ultra-Large Interlayer Spacing in Vanadium Oxides for High-Performance Aqueous Zinc-Ion Batteries","authors":"Weijian Li, Kaiyue Zhu, Weikang Jiang, Hanmiao Yang, Weili Xie, Zhengsen Wang, Weishen Yang","doi":"10.1039/d5sc01545f","DOIUrl":"https://doi.org/10.1039/d5sc01545f","url":null,"abstract":"Rechargeable aqueous zinc-ion batteries (ZIBs) have attracted increasing attention in the field of electrochemical energy storage (EES) because of their remarkable features, including high theoretical capacity, cost-effectiveness, environmental friendliness, and inherent safety. However, the realization of high-performance cathodes with both high specific capacity and outstanding cycling stability in ZIBs remains challenging. In this work, we present the design of a novel conductive polymer, poly-[2,2'-bipyridin]-5-amine (PBpyA), and report the successful in situ intercalation synthesis of PBpyA-intercalated V<small><sub>2</sub></small>O<small><sub>5</sub></small>·nH<small><sub>2</sub></small>O xerogels (designated as PBVO). PBVO exhibits exceptional structural stability, attributed to the robust π-conjugation within PBpyA, which effectively stabilizes V<small><sub>2</sub></small>O<small><sub>5</sub></small> bilayers. Moreover, PBVO features a significantly enlarged interlayer spacing of 14.1 Å, facilitating efficient intercalation/extraction of Zn<small><sup>2+</sup></small>. As a cathode material for ZIBs, PBVO demonstrates excellent electrochemical performance, delivering a high specific capacity of 454.6 mAh g<small><sup>-1</sup></small> at 0.1 A g<small><sup>-1</sup></small>) and exhibiting remarkable cycling stability, with 97 % capacity retention after 150 cycles at 0.2 A g<small><sup>-1</sup></small> and 84 % capacity retention after 2000 cycles at 5 A g<small><sup>-1</sup></small>. These findings position PBVO as a highly promising candidate for high-capacity and ultra-stable ZIB cathodes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"31 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143920238","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}
引用次数: 0
Phase effect of TiO2 on surface hydrogen adsorption/desorption in controlling photocatalytic methane conversion TiO2对表面氢吸附/解吸控制光催化甲烷转化的相效应
IF 8.4 1区 化学
Chemical Science Pub Date : 2025-05-08 DOI: 10.1039/d5sc00888c
Jiakang You, Ardeshir Baktash, Dazhi Yao, Yanzhao Zhang, Shanshan Ding, Jingwei Hou, Guangyu Zhao, Yonggang Jin, Zhiliang Wang, Lianzhou Wang
{"title":"Phase effect of TiO2 on surface hydrogen adsorption/desorption in controlling photocatalytic methane conversion","authors":"Jiakang You, Ardeshir Baktash, Dazhi Yao, Yanzhao Zhang, Shanshan Ding, Jingwei Hou, Guangyu Zhao, Yonggang Jin, Zhiliang Wang, Lianzhou Wang","doi":"10.1039/d5sc00888c","DOIUrl":"https://doi.org/10.1039/d5sc00888c","url":null,"abstract":"Identifying the rate-determining step is crucial for designing an effective photocatalytic system. The surface adsorption/desorption behaviour of reactants has received much less attention in photocatalyst design because the charge separation and transfer in the bulk is commonly regarded as a more sluggish process. In this work, we investigate photocatalytic methane (CH<small><sub>4</sub></small>) conversion (PMC) on various titanium oxide (TiO<small><sub>2</sub></small>) surfaces, including rutile and anatase, and reveal that the influence of surface CH<small><sub>4</sub></small> adsorption can outweigh the photogenerated charge separation and transfer. Specifically, the rutile TiO<small><sub>2</sub></small> surface is totally inert for CH<small><sub>4</sub></small> activation. Further theoretical calculations reveal the significance of the hydrogen-adsorption/desorption process during the initial C–H bond cleavage on the TiO<small><sub>2</sub></small> surface. A reversible hydrogen adsorption/desorption process with a small Gibbs free energy not only enables the activation of the first C–H bond in CH<small><sub>4</sub></small> but also ensures a timely clearance of surface-adsorbed species, leading to a continuous PMC process. The findings of the phase effect study on the interaction between the photocatalyst surface and hydrogen atoms provide new insights into the rational design of efficient photocatalysts towards PMC. It also highlights the gap in transferring the knowledge of photocatalytic water splitting into PMC.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"14 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143920294","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}
引用次数: 0
Li3.6In7S11.8Cl: an air- and moisture-stable superionic conductor Li3.6In7S11.8Cl:空气和水分稳定的超离子导体
IF 8.4 1区 化学
Chemical Science Pub Date : 2025-05-08 DOI: 10.1039/d5sc01907a
Ifeoluwa P. Oyekunle, Erica Truong, Tej P. Poudel, Yudan Chen, Yongkang Jin, Islamiyat A. Ojelade, Michael J. Deck, Bright Ogbolu, Md. Mahinur Islam, Pawan K. Ojha, J. S. Raaj Vellore Winfred, Dewen Hou, Hui Xiong, Chen Huang, Yan-Yan Hu
{"title":"Li3.6In7S11.8Cl: an air- and moisture-stable superionic conductor","authors":"Ifeoluwa P. Oyekunle, Erica Truong, Tej P. Poudel, Yudan Chen, Yongkang Jin, Islamiyat A. Ojelade, Michael J. Deck, Bright Ogbolu, Md. Mahinur Islam, Pawan K. Ojha, J. S. Raaj Vellore Winfred, Dewen Hou, Hui Xiong, Chen Huang, Yan-Yan Hu","doi":"10.1039/d5sc01907a","DOIUrl":"https://doi.org/10.1039/d5sc01907a","url":null,"abstract":"All-solid-state batteries (ASSBs) have drawn significant attention as future energy storage technologies. Sulfide-based solid electrolytes are promising due to their high ionic conductivity and favorable mechanical properties. However, their reactivity with moisture, leading to decomposition and release of toxic gases such as H<small><sub>2</sub></small>S, poses health and safety risks. In this study, a superionic conductor, Li<small><sub>3.6</sub></small>In<small><sub>7</sub></small>S<small><sub>11.8</sub></small>Cl, which exhibits high structural stability in the presence of water and air, is synthesized. At 25 °C, Li<small><sub>3.6</sub></small>In<small><sub>7</sub></small>S<small><sub>11.8</sub></small>Cl delivers an ionic conductivity of 1.1 mS cm<small><sup>−1</sup></small>, reaching 4.2 mS cm<small><sup>−1</sup></small> post-exposure to humid air. Multimodal investigations reveal that trapped water inside the Li<small><sub>3.6</sub></small>In<small><sub>7</sub></small>S<small><sub>11.8</sub></small>Cl pellet facilitates ion conduction, which can be reversibly removed without compromising the structural integrity. The structure features a cubic-closed-packed anion sublattice with Li<small><sup>+</sup></small> ions diffusing <em>via</em> a three-dimensional isotropic network, confirmed by <em>ab initio</em> molecular dynamics simulations. <small><sup>6</sup></small>Li NMR and relaxometry identify the Wyckoff 16c and 8a as active Li<small><sup>+</sup></small> sites for ion conduction. The high ionic conductivity, long-term stable cycling performance, and moisture stability of Li<small><sub>3.6</sub></small>In<small><sub>7</sub></small>S<small><sub>11.8</sub></small>Cl make it a preferable electrolyte candidate for high-performance ASSBs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"119 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143920235","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}
引用次数: 0
Transition Metal-Free vs. Metal-Catalyzed Cyclotrimerization of Didehydro[8]annulenes (COTynes): A Complex Pathway to Non-Planar PAHs – Dewar Benzenes vs. Benzotri[8]annulenes 二脱氢[8]环烯(COTynes)的过渡无金属与金属催化环三聚化:非平面PAHs -杜瓦苯与苯并三[8]环烯的复杂途径
IF 8.4 1区 化学
Chemical Science Pub Date : 2025-05-08 DOI: 10.1039/d5sc03035h
Jesús Bello García, Jesús A. Varela, Carlos Saá
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