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Tuning the Electrochemical Redox Mediated Mechanism of Oxygen Evolution on Cobalt sites by Hydroxide ions Coupling Chem. Sci. (IF 7.6) Pub Date : 2025-04-08
Wenjuan Song, Xiaoyue Duan, Poe Ei Phyu Win, Xiang Huang, Jiong WangHeterogeneous molecular catalysts (HMCs) with cobalt (Co) active sites are potent for electrochemical oxygen evolution reaction (OER) in the energy conversion applications. Such catalysts are typically operative through the classical redox mediated mechanism, where dynamic equilibriums of Co2+/3+ and Co3+/4+ redox are present before and throughout the OER cycle. The generation of low-valent Co2+ sites
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External Electric Field Drives the Formation of P?C Dative Bonds Chem. Sci. (IF 7.6) Pub Date : 2025-04-08
Tingting Ma, Xubin Wang, Xinru Peng, Jiayao Li, Shiwei Yin, Yirong Mo, Changwei WangChemical interactions driven by external electric fields (EFs) can serve as a catalytic force for molecular machines and linkers for smart materials. In this context, the EF-driven dative bond is demonstrated through the study of interactions between PH3 and curved carbon-based nanostructures. The P→C dative bonds emerge only in the presence of EFs, whereas the interactions in the absence of EFs lead
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Switchable Colossal Anisotropic Thermal Expansion in a Spin Crossover Framework Chem. Sci. (IF 7.6) Pub Date : 2025-04-08
Si-Guo Wu, Wen Cui, Ze-Yu Ruan, Zhao-Ping Ni, Ming-Liang TongAdvanced materials with tunable thermal expansion properties have garnered significant attention due to their potential applications in thermomechanical sensing and resistance to thermal stress. Here, switchable colossal anisotropic thermal expansion (ATE) behaviors are realized in a Hofmann-type framework [Fe(bpy-NH2){Au(CN)2}2]·iPrOH (Fe·iPrOH, bpy-NH2 = [4,4'-Bipyridin]-3-amine) through a three-in-one
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Discovery of a molecular adsorbent for efficient CO2/CH4 separation using a computation-ready experimental database of porous molecular materials Chem. Sci. (IF 7.6) Pub Date : 2025-04-08
Siyuan Yang, Qianqian Mao, Heng Ji, Dingyue Hu, Jinjin Zhang, Linjiang Chen, Ming LiuThe development and sharing of computational databases for metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) have significantly accelerated the exploration and application of these materials. Recently, molecular materials have emerged as a notable subclass of porous materials, characterized by their crystallinity, modularity, and processability. Among these, macrocycles and cages
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Redox Mediated Dimerisation of a cyclo-As8 Complex Chem. Sci. (IF 7.6) Pub Date : 2025-04-08
Christoph Riesinger, Manfred ScheerReduction as well as oxidation of the cyclo-As8 complex [{Cp’’Ta}2(?,η2:2:2:2:1:1-As8)] (A, Cp’’ = 1,3-tBu2C5H3) are demonstrated to afford controlled dimerisation to unprecedented As16 species. The dication [{Cp’’Ta}4(?4,η2:2:2:2:2:2:2:2:1:1:1:1-As16)]2+ slowly disproportionates in solution, yielding the largest polyarsenide species in a molecular complex known to date.
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Tailored Engineering of Primary Catalytic Sites and Secondary Coordination Spheres in Metalloenzyme-Mimetic MOF Catalysts for Boosting Efficient CO2 Conversion Chem. Sci. (IF 7.6) Pub Date : 2025-04-08
Jiawei Li, Fan Yang, Benling Yu, Zhongke Dai, Shiyuan Wei, Ying Wu, Liuqing He, Fa Zhou, Jianhan Huang, You-Nian LiuThe fabrication of metalloenzyme-mimetic artificial catalyst is a promising approach to achieve maximum catalytic efficiency, but the rational integration of sophisticatedly optimized primary catalytic sites (PCS) and secondary coordination spheres (SCS) for specific transformation poses a grand challenge. Here in this work, we reported the tailored engineering of Cu PCS and perfluoroalkyl SCS onto
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Pyridine-N-oxide Catalyzed Asymmetric N-Acylative Desymmetrization of Sulfonimidamides Chem. Sci. (IF 7.6) Pub Date : 2025-04-08
Cui-Mei Guo, Fang-Yuan Zhang, Yin Tian, Ming-Sheng Xie, Hai-Ming GuoA highly efficient enantioselective N-acylative desymmetrization of sulfonimidamides with chloroformates was reported using chiral 4-arylpyridine-N-oxide as the catalyst, affording N-acylative sulfonimidamides with sulfur(VI)-stereocenters in high yields and excellent enantioselectivities. Experiments and DFT calculations support an acyl transfer mechanism, and the nucleophilic substitution of sulfonimidamide
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Asymmetric Total Synthesis of Penicilfuranone A through NHC-Catalyzed Umpolung Chem. Sci. (IF 7.6) Pub Date : 2025-04-08
Yiming Ding, Xianwen Long, Jingwei Zhang, Qu Chunlei, Peng Wang, Xiaodong Yang, Pema-Tenzin Puno, Jun DengThe first asymmetric total synthesis of penicifuranone A was accomplished in eight steps through an NHC-catalyzed umpolung strategy. Key features of the synthesis include an Al-Salen catalyzed asymmetric cyanosilylation to install the tertiary alcohol of gregatin A, and an NHC catalyzed Stetter-Aldol cascade reaction. The umpolung strategy of benzyl aldehyde fragment facilitated a convergent formal
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Point defect formation at finite temperatures with machine-learning force fields Chem. Sci. (IF 7.6) Pub Date : 2025-04-08
Irea Mosquera-Lois, Johan Klarbring, Aron WalshPoint defects dictate the properties of many functional materials. The standard approach to modelling the thermodynamics of defects relies on a static description, where the change in Gibbs free energy is approximated by the internal energy. This approach has a low computational cost, but ignores contributions from atomic vibrations and structural configurations that can be accessed at finite temperatures
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Machine-learning based classification of 2D-IR liquid biopsies enables stratification of melanoma relapse risk Chem. Sci. (IF 7.6) Pub Date : 2025-04-07
Kelly Brown, Amy Farmer, Sabina Gurung, Matthew J. Baker, Ruth Board, Neil HuntNon-linear laser spectroscopy methods such as two-dimensional infrared (2D-IR) produce large, information-rich datasets, while developments in laser technology have brought substantial increases in data collection rates. This combination of data depth and quantity creates the opportunity to unite advanced data science approaches, such as Machine Learning (ML), with 2D-IR to reveal insights that surpass
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Exploring Solid-State Nanopore Approach for Single-Molecule Protein Detection from Single Cells Chem. Sci. (IF 7.6) Pub Date : 2025-04-07
Zi-Qi Zhou, Shao-Chuang Liu, Jia Wang, Ke-Le Chen, Bao-Kang Xie, Yi-Lun Ying, Yi-Tao LongDirect protein analysis from complex cellular samples is crucial for understanding cellular diversity and disease mechanisms. Here, we explored the potential of SiNx solid-state nanopores for single-molecule protein analysis from complex cellular samples. Using the LOV2 protein as model, we designed a nanopore electrophoretic driver protein and fused it with LOV2, thereby enhancing the capture efficiency
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Computational framework for discovery of degradation mechanisms of organic flow battery electrolytes Chem. Sci. (IF 7.6) Pub Date : 2025-04-07
Piotr de Silva, Xiaotong ZhangThe stability of organic redox-active molecules is a key challenge for the long-term viability of organic redox flow batteries (ORFBs). Electrolyte degradation leads to capacity fade, reducing the efficiency and lifespan of ORFBs. To systematically investigate degradation mechanisms, we present a computational framework that automates the exploration of degradation pathways. The approach integrates
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Photoelectron Circular Dichroism of Aqueous-Phase Alanine Chem. Sci. (IF 7.6) Pub Date : 2025-04-07
Dominik Stemer, Stephan Thürmer, Florian Trinter, Uwe Hergenhahn, Michele Pugini, Bruno Credidio, Sebastian Malerz, Iain Wilkinson, Laurent Nahon, Gerard Meijer, Ivan Powis, Bernd WinterAmino acids and other small chiral molecules play key roles in biochemistry. However, in order to understand how these molecules behave in vivo, it is necessary to study them under aqueous-phase conditions. Photoelectron circular dichroism (PECD) has emerged as an extremely sensitive probe of chiral molecules, but its suitability for application to aqueous solutions had not yet been proven. Here, we
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Interlayer Engineering-Induced Charge Redistribution in Bi2Te3 toward Efficient Zn2+ and NH4+ Storage Chem. Sci. (IF 7.6) Pub Date : 2025-04-05
Xiaojie Liang, Fangzhong Liu, Haonan Yue, Yaoyong Dong, Lijuan Chen, Ting Song, Yong Pei, Xianyou Wang, Bei Long, Yao Xiao, Xiong-Wei WuBismuth-based materials show promise for aqueous energy storage systems due to their unique layered structures and high storage capacity. Some bismuth-based materials have been applied to storage Zn2+ or NH4+, indicating that one bismuth-based compound may be innovatively used in both zinc-ion and ammonium-ion batteries (ZIBs and AIBs). Herein, we successfully design a poly(3,4-ethylenedioxythiophene)
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A Universal Strategy for Bridging Prussian Blue Analogues and Sodium Layered Oxide Cathodes: Direct Fast Conversion, Dynamic Structural Evolution, and Sodium Storage Mechanisms Chem. Sci. (IF 7.6) Pub Date : 2025-04-05
Hong-Wei Li, Jingqiang Wang, Jing Yu, Jia-Yang Li, Yan-Fang Zhu, Huanhuan Dong, Zhijia Zhang, Yong Jiang, Shi Xue Dou, Yao XiaoPrussian blue analogues (PBAs) are widely recognized as one of the most promising cathode materials for sodium-ion batteries (SIBs). However, many unqualified PBAs with unsatisfactory electrochemical performance are difficult to dispose of and pose a risk of environmental contamination. Additionally, the production process of layered oxides, another popular cathode material for SIBs, requires prolonged
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Electric-Field-Induced Covalent Condensation of Boronic Acids in Water Microdroplets Chem. Sci. (IF 7.6) Pub Date : 2025-04-04
Yue-Wen Zhou, Ming-Yang Jia, Jun-Lei Yang, Qinlei Liu, Zhenfeng CaiThe influence of electric fields (EFs) on chemical reactions has attracted significant interest due to their ability to modulate reaction rates, pathways, and selectivity. Although EFs have been experimentally demonstrated to facilitate various reactions, clearer evidence for their role in covalent condensation has remained limited. Herein, we provide experimental evidence of electric-field-induced
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Insights into the halogen-induced p-band center regulation promising high-performance lithium-sulfur batteries Chem. Sci. (IF 7.6) Pub Date : 2025-04-04
Hanzhang Fang, Wenshuo Hou, Chuanlong Li, Shuo Li, Fulu Chu, Xuting Li, Xianping Zhang, Linrui Hou, Changzhou Yuan, Yanwei MaSn-based halide perovskites are expected to solve the problems of shuttle effect and sluggish redox kinetics of lithium polysulfides (LiPSs) in lithium-sulfur batteries (LSBs) due to its high conductivity and electrocatalytic activity, but its intrinsic catalytic mechanism for LiPSs remains to be explored. Herein, halide perovskites of Cs2SnX6 (X = Cl, Br, I) with varying halide anions are purposefully
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Insights into Topochemical versus Stress-Induced High-Pressure Reactivity of Azobenzene by Single Crystal X-ray Diffraction Chem. Sci. (IF 7.6) Pub Date : 2025-04-04
Milo Agati, Sebastiano Romi, Samuele Fanetti, Krzysztof Radacki, Hanfland Michael, Holger Braunschweig, Todd B Marder, Stewart Clark, Alexandra Friedrich, ROBERTO BINIThis study addresses azobenzene's structural compression and reactivity under hydrostatic high-pressure conditions. Synchrotron X-ray diffraction data of single crystals compressed with neon as the pressure-transmitting medium allowed the refinement of the crystal structure up to 28 GPa, at which the onset of the reaction was observed. Analysis of the pressure-dependent lattice parameters reveals a
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Manipulating Room-Temperature Phosphorescence by Electron-Phonon Coupling Chem. Sci. (IF 7.6) Pub Date : 2025-04-04
Liangwei Ma, Muyu Cong, Siyu Sun, Xiang MaDesigning and optimizing efficient organic room-temperature phosphorescent (RTP) materials remains a captivating yet challenging endeavour due to the inherent difficulties in generating and stabilizing triplet excitons. Here, we report a suite of highly efficient phosphors characterized by near-unity intersystem crossing (ISC) yields. Surprisingly, upon doping these dyes into a polyvinyl alcohol matrix
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Controlling the spatial distribution of electronic excitation in asymmetric D-A-D’ and symmetric D’-A-D-A-D' Chem. Sci. (IF 7.6) Pub Date : 2025-04-04
Evangelos Balanikas, Tommaso Bianconi, Pietro Mancini, Nikhil Tewari, Manju Sheokand, Rajneesh Misra, benedetta. carlotti, Eric VautheyUnderstanding how electronic energy is funnelled towards a specific location in a large conjugated molecule is of primary importance for the development of a site-specific photochemistry. To this end, we investigate here how electronic excitation redistributes spatially in a series of electron donor-acceptor (D-A) molecules containing two different donors, D and D', and organised in both linear D-A-D'
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Atomic Surface Structure for Unraveling the Trade-off between the Propane Dehydrogenation Activity and Anti-Deactivation of PtSn Catalysts Chem. Sci. (IF 7.6) Pub Date : 2025-04-04
Mingxin Lv, Qiang Li, Fan Xue, Zhiguo Li, Peixi Zhang, Yue Zhu, Longlong Fan, Jianrong Zeng, Qiheng Li, Xin Chen, Kun Lin, Jinxia Deng, Xianran XingIn commercial Pt-based propane dehydrogenation catalysts, Sn doping is a fascinating strategy to suppress side reactions and optimizing selectivity. Nevertheless, excessive Sn incorporation results in a decline of surface Pt sites, leading to a significant reduction in catalytic activity. It challenges the precision of surface chemical design and the atomic unraveling of surface coordination are critical
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Mechanically Tunable Porous Gels Constructed via the Dual Co-ordination/Covalent Polymerization of Coumarin-Functionalized Rhodium-Organic Cuboctahedra Chem. Sci. (IF 7.6) Pub Date : 2025-04-03
David W. Burke, Masataka Yamashita, Zaoming Wang, Mako Kuzumoto, Kenji Urayama, Kei Saito, Shuhei FurukawaPolymer-based soft materials constructed from defined molecular pores, such as metal-organic polyhedra (MOPs), promise to merge the outstanding and diverse mechanical properties of conventional nonporous polymers with atomically-precise molecular recognition capabilities. Thus far, soft MOP networks have been constructed primarily using rigid, labile coordination bonds or dynamic covalent bonds, providing
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Base-Stabilized Acyclic Amino(ylidyl)silylenes: Electron-Rich Donors for the Stabilization of Silicon-Element Multiple Bonds Chem. Sci. (IF 7.6) Pub Date : 2025-04-03
Felix Krischer, Stephan Mayer, Lennart Hensle, Daniel Knyszek, Heidar Darmandeh, Viktoria H. GessnerIncreasing the donor strength of Lewis bases is a viable strategy to stabilize reactive species. Herein, we utilize the strong electron-releasing power of ylide substituents to gain access to electron-rich silylenes. Based on the Roesky’s amidinato chlorosilylene scaffold, we succeeded in isolating two amino(ylidyl)silylenes with a tosyl and cyano group in the ylide backbone, respectively. The tosyl
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Electrocatalytic hydrogenation of alkyne and alkene using proton conductive graphene oxide membrane Chem. Sci. (IF 7.6) Pub Date : 2025-04-03
Muhammad Sohail Ahmad, Taiga Kodama, Imam Sahroni, Kazuto Hatakeyama, Tetsuya KidaGraphene-based membranes are emerging as promising materials for energy and chemical conversion due to their exceptional proton conductivity and stability. In this study, we report a graphene oxide (GO) nanosheets membrane for electrochemical hydrogenation reactions. The GO membrane demonstrates excellent proton conductivity, confirmed through concentration cell measurement and complex impedance spectroscopy
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Double helicene possessing B-N dative bonds built on 1,4-dihydropyrrolo[3,2-b]pyrrole core Chem. Sci. (IF 7.6) Pub Date : 2025-04-02
Wojciech Petrykowski, Nicolas Vanthuyne, Carmelo Naim, Francesco Bertocchi, Yevgen P Poronik, Arkadiusz Ciesielski, Michal Ksawery Cyranski, Francesca Terenziani, Denis Jacquemin, Daniel T GrykoJust four steps are required to transform 2-nitrobenzaldehyde into centrosymmetric, quadrupolar N,B-doped nanographenes possessing two nitrogen-boron dative bonds. A convergent fragment coupling strategy allowed rapid access to key intermediates bearing the 1,4-dihydropyrrolo[3,2-b]pyrrole core. 2,6-Di-tert-butylpyridine turned out to be the best base for the formation of B←N bonds. This synthetic
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(3+2)-Cycloaddition of bicyclobutanes and thioketones: access to 2-thiabicyclo[2.1.1]hexanes without the use of catalysts or light Chem. Sci. (IF 7.6) Pub Date : 2025-04-02
Daniel B. Werz, Malini George, Daniil A. KnyazevA novel approach to the synthesis of the 2-thiabicyclo[2.1.1]hexane scaffold has been described. The method utilizes two highly reactive species: bicycle[1.1.0]butanes (BCBs) and thioketones. Their high reactivity enabled the formation of the desired product to occur under ambient conditions, without the need for catalysts, additives or light irradiation. To the best of our knowledge, this is the first
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Catalytic asymmetric construction of 1,5-remote Si- and C-stereocenters via desymmetrizing ene reaction of bis(methallyl)silanes Chem. Sci. (IF 7.6) Pub Date : 2025-04-01
Qiuhui Cao, Yuntian Yang, Yiwen Mei, Minghui Ji, Fei Wang, Xiaoming Feng, Weidi CaoCatalytic enantioselective synthesis of chiral silanes has long been a challenging pursuit. Achieving simultaneous construction of remote Si- and C-stereogenic centers in an acyclic molecule via desymmetrization is particularly difficult. Herein, we realized an example of a chiral nickel(II) complex catalyzed desymmetrizing carbonyl-ene reaction of bis(methallyl)silanes with α-keto aldehyde monohydrates
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Correlating halide segregation of wide-bandgap perovskites with methoxy group in organic hole-selective materials Chem. Sci. (IF 7.6) Pub Date : 2025-04-01
Xiaoyu Ji, Yun Zhao, Xiaofeng Chen, Shuo Zhang, Liqing Zhan, Huidong Zhang, Weizhong Zheng, Weihong Zhu, Yongzhen WuMixed-halide wide-bandgap (WBG) perovskites are widely used in constructing tandem photovoltaics, but their practical applications are challenged by a phenomenon called photo-induced halide segregation (PIHS), which is detrimental to stability of the devices. The origin of such PIHS is not fully understood yet, restricting their further advancement. Here, we report a serendipitous discovery that PIHS
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Hierarchical Interface Engineering for Advanced Magnesium-Based Hydrogen Storage: Synergistic Effects of Structural Design and Compositional Modification Chem. Sci. (IF 7.6) Pub Date : 2025-04-01
Han Jiang, Zhao Ding, Yuting Li, Guo Lin, Shaoyuan Li, Wenjia Du, Yu'an Chen, Leon L Shaw, Fusheng PanInterface engineering fundamentally revolutionizes magnesium-based hydrogen storage systems by orchestrating atomic-scale interactions and mass transport pathways through precisely engineered structural architectures and chemical environments. This review presents a paradigm-shifting framework that transcends conventional surface modification approaches, establishing interface engineering as a cornerstone
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Genetically Encoded 3-Aminotyrosine as Catalytic Residue in a Designer Friedel-Crafts Alkylase Chem. Sci. (IF 7.6) Pub Date : 2025-03-31
Bart Brouwer, Franco Della Felice, Andy-Mark Thunnissen, Gerard RoelfesGenetic incorporation of noncanonical amino acids (ncAAs) harbouring catalytic side chains into proteins allows the creation of enzymes able to catalyse reactions that have no equivalent in nature. Here, we present for the first time the use of the ncAA 3-aminotyrosine (aY) as catalytic residue in a designer enzyme for iminium activation catalysis. Incorporation of aY into protein scaffold LmrR gave
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IMPRESSION Generation 2 – Accurate, fast and generalised neural network model for predicting NMR parameters in place of DFT. Chem. Sci. (IF 7.6) Pub Date : 2025-03-31
Calvin Yiu, Ben Honoré, Will Gerrard, Jose Napolitano, Dave Russell, Iuni Margaret Laura Trist, Ruth Dooley, Craig Philip ButtsPredicting 3D-aware Nuclear Magnetic Resonance (NMR) properties is critical for determining the 3D structure and dynamics, both stereochemical and conformational, of molecules in solution. Existing tools for such predictions are limited, being either relatively slow quantum chemical methods such as Density Functional Theory (DFT), or niche parameterised empirical or machine learning methods that only
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Coordination-Driven Assembly of a Ferrocene-Functionalized Lead Iodide Framework with Enhanced Stability and Charge Transfer for Photocatalytic CO2-to-CH3OH Conversion Chem. Sci. (IF 7.6) Pub Date : 2025-03-31
Jinlin Yin, Yani He, Chen Sun, Yilin Jiang, Honghan FeiHybrid lead halides are promising photocatalysts due to high structural tunability and excellent photophysical properties, but their ionic structures suffer from instability in polar environment and suppressed charge transfer between lead halide units and organic components. Herein, we successfully incorporated a ferrocene-based light-harvesting antenna into a lead iodide framework by coordination-driven
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Computational Discovery and Systematic Analysis of Protein Entangling Motifs in Nature: From Algorithm to Database Chem. Sci. (IF 7.6) Pub Date : 2025-03-31
Puqing Deng, Yuxuan Zhang, Lianjie Xu, Jinyu Lyu, Linyan Li, Fei Sun, Wen-Bin Zhang, Hanyu GaoNontrivial protein topology has potential to revolutionize protein engineering by enabling the manipulation of proteins’ stability and dynamics. However, the rarity of topological proteins in nature poses a challenge for their design, synthesis and application, primarily due to the limited number of available entangling motifs as synthetic templates. Discovering these motifs is particularly difficult
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Redox-active Polymer-Grafted Particles as Redox Mediators for Enhanced Charge Transport in Solution-State Electrochemical Systems Chem. Sci. (IF 7.6) Pub Date : 2025-03-27
Mohd Avais, Ratul Mitra Thakur, Evan Fox, Jodie Lutkenhaus, Emily PentzerEfficient charge transport pathways in solutions of redox-active polymers are essential for advancing next-generation energy storage systems. Herein, we report the grafting of (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) and poly(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl methacrylate) (PTMA) polymer brushes onto silica particles with different molecular weights and grafting densities, and the impact
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Silane cooperation with Ce (III) to construct efficient protective layer and induce uniform deposition of Zn2+ for ultra-stable Zn anode Chem. Sci. (IF 7.6) Pub Date : 2025-03-26
Luyan Yu, Sidan He, Mingrui Zhang, Baohua Liu, Houyi Ma, Chao Wang, Qinghong WangAqueous Zn ion batteries (ZIBs) are gaining interest in large-scale energy storage systems due to their intrinsic safety, low cost and sustainability. Unfortunately, water-induced side reactions and dendrite growth on Zn anode have severely hampered the further development. Herein, 3-aminopropyltrimethoxysilane (KH-540) was employed as an electrolyte additive to construct an organic-inorganic solid/electrolyte
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A Highly Selective C-H Bond Fluorination Unlocks Conformational Reporting in a Complex Natural Product Derivative Chem. Sci. (IF 7.6) Pub Date : 2025-03-26
Jonah Ruskin, Roxanne Dekeyser, Nathaniel Garrison, Phoebe Williams, Maya Kramer-Johansen, Ananya Majumdar, Travis Dudding, Adam Huczynski, Thomas LectkaThe site-selective C-H bond fluorination of complex natural products is one of the more sought-after transformations in organic and medicinal chemistry. In many radical-based fluorinations, however, a tempest of poor regio- and stereoselectivity, multiple additions of fluorine, and difficult separations of products conspire to make selective monofluorination appear out of reach. In our fluorination
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Reassessing Anionic Redox in Conventional Layered Oxide Cathodes for Li-Ion Batteries: Ionic and Covalent Mechanisms Chem. Sci. (IF 7.6) Pub Date : 2025-03-20
Jianhua Yin, Zixin Wu, Kai Fang, Yuanlong Zhu, Kang Zhang, Haitang Zhang, Yilong Chen, Li Li, Longlong Fan, Kang Dong, Lirong Zheng, Qingsong Wang, Huan Huang, Jing Zhang, Yu Qiao, Shi-Gang SunEfforts to improve the specific capacity and energy density of lithium nickel-cobalt-manganese oxide (NCM) cathodes focus on operating at high voltages or increasing nickel content. However, both approaches necessitate a thorough understanding of the charge compensation mechanism. Traditional ionic-bonding models which separate transition metal (TM) and oxygen redox processes, prove inadequate as anionic
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Retro-forward synthesis design and experimental validation of potent structural analogs of known drugs Chem. Sci. (IF 7.6) Pub Date : 2025-03-19
Ahmad Makkawi, Wiktor Beker, Agnieszka Wolos, Sabyasachi Manna, Rafal Roszak, Sara Szymkuc, Martyna Moskal, Aleksei Koshevarnikov, Karol Molga, Anna Zadlo, Bartosz Andrzej GrzybowskiGeneration of structural analogs to “parent” molecule(s) of interest remains one of the important elements of drug development. Ideally, such analogs should be synthesizable by concise and robust synthetic routes. The current work illustrates how this process can be facilitated by a computational pipeline spanning (i) diversification of the parent via bioisosteric replacements, (ii) retrosynthesis
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Imaging biomineralizing bacteria in the native-state with X-ray fluorescence microscopy Chem. Sci. (IF 7.6) Pub Date : 2025-03-03
Daniel M. Chevrier, Elisa Cerdá-Do?ate, Lucía Gandarias, Miguel A Gomez Gonzalez, Sufal Swaraj, PAUL EDUARDO DAVID SOTO RODRIGUEZ, Antoine Fraisse, Tom Robinson, Damien FaivreUnderstanding the interactions between metal-based nanoparticles and biological systems in complex environments (e.g., the human body, soils, and marine settings) remains challenging, especially at the single-cell and nanoscale levels. Capturing the dynamics of these interactions, such as metal distribution, nanoparticle growth, or degradation, in their native state (in vivo) is particularly difficult
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Two- and three-photon processes during photopolymerization in 3D laser printing Chem. Sci. (IF 7.6) Pub Date : 2024-07-15
Anna Mauri, Pascal Kiefer, Philipp Neidinger, Tobias Messer, N. Maximilian Bojanowski, Liang Yang, Sarah L. Walden, Andreas Neil Unterreiner, Christopher Barner-Kowollik, Martin Wegener, Wolfgang Wenzel, Mariana KozlowskaThe performance of a photoinitiator is key to control efficiency and resolution in 3D laser nanoprinting. Upon light absorption, a cascade of competing photophysical processes leads to photochemical reactions toward radical formation that initiates free radical polymerization (FRP). Here, we investigate 7-diethylamino-3-thenoylcoumarin (DETC), belonging to efficient and frequently used photoinitiators
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Local Solvation Structures Govern the Mixing Thermodynamics of Glycerol-Water Solutions Chem. Sci. (IF 7.6) Pub Date : 2023-06-16
Debasish Das Mahanta, Dennis Robinson Brown, Simone Pezzotti, Gerhard Schwaab, Songi Han, M. Scott Shell, Martina Havenith -
Fe2(MoO4)3 assembled by cross-stacking of porous nanosheets enables a high-performance aluminum-ion battery Chem. Sci. (IF 7.6) Pub Date : 2022-11-12
Hongsen Li, Huanyu Liang, Yongshuai Liu, Fengkai Zuo, Cunliang Zhang, Li Yang, Linyi Zhao, Yuhao Li, Yifei Xu, Tiansheng Wang, Xia Hua, Yue ZhuRechargeable aluminum-ion batteries have attracted increasing attention owing to the advantageous multivalent ion storage mechanism thus high theoretical capacity as well as inherent safety and low cost of using aluminum. However, their development has been largely impeded by the lack of suitable positive electrodes to provide both sufficient energy density and satisfactory rate capability. Here we
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Anode Optimization Strategies for Aqueous Zinc-ion Batteries Chem. Sci. (IF 7.6) Pub Date : 2022-10-30
Yiyang Zhang, Xiaobo Zheng, Nana Wang, Wei-Hong Lai, Yong Liu, Shulei Chou, Huakun Liu, Shi Xue Dou, Yunxiao WangZinc-ion batteries (ZIBs) have received much research and attention due to their advantages of safety, non-toxicity, simple manufacture, and element abundance. Nevertheless, serious problems still remain for their anodes, with dendrite development, corrosion, passivation, and the parasitic hydrogen evolution reaction due to their unique aqueous electrolyte system constituting the main issues that must
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Fast Predictions of Liquid-Phase Acid-Catalyzed Reaction Rates Using Molecular Dynamics Simulations and Convolutional Neural Networks Chem. Sci. (IF 7.6) Pub Date : 2020-10-19
Alex K. Chew, Shengli Jiang, Weiqi Zhang, Victor M Zavala, Reid C Van LehnThe rates of liquid-phase, acid-catalyzed reactions relevant to the upgrading of biomass into high-value chemicals are highly sensitive to solvent composition and identifying suitable solvent mixtures is theoretically and experimentally challenging. We show that the complex atomistic configurations of reactant-solvent environments generated by classical molecular dynamics simulations can be exploited
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Cobalt-Catalyzed Intramolecular Decarbonylative Coupling of Acylindoles and Diarylketones through the Cleavage of C?C Bonds Chem. Sci. (IF 7.6) Pub Date : 2020-10-16
Tian-Yang Yu, Wenhua Xu, Hong Lu, Hao WeiWe report here cobalt?N-heterocyclic carbene catalytic systems for the intramolecular decarbonylative coupling through the chelation-assisted C?C bond cleavage of acylindoles and diarylketones. The reaction tolerates a wide range of functional groups such as alkyl, aryl, and heteroaryl groups, giving the decarbonylative products in moderate to excellent yields. This transformation involves the cleavage
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Access to Substituted Cyclobutenes by Tandem [3,3]-Sigmatropic Rearrangement/[2+2] Cycloaddition of Dipropargylphosphonates under Ag/Co Relay Catalysis Chem. Sci. (IF 7.6) Pub Date : 2020-10-16
Qijian Ni, Xiaoxiao Song, Chin Wen Png, Yongliang Zhang, Yu ZhaoWe present herein an unconventional tandem [3,3]-sigmatropic rearrangement/[2+2] cycloaddition of simple dipropargylphosphonates to deliver a range of bicyclic polysubstituted cyclobutenes and cyclobutanes under Ag/Co relay catalysis. An interesting switch from allene-allene to allene-alkyne cycloaddition was observed based on the substitution of the substrates, which further diversified the range
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Iron-Catalyzed α-C–H functionalization of π-Bonds: Cross-Dehydrogenative Coupling and Mechanistic Insights Chem. Sci. (IF 7.6) Pub Date : 2020-10-16
Yidong Wang, Jin Zhu, Rui Guo, Haley Lindberg, Yiming WangThe deprotonation of propargylic C–H bonds for subsequent functionalization typically requires stoichiometric metal alkyl or amide reagents. In addition to the undesirable generation of stoichiometric metallic waste, these conditions limit the functional group compatibility and versatility of this functionalization strategy and often result in regioisomeric mixtures. In this Article, we report the
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Photoresponsive molecular tools for emerging applications of light in medicine Chem. Sci. (IF 7.6) Pub Date : 2020-10-15
Ilse M. Welleman, Mark W. H. Hoorens, Ben L Feringa, Hendrikus H. Boersma, Wiktor SzymanskiLight-based therapeutic and imaging modalities, which emerge in clinical applications, rely on molecular tools, such as photocleavable protecting groups and photoswitches, that respond to photonic stimulus and translate it into a biological effect. However, optimisation of their key parameters (activation wavelength, band separation, fatigue resistance and half-life) is necessary to enable application
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Efficient Cleavage of Tertiary Amide Bonds via Radical-Polar Crossover Using a Copper(II) Bromide/Selectfluor Hybrid System Chem. Sci. (IF 7.6) Pub Date : 2020-10-14
Zhe Wang, Akira Matsumoto, Keiji MaruokaA novel approach for the efficient cleavage of the amide bonds in tertiary amides is reported. Based on the selective radical abstraction of a benzylic hydrogen atom by a?CuBr2/Selectfluor hybrid system?followed by a?selective cleavage of an N–C bond, an acyl fluoride intermediate is formed. This intermediate may then be derivatized in a one-pot fashion. The reaction proceeds under mild conditions
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Synthesis, crystal structure and charge transport characteristics of stable peri-tetracene analogues Chem. Sci. (IF 7.6) Pub Date : 2020-10-14
Masashi Mamada, Ryota Nakamura, Chihaya AdachiPeri-acenes have shown great potential for use as functional materials because of their open-shell singlet biradical character. However, only a limited number of peri-acene derivatives larger than peri-tetracene have been synthesized to date, presumably owing to the low stability of the target compounds in addition to the complicated synthesis scheme. Here, a very simple synthesis route for the tetrabenzo[a
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Photocatalytic Redox-Neutral Hydoxyalkylation of N-Heteroaromatics with Aldehydes Chem. Sci. (IF 7.6) Pub Date : 2020-10-12
Hiromu Fuse, Hiroyasu Nakao, Yutaka Saga, Arisa Fukatsu, Mio Kondo, Shigeyuki Masaoka, Harunobu Mitsunuma, Motomu KanaiA hydroxyalkylation of N-heteroaromatics with aldehydes was achieved using a binary hybrid catalyst system comprising an acridinium photoredox catalyst and a thiophosphoric acid organocatalyst. The reaction proceeded through the following sequence: 1) photoredox-catalyzed single-electron oxidation of a thiophosphoric acid catalyst to generate a thiyl radical, 2) cleavage of the formyl C?H bond of the
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Aromatic foldamers as scaffolds for metal second coordination sphere design Chem. Sci. (IF 7.6) Pub Date : 2020-10-12
Antoine Meunier, Michael Singleton, Brice Kauffmann, Thierry Granier, Guillaume Lautrette, Yann Ferrand, Ivan HucAs metalloproteins exemplify, the chemical and physical properties of metal centers depend not only on their first but also on their second coordination sphere. Installing arrays of functional groups around the first coordination sphere of synthetic metal complexes is thus highly desirable, but it remains a challenging objective. Here we introduce a novel approach to produce tailored second coordination
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Enhancing the ROS Generation Ability of a Rhodamine-Decorated Iridium(III) Complex by Ligand Regulation for Endoplasmic Reticulum-Targeted Photodynamic Therapy Chem. Sci. (IF 7.6) Pub Date : 2020-10-12
Lihua Zhou, Keith Man-Chung Wong, Lintao Cai, Ping Gong, Pengfei Zhang, Chunbin Li, Chuangjun Liu, Jingjing Xiang, Fangfang Wei, Hongfeng LiThe endoplasmic reticulum (ER) is a very important organelle responsible for crucial biosynthetic, sensing, and signalling functions in eukaryotic cells. In this work, we established a strategy of ligand regulation to enhance the singlet oxygen generation capacity and subcellular organelle localization ability of a rhodamine-decorated iridium(III) complex by variation of the cyclometallating ligand
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Bis[Pyrrolyl Ru(II)] Triads: a New Class of Photosensitizers for Metal-Organic Photodynamic Therapy Chem. Sci. (IF 7.6) Pub Date : 2020-10-06
Deborah A. Smithen, Susan Monro, Mitch A. Pinto, John A Roque III, Roberto Diaz-Rodriguez, Huimin Yin, Colin G. Cameron, Alison Thompson, Sherri Ann McFarlandA new family of ten dinuclear Ru(II) complexes based on the bis[pyrrolyl Ru(II)] triad scaffold, where two Ru(bpy)2centers are separated by a variety of organic linkers, was prepared to evaluate the influence of the organic chromophore on the spectroscopic and in vitro photodynamic therapy (PDT) properties of the compounds. The bis[pyrrolyl Ru(II)] triads absorbed strongly throughout the visible region
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Shaping non-noble metal nanocrystals via colloidal chemistry Chem. Sci. (IF 7.6) Pub Date : 2020-10-05
Valeria Mantella, Laia Castilla i Amoròs, Raffaella BuonsantiNon-noble metal nanocrystals with well-defined shapes have been attracting increasingly more attention in the last decade as potential alternatives to noble metals, by virtue of their Earth abundance combined with intriguing physical and chemical properties relevant for both fundamental studies and technological applications. Nevertheless, their synthesis is still primitive when compared to noble metals
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Unveiling the molecular mechanism of SARS-CoV-2 main protease inhibition from 137 crystal structures using algebraic topology and deep learning Chem. Sci. (IF 7.6) Pub Date : 2020-09-30
Duc Nguyen, Kaifu Gao, Jiahui Chen, Rui Rui Wang, Guowei WeiCurrently, there is no effective antiviral drugs nor vaccine for coronavirus disease 2019 (COVID-19)caused by acute respiratory syndrome coronavirus 2 (SARS-CoV-2). Due to its high conservativeness andlow similarity with human genes, SARS-CoV-2 main protease (Mpro) is one of the most favorable drug targets.However, the current understanding of the molecular mechanism of Mpro inhibition is limited by
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Inorganic nanocrystal-dynamic porous polymer assemblies with effective energy transfer for sensitive diagnosis of urine copper Chem. Sci. (IF 7.6) Pub Date : 2020-09-23
Xujiao Ma, Yajie Yang, Rongchen Ma, Yunfeng Zhang, Xiaoqin Zou, Shoujun Zhu, Xin Ge, Ye Yuan, Wei Zhang, Guangshan ZhuDespite the remarkable mechanical/optical/electrical properties, the inorganic particles and dynamic polymer assemblies encountered the difficulties in compatibility with structural order and complexity. Here, covalent organic frameworks (COFs) constructed through reversible coupling reactions were exploited as dynamic porous polymers to prepare the inorganic nanocrystal-polymer assemblies. Experiencing
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Modulating the ground state, stability and charge transport in OFETs of biradicaloid Hexahydro-diindenopyrene derivatives and a proposed method to estimate the biradical character Chem. Sci. (IF 7.6) Pub Date : 2020-09-16
Tanguy Jousselin-Oba, Masashi Mamada, Atsushi Okazawa, Jérome Marrot, Takayuki Ishida, Chihaya Adachi, Abderrahim Yassar, Michel FrigoliBiradicaloid compounds with an open-shell ground state have been the subject of intense research in the past decade. Although diindenoacenes are one of the most developed families, only few examples have been reported as active layer in organic field-effect transistors (OFETs) with charge mobility of around 10?3 cm2 V?1 s?1 due to a steric disadvantage of the mesityl group to kinetically stabilize
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Oxygen accelerated scalable synthesis of highly fluorescent sulfur quantum dots Chem. Sci. (IF 7.6) Pub Date : 2019-11-27
Yiheng Song, Jisuan Tan, Guan Wang, Pengxiang Gao, Jiehao Lei, Li Zhou -
Single electron transfer events and dynamical heterogeneity in the small protein azurin from Pseudomonas aeruginosa Chem. Sci. (IF 7.6) Pub Date : 2019-11-27
Biswajit Pradhan, Christopher Engelhard, Sebastiaan Van Mulken, Xueyan Miao, Gerard W. Canters, Michel Orrit