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Redox regulation of Ni hydroxides with controllable phase composition towards biomass-derived polyols electro-refinery Chem. Sci. (IF 8.4) Pub Date : 2024-04-23 Yi Tang, Zhuxin Gui, Yingshuai Jia, Xianping Liao, Tianlan Yan, Boxu Gao, Wenbiao Zhang, Li Chen, Qingsheng Gao, Yahong Zhang
Electrocatalytic refinery from biomass-derived glycerol (GLY) to formic acid (FA), one of the most promising candidates of green H2 carrier, has driven widespread attention for its sustainability. Herein, we fabricated a series of monolithic Ni hydroxides-based electrocatalysts by a facile and in-situ electrochemical method through the manipulation of local pH near electrode. The as-synthesized Ni(OH)2@NF-1
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Understanding Electrochemical Interfaces through Comparing Experimental and Computational Charge Density-Potential Curves Chem. Sci. (IF 8.4) Pub Date : 2024-04-23 Nandita Mohandas, Sumit Bawari, Jani J.T. Shibuya, Soumya Ghosh, Jagannath Mondal, Tharangattu N. Narayanan, Angel Cuesta
Electrode-electrolyte interfaces play a decisive role in electrochemical charge accumulation and transfer processes. Theoretical modelling of these interfaces is critical to decipher the microscopic details of such phenomena. Different force field-based molecular dynamics protocols are compared here in a view to connect calculated and experimental charge density-potential relationships. Platinum-aqueous
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Enantioselective synthesis of α-aryl α-hydrazino phosphonates Chem. Sci. (IF 8.4) Pub Date : 2024-04-23 Saul Alberca, Javier Romero-Parra, Israel Fernandez, Rosario Fernández, Jose M. Lassaletta, David Monge
Catalysts generated in situ by the combination of pyridine-hydrazone N,N-ligands and Pd(TFA)2 have been applied to the addition of arylboronic acids to formylphosphonate-derived hydrazones, yielding α-aryl α-hydrazino phosphonates in excellent enantioselectivities (96−>99% ee). Subsequent removal of the benzyloxycarbonyl (Cbz) N-protecting group afforded key building blocks en route to appealing artificial
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Monolithic 3D nanoelectrospray emitters based on continuous fluid-assisted etching strategy for glass droplet microfluidic chip-mass spectrometry Chem. Sci. (IF 8.4) Pub Date : 2024-04-23 Yaoyao Zhao, Ziyang Guo, Yingqi Zhao, Zhao Jin, Yaran Chang, Xiayan Wang, Guangsheng Guo
Glass microfluidic chips are suitable for coupling with mass spectrometry (MS) due to their flexible design, optical transparency and resistance to organic reagents. However, due to the high hardness and brittleness of glass, there is a lack of simple and feasible technology to manufacture a monolithic nanospray ionization (nESI) emitter on a glass microchip, which hinders its coupling with mass spectrometry
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Photo-Thermal Synergistic CO2 Hydrogenation towards CO over PtRh Bimetal-Decorated GaN Nanowires/Si Chem. Sci. (IF 8.4) Pub Date : 2024-04-23 Jinglin Li, Bowen Sheng, Liang Qiu, Jiajia Yang, Ping Wang, Yixin Li, Tianqi Yu, Hu Pan, Ying Li, Muhan Li, Lei Zhu, Xinqiang Wang, Zhen Huang, Baowen Zhou
Photo-thermal-synergistic hydrogenation is a promising strategy for upcycling carbon dioxide into fuels and chemicals by maximally utilizing full-spectrum solar energy. Herein, by immobilizing Pt-Rh bimetal onto a well-developed GaN NWs/Si platform, CO2 was photo-thermo-catalytically hydrogenated towards CO under concentrated light illumination without extra energies. The as-designed architecture demonstrates
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Optoelectronic insights of lead-free layered halide perovskites Chem. Sci. (IF 8.4) Pub Date : 2024-04-23 Vishwadeepa Hazra, Arnab Mandal, Sayan Bhattacharyya
Two-dimensional organic-inorganic halide perovskites have emerged as promising candidates for a multitude of optoelectronic technologies, owing to their versatile structure and electronic properties. The optical and electronic properties are harmoniously integrated with both the inorganic metal halide octahedral slab, and the organic spacer layer. The inorganic octahedral layers can also assemble into
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1,5-Hydrogen Atom Transfer of α-Iminyl Radical Cations: A New Platform for Relay Annulation towards Pyridine Derivatives and Axially Chiral Heterobiaryls Chem. Sci. (IF 8.4) Pub Date : 2024-04-23 Yu-Qiang Zhou, Kui-Cheng He, Wei-Hao Zheng, Jing-Fang Lv, Shi-Mei He, Ning Yu, Yun-Bo Yang, Lv-Yan Liu, Kun Jiang, Ye Wei
The exploitation of new reactive species and novel transformation modes for their synthetic applications have significantly promoted the development of synthetic organic methodology, drug discovery, and advanced functional materials. α-Iminyl radical cations, a class of distonic ions, exhibit great synthetic potential towards the synthesis of valuable molecules. For their generation, radical conjugate
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Highly intense NIR emissive Cu4Pt2 bimetallic clusters featuring Pt(I)-Cu4-Pt(I) sandwich kernel Chem. Sci. (IF 8.4) Pub Date : 2024-04-23 Rui-Ru Zhong, Mo Xie, Cui-Zhou Luan, Lin-Mei Zhang, De-Bo Hao, Shang-Fu Yuan, Tao Wu
Metal nanoclusters (NCs) capable of near-infrared (NIR) photoluminescence (PL) are gaining increasing interest for their potential applications in bioimaging, cell labelling, and phototherapy. However, the limited quantum yield (QY) of NIR emission in metal NCs, especially those emitting beyond 800 nm, hinders their widespread applications. Herein, we present a bright NIR luminescence (PLQY up to 36%
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Observation of Super-Nernstian Proton-Coupled Electron Transfer and Elucidation of Nature of Charge Carriers in a Multiredox Conjugated Polymer Chem. Sci. (IF 8.4) Pub Date : 2024-04-22 Duyen K. Tran, Sarah M. West, Elizabeth M. K. Speck, Samson A. Jenekhe
Nernstian proton-coupled electron transfer (PCET) is a fundamental process central to many physical and biological systems, such as electrocatalysis, enzyme operation, DNA biosynthesis, pH-/bio-sensors, and electrochemical energy storage devices. We report herein the discovery of super-Nernstian PCET behavior with two protons per electron transferred in the electrochemical doping of a redox conjugated
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DNA-Directed Formation of Plasmonic Core-Satellite Nanostructures for Quantification of Hepatitis C Viral RNA Chem. Sci. (IF 8.4) Pub Date : 2024-04-22 Samuel Mabbott, Siddhant Jaitpal, Ka Wai Ng, Angela Michelle San Juan, Cecilia Martinez, Christian Phillips, Sayantan Tripathy
Hepatitis C virus (HCV) continues to be a significant public health challenge, affecting an estimated 71 million people globally and posing risks of severe liver diseases. Despite advancements in treatments, diagnostic limitations hinder the global elimination efforts targeted by 2030. This study introduces an innovative diagnostic approach, integrating catalytic hairpin assembly (CHA) with plasmonic
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Copper-catalyzed Remote Double Functionalization of Allenynes Chem. Sci. (IF 8.4) Pub Date : 2024-04-20 Shengming Ma, Yulong Song, Chunling Fu, Jian Zheng
Addition reactions of molecules with conjugated or non-conjugated multiple unsaturated C-C bonds are very attractive yet challenging due to the versatile issues of chemo-, regio-, and stereo-selectivities. Especially for the readily available conjugated allenynes compounds, the reactivities have not been explored. The first example of copper-catalyzed 2,5-hydrofunctionalization and 2,5-difunctionalization
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Halogen-Bonded Charge-Transfer Co-crystal Scintillators for High-Resolution X-ray Imaging Chem. Sci. (IF 8.4) Pub Date : 2024-04-20 Mei-Jin Lin, Yu-Hua Chen, Guo-Zhen Zhang, Fu-Hai Chen, Shuquan Zhang, Xin Fang, Hong-Ming Chen
The development of high-quality organic scintillators encounters challenges primarily associated with the weak X-ray absorption ability resulting from the presence of low atomic number elements. An effective strategy involves the incorporation of halogen-containing molecules into the system through co-crystal engineering. Herein, we synthesized a highly fluorescent dye, 2,5-di(4-pyridyl)thiazolo[5
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Boron-containing helicenes as new generation of chiral materials: opportunities and challenges of leaving the flatland Chem. Sci. (IF 8.4) Pub Date : 2024-04-19 Agnieszka Nowak-Krol, Patrick T. Geppert, Kenkera Rayappa Naveen
Increased interest in chiral functional dyes has stimulated activity in the field of boron-containing helicenes over the past few years. Despite the fact that the introduction of boron endows π-conjugated scaffolds with attractive electronic and optical properties, boron helicenes have long remained underdeveloped compared to other helicenes containing main group elements. The main reason was the lack
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High-Mobility Organic Mixed Conductors with a Low Synthetic Complexity Index via Direct Arylation Polymerization Chem. Sci. (IF 8.4) Pub Date : 2024-04-19 Joost Kimpel, Youngseok Kim, Jesika Asatryan, Jaime Martin, Renee Kroon, Christian Müller
Through direct arylation polymerization, a series of mixed ion-electron conducting polymers with a low synthetic complexity index is synthesized. A thieno[3,2-b]thiophene monomer with oligoether side chains is used in direct arylation polymerization together with a wide range of aryl bromides with varying electronic character from electron-donating thiophene to electron-accepting benzothiadiazole.
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A High-Resolution Structural Characterization and Physicochemical Study of How a Peptoid Binds to an Oncoprotein MDM2 Chem. Sci. (IF 8.4) Pub Date : 2024-04-19 Marin Yokomine, Jumpei Morimoto, Yasuhiro Fukuda, Takumi Ueda, Koh Takeuchi, Koji Umezawa, Hideo Ago, Hiroaki Matsuura, Go Ueno, Akinobu Senoo, Satoru Nagatoishi, Kouhei Tsumoto, Shinsuke Sando
Peptoids are a promising drug modality targeting disease-related proteins, but how a peptoid engages in protein binding is poorly understood. This is primarily due to a lack of high-resolution peptoid–protein complex structures and systematic physicochemical studies. Here, we present the first crystal structure of a peptoid bound to a protein, providing high-resolution structural information about
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A Highly Efficient Catalytic Method for the Synthesis of Phosphite Diesters Chem. Sci. (IF 8.4) Pub Date : 2024-04-17 Yuki Saito, Soomin Cho, Luca Danieli, Akira Matsunaga, Shu Kobayashi
In contrast to conventional methods that rely on stoichiometric activation of phosphonylating reagents, we have developed a highly efficient catalytic method for the synthesis of phosphite diesters using a readily available phosphonylation reagent and alcohols with environmentally benign Zn(II) catalysts. Two alcohols could be introduced consecutively on the P center with release of trifluoroethanol
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An Adsorbate Biased Dynamic 3D Porous Framework for Inverse CO2 Sieving over C2H2 Chem. Sci. (IF 8.4) Pub Date : 2024-04-17 Nivedita Sikdar, Subhajit Laha, Rohan Jena, Anupam Dey, Faruk Ahamed Rahimi, Tapas Kumar Maji
Separating carbon dioxide (CO2) from acetylene (C2H2) is one of the most critical and complex industrial separations due to similarities in physicochemical properties and molecular dimensions. Herein, we report a novel Ni-based three-dimensional framework {[Ni4(μ3-OH)2(μ2-OH2)2(1,4-ndc)3](3H2O)}n (1,4-ndc = 1,4-naphthalenedicarboxylate) with one-dimensional pore channel (3.05 × 3.57 Å2), that perfectly
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Carborane-Arene Fused Boracyclic Analogues of Polycyclic Aromatic Hydrocarbons Accessed by Intramolecular Borylation Chem. Sci. (IF 8.4) Pub Date : 2024-04-16 Yijie Li, Tamizmani Masilamani, Manjur Oyasim O. Akram, Caleb Daniel Martin
Arenes are 2D aromatics while dicarbadodecaborane clusters are branded as 3D aromatic molecules. In this work we prepare molecules that feature fused 2D/3D aromatic systems that represent boron-doped analogues of polycyclic aromatic hydrocarbons. The electron withdrawing nature of the ortho-carborane substituent enables swift arene borylation on boron bromide or hydride precursors to furnish five-
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Amorphous Conversion in Pyrolytic Symmetric Trinuclear Nickel Clusters Trigger Trifunctional Electrocatalysts Chem. Sci. (IF 8.4) Pub Date : 2024-04-16 Li Li, Huifeng Zhao, Meixing Gan, Tao Zhang, Jianing Li, Shi Tao, Jing Peng, Hai-Bin Yu, Xu Peng
The pursuit of multifunctional electrocatalysts holds significant importance due to their foundational comprehension of material chemistry. Amorphous materials are particularly appealing, yet they pose challenges in terms of rational design due to their structure disorder and thermal instability. Herein, we propose a strategy that entails the tandem (low-temperature/250-350 oC) pyrolysis of molecular
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Thiophene-fused γ-lactams inhibit the SARS-CoV-2 main protease via reversible covalent acylation Chem. Sci. (IF 8.4) Pub Date : 2024-04-16 Gayatri Gayatri, Lennart Brewitz, Lewis Ibbotson, Eidarus Saleh, Shyam Basak, Hani Choudhry, Christopher J Schofield
Enzyme inhibitors working by O-acylation of nucleophilic serine residues are of immense medicinal importance, as exemplified by the β-lactam antibiotics. By contrast, inhibition of nucleophilic cysteine enzymes by S-acylation has not been widely exploited for medicinal applications. The SARS-CoV-2 main protease (Mpro) is a nucleophilic cysteine protease and a validated therapeutic target for COVID-19
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¬The impact of earth-abundant metals as a replacement for Pd in cross coupling reactions Chem. Sci. (IF 8.4) Pub Date : 2024-04-16 Michael U. Luescher, Fabrice Gallou, Bruce H. Lipshutz
Substitution of one metal catalyst for another is not straightforward as simply justifying this change based on the availability and/or cost of the metals. A life cycle-like assessment was performed leading to the conclusion that the commonly held view that use of earth-abundant metals (and in this case study, Ni) are replacements for palladium most notably in cross coupling reactions, and Suzuki-Miyaura
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Nanoelectrochemistry reveals how presynaptic neurons regulate vesicle release to sustain synaptic plasticity under repetitive stimuli Chem. Sci. (IF 8.4) Pub Date : 2024-04-15 Fu-Li Zhang, Xiao-Ke Yang, Yu-Ting Qi, Si-Yu Tian, Wei-Hua Huang
Synaptic plasticity is the ability of synapses to modulate synaptic strength in response to dynamic self and environment change. Although great attention has been paid on protein expression and receptor migration in different categories of synaptic plasticity, the contribution and impact of presynaptic vesicle release and neurotransmitter level towards plasticity still remain largely unclear. Herein
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Therapeutic Coordination Polymers: Tailoring Drug Release through Metal-Ligand Interactions Chem. Sci. (IF 8.4) Pub Date : 2024-04-11 Vedran Nicholas Vukotic, Jennifer Murphy, Joy-Lynn Kobti, Michelle Dao, Darcy Wear, Michael Okoko, S. Pandey
Developing tunable materials which exhibit sustained drug release is a considerable challenge. Herein, we report the concept of Therapeutic Coordination Polymers (TCPs); non-porous coordination polymers constructed from biocompatible components which demonstrate tunable zero-order drug release kinetics upon degradation of metal-ligand bonds. TCPs were constructed from three principal components: i)
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P-doped spherical hard carbon with high initial Coulombic efficiency and enhanced capacity for sodium ion batteries Chem. Sci. (IF 8.4) Pub Date : 2024-04-11 Zhengguang Liu, Jiahua Zhao, Hao Yao, Xiangxi He, Hang Zhang, Yun Qiao, Xingqiao Wu, Li Li, Shulei Chou
Hard carbon (HC) is one of the most promising anode materials for sodium-ion batteries (SIBs) due to its cost-effectiveness, and low-voltage plateau capacity. Heteroatom doping is considered as an effective strategy to improve the sodium storage capacity of HC. However, most of the previous heteroatom doping strategies are occurred at a relatively low temperature, which could not be utilized to raise
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Binding of carbon dioxide and acetylene to free carboxylic-acid sites in a metal-organic framework Chem. Sci. (IF 8.4) Pub Date : 2024-04-10 Martin Schroder, Christopher Marsh, Xue Han, Zhenzhong Lu, Ivan da Silva, Yongqiang Cheng, Luke L. Daemen, Sarah Day, Stephen Thompson, Anibal Javier Ramirez-Cuesta, Sihai Yang
The functionalisation of organic linkers in metal-organic frameworks (MOFs) to improve gas uptake is well-documented. Although the positive role of free carboxylic acid sites in MOFs for binding gas molecules has been proposed in computational studies, relatively little experimental evidence has been reported in support of this. Primarily this is because of the inherent synthetic difficulty to prepare
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Ultrafast photogeneration of a metal-organic nitrene from 1,1’-diazidoferrocene Chem. Sci. (IF 8.4) Pub Date : 2024-04-09 Frederik Scherz, Markus Bauer, Luis Domenianni, Carolin Hoyer, Jonas Schmidt, Biprajit Sarkar, Peter Vöhringer, Vera Krewald
Ferrocene and its derivatives have fascinated chemists for more than 70 years, not least due to the analogies with the properties of benzene. Despite these similarities, the obvious difference between benzene and ferrocene is the presence of an iron ion and hence the availability of d-orbitals for properties and reactivity. Phenylnitrene with its rich photochemistry can be considered an analogue of
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High-throughput single-cell mass spectrometry enables metabolic network analysis by resolving phospholipid C=C isomers Chem. Sci. (IF 8.4) Pub Date : 2024-04-04 Simin Cheng, Chenxi Cao, Yao Qian, Huan Yao, Xiaoyun Gong, Xinhua Dai, Zheng Ouyang, Xiaoxiao Ma
Single-cell mass spectrometry (MS) is an essential technology for sensitive and multiplexed analysis of metabolites and lipids for cell phenotyping and pathway studies. However, the structural elucidation of lipids from single cells remains a challenge, especially in the high-throughput scenario. Technically, there is a contradiction between the inadequate sample amount (i.e. a single cell, 0.5-20
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De novo Design of Peptides that Bind Specific Conformers of α-Synuclein Chem. Sci. (IF 8.4) Pub Date : 2024-03-30 Hailey M Wallace, Hyunjun Yang, Sophia K Tan, Henry S Pan, Rose Yang, Junyi Xu, Hyunil Jo, Carlo Condello, Nicholas F Polizzi, Bill DeGrado
Insoluble amyloids rich in cross-β fibrils are observed in a number of neurodegenerative diseases. Depending on the clinicopathology, the amyloids can adopt distinct supramolecular assemblies, termed conformational strains. However, rapid methods to study amyloid in a conformationally specific manner are lacking. We introduce a novel computational method for de novo design of peptides that tile the
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Ag1+ Incorporation via Zr4+-Anchored Metalloligand: Fine-Tuning the Catalytic Ag Sites in Zr/Ag Bimetallic Clusters for Enhanced eCO2RR-to-CO activity Chem. Sci. (IF 8.4) Pub Date : 2024-03-25 Chao Liu, Liang-Jun Li, Wen-Lei Mu, Yi-Qi Tian, Weidong Yu, Lanyan Li, Jun Yan
Attaining meticulous dominion over the binding milieu of catalytic metal sites remains an indispensable pursuit to tailor product selectivity and elevate catalytic activity. By harnessing the distinctive attributes of a Zr4+-anchored thiacalix[4]arene (TC4A) metalloligand, we have pioneered a methodology for incorporating catalytic Ag1+ sites, resulting in the first Zr-Ag bimetallic cluster, Zr2Ag7
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Cluster dynamics of heterometallic trinuclear clusters during ligand substitution, redox chemistry, and group transfer processes Chem. Sci. (IF 8.4) Pub Date : 2024-02-15 Cristin E. Juda, Rex Handford, Amymarie K. Bartholomew, Tamara Powers, Nina X. Gu, Elisabeth Meyers, Nikolaj Roth, Yu-Sheng Chen, Shao-Liang Zheng, Theodore Betley
Stepwise metalation of the hexadentate ligand tbsLH6 (tbsLH6 = 1,3,5-C6H9(NHC6H4-o-NHSiMe2tBu)3) affords bimetallic trinuclear clusters (tbsL)Fe2Zn(thf) and (tbsL)Fe2Zn(py). Reactivity studies were pursued to understand metal atom lability as the clusters undergo ligand substitution, redox chemistry, and group transfer processes. Chloride addition to (tbsL)Fe2Zn(thf) resulted in a mixture of species
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Local Solvation Structures Govern the Mixing Thermodynamics of Glycerol-Water Solutions Chem. Sci. (IF 8.4) Pub Date : 2023-06-16 Debasish Das Mahanta, Dennis Robinson Brown, Simone Pezzotti, Gerhard Schwaab, Songi Han, M. Scott Shell, Martina Havenith
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Fe2(MoO4)3 assembled by cross-stacking of porous nanosheets enables a high-performance aluminum-ion battery Chem. Sci. (IF 8.4) 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 Zhu
Rechargeable 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 8.4) Pub Date : 2022-10-30 Yiyang Zhang, Xiaobo Zheng, Nana Wang, Wei-Hong Lai, Yong Liu, Shulei Chou, Huakun Liu, Shi Xue Dou, Yunxiao Wang
Zinc-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 8.4) Pub Date : 2020-10-19 Alex K. Chew, Shengli Jiang, Weiqi Zhang, Victor M Zavala, Reid C Van Lehn
The 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 8.4) Pub Date : 2020-10-16 Tian-Yang Yu, Wenhua Xu, Hong Lu, Hao Wei
We 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 8.4) Pub Date : 2020-10-16 Qijian Ni, Xiaoxiao Song, Chin Wen Png, Yongliang Zhang, Yu Zhao
We 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 8.4) Pub Date : 2020-10-16 Yidong Wang, Jin Zhu, Rui Guo, Haley Lindberg, Yiming Wang
The 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 8.4) Pub Date : 2020-10-15 Ilse M. Welleman, Mark W. H. Hoorens, Ben L Feringa, Hendrikus H. Boersma, Wiktor Szymanski
Light-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 8.4) Pub Date : 2020-10-14 Zhe Wang, Akira Matsumoto, Keiji Maruoka
A 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 8.4) Pub Date : 2020-10-14 Masashi Mamada, Ryota Nakamura, Chihaya Adachi
Peri-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 8.4) Pub Date : 2020-10-12 Hiromu Fuse, Hiroyasu Nakao, Yutaka Saga, Arisa Fukatsu, Mio Kondo, Shigeyuki Masaoka, Harunobu Mitsunuma, Motomu Kanai
A 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 8.4) Pub Date : 2020-10-12 Antoine Meunier, Michael Singleton, Brice Kauffmann, Thierry Granier, Guillaume Lautrette, Yann Ferrand, Ivan Huc
As 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 8.4) 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 Li
The 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 8.4) 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 McFarland
A 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 8.4) Pub Date : 2020-10-05 Valeria Mantella, Laia Castilla i Amoròs, Raffaella Buonsanti
Non-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 8.4) Pub Date : 2020-09-30 Duc Nguyen, Kaifu Gao, Jiahui Chen, Rui Rui Wang, Guowei Wei
Currently, 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 8.4) Pub Date : 2020-09-23 Xujiao Ma, Yajie Yang, Rongchen Ma, Yunfeng Zhang, Xiaoqin Zou, Shoujun Zhu, Xin Ge, Ye Yuan, Wei Zhang, Guangshan Zhu
Despite 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 8.4) Pub Date : 2020-09-16 Tanguy Jousselin-Oba, Masashi Mamada, Atsushi Okazawa, Jérome Marrot, Takayuki Ishida, Chihaya Adachi, Abderrahim Yassar, Michel Frigoli
Biradicaloid 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 8.4) Pub Date : 2019-11-27 Yiheng Song, Jisuan Tan, Guan Wang, Pengxiang Gao, Jiehao Lei, Li Zhou
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Single electron transfer events and dynamical heterogeneity in the small protein azurin from Pseudomonas aeruginosa Chem. Sci. (IF 8.4) Pub Date : 2019-11-27 Biswajit Pradhan, Christopher Engelhard, Sebastiaan Van Mulken, Xueyan Miao, Gerard W. Canters, Michel Orrit
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NIR nanoprobe-facilitated cross-referencing manifestation of local disease biology for dynamic therapeutic response assessment Chem. Sci. (IF 8.4) Pub Date : 2019-11-27 Zhimin Wang, Xiangzhao Ai, Zhijun Zhang, Yong Wang, Xiangyang Wu, Richard Haindl, Edwin K. L. Yeow, Wolfgang Drexler, Mingyuan Gao, Bengang Xing
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Chain propagation determines the chemo- and regioselectivity of alkyl radical additions to C–O vs. C–C double bonds Chem. Sci. (IF 8.4) Pub Date : 2019-11-26 Tiffany O. Paulisch, Felix Strieth-Kalthoff, Christian Henkel, Lena Pitzer, Dirk M. Guldi, Frank Glorius
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A photo-regulated aptamer sensor for spatiotemporally controlled monitoring of ATP in the mitochondria of living cells Chem. Sci. (IF 8.4) Pub Date : 2019-11-26 Shanni Hong, Xiaoting Zhang, Ryan J. Lake, Gregory T. Pawel, Zijian Guo, Renjun Pei, Yi Lu
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A novel photoredox-active group for the generation of fluorinated radicals from difluorostyrenes Chem. Sci. (IF 8.4) Pub Date : 2019-11-26 Mikhail O. Zubkov, Mikhail D. Kosobokov, Vitalij V. Levin, Vladimir A. Kokorekin, Alexander A. Korlyukov, Jinbo Hu, Alexander D. Dilman
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III–V colloidal nanocrystals: control of covalent surfaces Chem. Sci. (IF 8.4) Pub Date : 2019-11-26 Youngsik Kim, Jun Hyuk Chang, Hyekyoung Choi, Yong-Hyun Kim, Wan Ki Bae, Sohee Jeong
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Two-dimensional lanthanide coordination polymer nanosheets for detection of FOX-7 Chem. Sci. (IF 8.4) Pub Date : 2019-11-26 Tufan Singha Mahapatra, Ananta Dey, Harwinder Singh, Sk Saddam Hossain, Amal Kumar Mandal, Amitava Das
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Construction of a self-directed replication system for label-free and real-time sensing of repair glycosylases with zero background. Chem. Sci. (IF 8.4) Pub Date : 2019-11-26 Li-Juan Wang,Ying-Ying Lu,Chun-Yang Zhang
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Persistent organic room temperature phosphorescence: what is the role of molecular dimers? Chem. Sci. (IF 8.4) Pub Date : 2019-11-25 Yunsheng Wang, Jie Yang, Yu Tian, Manman Fang, Qiuyan Liao, Liwei Wang, Wenping Hu, Ben Zhong Tang, Zhen Li
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Chiral cis-iron(II) complexes with metal- and ligand-centered chirality for highly regio- and enantioselective alkylation of N-heteroaromatics Chem. Sci. (IF 8.4) Pub Date : 2019-11-25 Jinhu Wei, Bei Cao, Chun-Wai Tse, Xiao-Yong Chang, Cong-Ying Zhou, Chi-Ming Che
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Reduction of a dihydroboryl cation to a boryl anion and its air-stable, neutral hydroboryl radical through hydrogen shuttling. Chem. Sci. (IF 8.4) Pub Date : 2019-11-25 Stephan Hagspiel,Merle Arrowsmith,Felipe Fantuzzi,Alexander Hermann,Valerie Paprocki,Regina Drescher,Ivo Krummenacher,Holger Braunschweig