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Combining Geometric Constraint and Redox Non-Innocence within an Ambiphilic PBiP Pincer Ligand Chem. Sci. (IF 8.4) Pub Date : 2024-03-18 Peter Coburger, Ana Guilherme Buzanich, Franziska Emmerling, Josh Abbenseth
The synthesis of the first pincer ligand featuring a strictly T-shaped group 15 element and its coordination behaviour towards transition metals is described. The platform is itself derived from a trianionic redox non-innocent NNN scaffold. In addition to providing a rigid coordination environment to constrain a Bi centre in a T-shaped geometry to manipulate its frontier molecular orbital constitution
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Temperature Modulated Sustainable on/off Photosynthesis Switching of Microalgae towards Hydrogen Evolution Chem. Sci. (IF 8.4) Pub Date : 2024-03-18 Shangsong Li, Zhijun Xu, Song Lin, Luxuan Li, Yan Huang, Xin Qiao, Xin Huang
Despite of great progress in the active interfacing between various abiotic material and living organisms, the develop of smart polymer matrix with modulated functionality of algae towards the application of green bioenergy is still rare. Herein, we design a thermal sensitive poly(N-isopropylacrylamide)-co-poly(butyl acrylate) with LCST (ca. 25 °C) as a chassis, which could co-assemble with algae cells
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Non-invasive Diagnosis of Bacterial and Non-Bacterial Inflammations Using a Dual-Enzyme-Responsive Fluorescent Indicator Chem. Sci. (IF 8.4) Pub Date : 2024-03-18 Yue He, majun yang, Jingyi Cui, Can Zhao, Bin Jiang, Jiayun Guan, Xiaobo Zhou, Miao He, Yaya Zhen, Yuxue zhang, rongrong jing, Qi Wang, Yuling Qin, Li Wu
Bacterial infections, as the second leading cause of global death, are commonly treated with antibiotics. However, the improper use of antibiotics contributes to the development of bacterial resistance. Therefore, the accurate differentiation between bacterial and non-bacterial inflammations is of utmost importance in the judicious administration of clinical antibiotics and the prevention of bacterial
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Efficient mRNA display protocol yields potent bicyclic peptide inhibitors for FGFR3c: outperforming linear and monocyclic formats in affinity and stability Chem. Sci. (IF 8.4) Pub Date : 2024-03-18 Camille Villequey, Silvana Smilla Zurmühl, Christian N. Cramer, Bhaskar Bhushan, Brigitte Andersen, Qiansheng Ren, Haimo Liu, Xinping Qu, Jia Pan, Yang Yang, Chen Qiujia, Martin Münzel
Macrocyclization has positioned itself as a powerful method for engineering potent peptide drug candidates. Introducing one or multiple cyclisations is a common strategy to improve properties such as affinity, bioavailability and proteolytic stability. Consequently, methodologies to create large libraries of polycyclic peptides by phage or mRNA display have emerged, allowing the rapid identification
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Restraining the shuttle effect of polyiodide and modulating the deposition of zinc ions to enhance the cycle lifespan of aqueous Zn-I 2 battery Chem. Sci. (IF 8.4) Pub Date : 2024-03-18 Qu Yue, Yu Wan, Xiaoqin Li, Qian Zhao, Taotao Gao, Guowei Deng, Bing Li, Dan Xiao
The boom of aqueous Zn-based energy storage devices, such as zinc-iodine (Zn-I2) batteries, is quite suitable for safe and sustainable energy storage technologies. However, in rechargeable aqueous Zn-I2 batteries, the shuttle phenomenon of polyiodide ions usually leads to irreversible capacity loss resulting from both the iodine cathode and the zinc anode, and thus impinges on the cycle lifespan of
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HgBr2: An Easily Growing Wide-Spectrum Birefringent Crystal Chem. Sci. (IF 8.4) Pub Date : 2024-03-16 Ming-Shu Zhang, Wen-Dong Yao, Shao-Min Pei, Bin-Wen Liu, Xiao-Ming Jiang, Guo-Cong Guo
Birefringent materials are of great significance to the development of modern optical technology; however, research on halide birefringent crystals with a wide transparent range remains limited. In this work, mercuric bromide (HgBr2) has been investigated for the first time as a promising birefringent material with a wide transparent window spanning from ultraviolet (UV) to far-infrared (far-IR) spectral
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Outer-sphere effects on the O2 sensitivity, catalytic bias and catalytic reversibility of hydrogenases Chem. Sci. (IF 8.4) Pub Date : 2024-03-15 Christophe Léger, Vincent Fourmond, Andrea Fasano
The comparison of homologous metalloenzymes, in which the same inorganic active site is surrounded by a variable protein matrix, has demonstrated that residues that are remote from the active site may have a great influence on catalytic properties. In this review we summarise recent findings on the diverse molecular mechanisms by which the protein matrix may define the oxygen tolerance, catalytic directionality
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Critical assessment on the interactions between ct-DNA and choline based magnetic ionic liquids: Evidences of compaction Chem. Sci. (IF 8.4) Pub Date : 2024-03-15 Kiran Devi Tulsiyan, Saroj Kumar Panda, Malay Kumar Rana, Himansu S. Biswal
The ionic liquids (ILs) have become an alternate green solvent for storage and stability of DNA. However, it needs an in depth understanding of the binding and molecular interactions between ILs and DNA. Magnetic ILs (MILs) in this regard are promising IL due to their tunable physicochemical properties. Various spectroscopic techniques and molecular simulations have been employed to unravel the critical
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Facile preparation of high-efficiency peroxidase mimics: Modulation catalytic microenvironment of LDH nanozymes through defect engineering induced by amino acids intercalation Chem. Sci. (IF 8.4) Pub Date : 2024-03-15 Dong Han, Kui Yang, Lanlan Chen, Zhaosheng Zhang, Chen Wang, Hongyuan Yan, Jia Wen
Nanozymes have gained much attention as the replacement of natural enzymes duo to their unique advantages. Two-dimensional layered double hydroxide (LDH) nanomaterials with high physicochemical plasticity are emerging as main forces for the construction of nanozymes. Unfortunately, high-performance LDH nanozymes are still scarce. Recently, defects in nanomaterials have been verified to play a significant
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Benchmarking pH-Field Coupled Microkinetic Modeling Against Oxygen Reduction in Large-Scale Fe-Azaphthalocyanine Catalysts Chem. Sci. (IF 8.4) Pub Date : 2024-03-15 Di Zhang, Yutaro Hirai, Koki Nakamura, Koju Ito, Yasutaka Matsuo, Kosuke Ishibashi, Yusuke Hashimoto, Hiroshi Yabu, Hao Li
Molecular metal-nitrogen-carbon (M-N-C) catalysts with well-defined structures and metal-coordination environments exhibit distinct structural properties and excellent electrocatalytic performance, notably in oxygen reduction reaction (ORR) for fuel cells. Metal-doped azaphthalocyanine (AzPc) catalysts, a variant of molecular M-N-Cs, can be structured with unique long stretching functional groups,
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On the Origin of Cooperativity Effects in the Formation of Self-Assembled Molecular Networks at the Liquid/Solid Interface Chem. Sci. (IF 8.4) Pub Date : 2024-03-14 Tamara Rinkovec, Demian Kalebic, Wim Dehaen, Stephen Whitelam, Jeremy Harvey, Steven De Feyter
In this work we investigate the behaviour of molecules at the nanoscale using scanning tunnelling microscopy in order to explore the origin of the cooperativity in the formation of self-assembled molecular networks (SAMNs) at the liquid/solid interface. By studying concentration dependence of alkoxylated dimethylbenzene, a molecular analogue to 5-alkoxylated isophthalic derivatives, but without hydrogen
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Cobalt- or Rhodium-Catalyzed Synthesis of 1,2-Dihydrophosphete Oxides via C–H Activation and Formal Phosphoryl Migration Chem. Sci. (IF 8.4) Pub Date : 2024-03-14 Shengbo Xu, Rui-Jie Mi, Guangfan Zheng, Xingwei Li
A highly stereo- and chemoselective intermolecular coupling of diverse heterocycles with dialkynylphosphine oxides has been realized via cobalt/rhodium-catalyzed C−H bond activation. This protocol provides an efficient synthetic entry to functionalized 1,2-dihydrophosphete oxides in excellent yields via merger of C-H bond activation and formal 1,2-migration of the phosphoryl group. Compared with traditional
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Mn2+-Induced Structural Flexibility Enhances the Entire Catalytic Cycle and the Cleavage of Mismatches in Prokaryotic Argonaute Proteins Chem. Sci. (IF 8.4) Pub Date : 2024-03-14 Lirong Zheng, Bingxin Zhou, Yu Yang, bing zan, Bozitao Zhong, Banghao Wu, Yan Feng, Qian Liu, Hong Liang
Prokaryotic Argonaute (pAgo) proteins, a class of DNA/RNA-guided programmable endonucleases, have been extensively utilized in nucleic acid-based biosensors. The specific binding and cleavage of nucleic acids by pAgo proteins, which are crucial processes for their applications, are dependent on the presence of Mn2+ bound in the pockets, as verified through X-ray crystallography. However, a comprehensive
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Aza-Achmatowicz Rearrangement Coupled with Intermolecular Aza-Friedel-Crafts Enables Total Syntheses of Uleine and Aspidosperma Alkaloids Chem. Sci. (IF 8.4) Pub Date : 2024-03-14 Foqing Ma, Yunlong Li, Kornkamon Akkarasereenon, Huiying Qiu, Yuen Tsz Cheung, Zhihong Guo, Rongbiao Tong
Aspidosperma and uleine alkaloids belong to the large family of monoterpene indole alkaloids with diverse biological activities and thus have attracted extensive synthetic interests. Reported is the development of a new synthetic strategy that allows direct C3-C2′ linkage of indoles with functionalized 2-hydroxypiperidines to construct the core common to all aspidoserma and uleine alkaloids. Such indole-piperidine
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Engineering the passivation routes of the perovskite films towards high performance solar cells Chem. Sci. (IF 8.4) Pub Date : 2024-03-13 Liangzheng Zhu, Shendong Xu, Guozhen Liu, Long Liu, Han Zhou, Zhiqiang Ai, Xu Pan, Fapei Zhang
Passivation treatment is an effective method to suppress various defects in perovskite solar cells (PSCs), such as cation vacancies, under-coordinated Pb2+ or I-, and Pb-I antisite defects. A thorough understanding to the diversified impacts of different defect passivation methods (DPMs) on the device performance will be beneficial for making wise DPMs choices. Herein, we choose a hydrophobic Lewis
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Electrostatic [FeFe]-hydrogenase–carbon nitride assemblies for efficient solar hydrogen production Chem. Sci. (IF 8.4) Pub Date : 2024-03-13 Yongpeng Liu, Carolina Pulignani, Sophie Webb, Samuel James Cobb, Santiago Rodríguez-Jiménez, Dongseok Kim, Ross D. Milton, Erwin Reisner
The assembly of semiconductors as light absorbers and enzymes as redox catalysts offers a promising approach for sustainable chemical synthesis driven by light. However, achieving the rational design of such semi-artificial systems requires a comprehensive understanding of the abiotic-biotic interface, which poses significant challenges. In this study, we demonstrate an electrostatic interaction strategy
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Streamlining the Automated Discovery of Porous Organic Cages Chem. Sci. (IF 8.4) Pub Date : 2024-03-13 Annabel Basford, Steven Bennett, Muye Xiao, Lukas Turcani, Jasmine Allen, Kim E. Jelfs, Rebecca L Greenaway
Self-assembly through dynamic covalent chemistry (DCC) can yield a range of multi-component organic assemblies. The reversibility and dynamic nature of DCC has made prediction of reaction outcome particularly difficult and thus slows the discovery rate of new organic materials. In addition, traditional experimental processes are time-consuming and often rely on serendipity. Here, we present a streamlined
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Near-IR Ratiometric Fluorescent Probe for the Precise Tracking of Senescence: A Multidimensional Sensing Assay of Biomarkers in Cell Senescence Pathways Chem. Sci. (IF 8.4) Pub Date : 2024-03-13 Haihong Liu, Ruidian Lv, Fuxiang Song, Yaqun Yang, Fei Zhang, Liantao Xin, Peng Zhang, Qian Zhang, Caifeng Ding
Senescence is a complex physiological process that can be induced by a range of factors, and cellular damage caused by reactive oxygen species (ROS) is one of the major triggers. In order to learn and solve age-related diseases, tracking strategies through biomarkers, including senescence-associated β-galactosidase (SA-β-gal), with high sensitivity and accuracy, have been considered as a promising
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Efficient Red Thermally Activated Delayed Fluorescence Emitter Achieved Through Precise Control of Excited State Energy Levels Chem. Sci. (IF 8.4) Pub Date : 2024-03-12 Dongdong Wang, BoHua Zhang, Siqi Liu, Jiangxue Pei, MeiTing Luo, Yi Chen, Qingyu Jia, Zhaoxin Wu
The variety of highly efficient red/near-infrared (NIR) materials with thermally activated delayed fluorescence (TADF) feature are extremely limited so far, and it is necessary to expand the candidate pool of excellent red/deep-red emitters. However, how to control the energy level alignment of the 1CT (singlet charge transfer) state and the 3LE (triplet local excitation) state to improve the emission
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Organocatalyst-mediated asymmetric one-pot/two domino/three-component coupling reactions for the synthesis of trans-hydrindanes Chem. Sci. (IF 8.4) Pub Date : 2024-03-12 Naoki Mori, Toshiki Tachibana, Nariyoshi Umekubo, Yujiro Hayashi
Highly substituted trans-hydrindanes were synthesized by the three-component coupling reactions of 1,3-diethyl 2-(2-oxopropylidene)propanedioate and two different α,β-unsaturated aldehydes catalyzed by diphenylprolinol silyl ether. The reaction proceeds via two successive independent catalytic domino reactions in a one-pot reaction by a single chiral catalyst. Domino reactions involve Michael/Michael
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Electronic Lieb lattice signatures embedded in two-dimensional polymers with square lattice Chem. Sci. (IF 8.4) Pub Date : 2024-03-12 Yingying Zhang, Shuangjie Zhao, Miroslav Polozij, Thomas Heine
Exotic band features, such as Dirac cones and flat bands, arise directly from the lattice symmetry of materials. The Lieb lattice is one of the most intriguing topologies, because it possesses both Dirac cones and flat bands which intersect at the Fermi level. However, the synthesis of Lieb lattice materials remains a challenging task. Here, we explore two-dimensional polymers (2DPs) derived from zinc-phthalocyanine
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Predicting Valence Tautomerism in Diverse Cobalt-Dioxolene Complexes: Elucidation of the Role of Ligands and Solvent Chem. Sci. (IF 8.4) Pub Date : 2024-03-12 Fathima Zahra Mohamed Zahir, Moya Hay, Jett Tao Janetzki, Robert William Gable, Lars Goerigk, Colette Boskovic
The ability of molecular switches to reversibly interconvert between different forms promises potential applications at the scale of single molecules up to bulk materials. One type of molecular switch comprises cobalt-dioxolene compounds that exhibit thermally-induced valence tautomerism (VT) interconversions between low spin Co(III)-catecholate (LS-CoIII-cat) and high spin Co(II)-semiquinonate (HS-CoII-sq)
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A novel hydrophobic carborane-hybrid microporous material for reversed C2H6 adsorption and efficient C2H4/C2H6 separation under humid conditions Chem. Sci. (IF 8.4) Pub Date : 2024-03-12 Lingyao Wang, Shuangshuang Wu, Jianbo Hu, Yunjia Jiang, Jiahao Li, Yan Han, Yongqi Hu, Teng Ben, Banglin Chen, Yuanbin Zhang
Since ethylene (C2H4) is an important feedstock in the chemical industry, developing economical and energy-efficient adsorption separation techniques based on ethane (C2H6)-selective adsorbents to replace the energy-intensive cryogenic distillation is highly demanded, which however remains a daunting challenge. While previous anionic boron cluster hybrid microporous materials display C2H4 selective
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4-Fluorobenzyl Cyanide, Sterically-Hindered Solvent Expediting Interfacial Kinetics in Lithium-ion Batteries Chem. Sci. (IF 8.4) Pub Date : 2024-03-12 Mingsheng Qin, Ziqi Zeng, Qiang Wu, Xiaowei Liu, Qijun Liu, Shijie Cheng, Jia Xie
The electrochemical performance of lithium-ion batteries (LIBs) is plagued by sluggish interfacial kinetics and interfacial exacerbation. Fortunately, Li+ solvation structure bridges bulk electrolyte and interfacial chemistry, providing an innovative path for promoting electrochemical kinetics in LIBs. Here, we expedite the interfacial kinetics by tuning Li+ coordination chemistry based on solvent
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The Status and Challenging Perspectives of 3D-Printed Micro-Batteries Chem. Sci. (IF 8.4) Pub Date : 2024-03-12 Jiaxin Ma, Shuanghao Zheng, Yinghua Fu, Xiao Wang, Jie-Qiong Qin, Zhong-Shuai Wu
In the era of Internet of Things and wearable electronics, 3D-printed micro-battery with miniaturization, aesthetic diversity and high aspect ratio, has emerged as a recent innovation, which solves the problems of scare design diversity, poor flexibility and low mass loading of materials associated with traditional power sources restricted by the slurry-cast method. Comprehensive understanding the
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Open Shell (4n+2)π and Closed Shell 4nπ Planar Core-Modified Decaphyrins Chem. Sci. (IF 8.4) Pub Date : 2024-03-11 Pragati Shukla, Madan Ambhore, Venkataramanarao Govindan Anand
Planar 44π and 46π core-modified decaphyrins with ten thiophene units have been synthesized from short thiophene oligomers. They have been structurally characterized by single crystal X-ray diffraction with further support from spectroscopic analysis and quantum chemical calculations. Our analysis revealed diradicaloid characteristics for the 46π species in contrast to the closed shell property for
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Two-Dimensional Radial-π-Stacks in Solution Chem. Sci. (IF 8.4) Pub Date : 2024-03-11 Feng Su, Yongseok Hong, Guilan Zhang, Kongchuan Wu, Juno Kim, Zhi Chen, Hui-Jun Zhang, Dongho Kim, Jianbin Lin
Highly organized π-aggregate architectures can strongly affect electronic couplings, leading to important photophysical behaviors. With the escalating interest in two-dimensional (2D) materials attributed to their exceptional electronic and optical characteristics, there is a growing anticipation that 2D radial-π-stacks built upon radial π-conjugation nanorings, incorporating intra- and inter-ring
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Single-atom and cluster catalysts for thermocatalytic ammonia synthesis at mild conditions Chem. Sci. (IF 8.4) Pub Date : 2024-03-08 Xuanbei Peng, Mingyuan Zhang, Tianhua Zhang, Yanliang Zhou, Jun Ni, Xiuyun Wang, Lilong Jiang
Ammonia (NH3) is closely related to the fields of food and energy that humans depend on. The exploitation of advanced catalysts for NH3 synthesis is still a research hotspot despite more than one hundred years. Previous researches have shown that the Ru B5 sites (step sites on the Ru (0001) surface uniquely arranged with five Ru atoms) and Fe C7 sites (iron atoms with seven nearest neighbors) over
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Structure and photochemistry of di-tert-butyldiphosphatetrahedrane Chem. Sci. (IF 8.4) Pub Date : 2024-03-08 Gabriele Hierlmeier, Roger Jan Kutta, Peter Coburger, Georg Stammler, Jan Schwabedissen, Norbert Werner Mitzel, Maria Dimitrova, Raphael Berger, Patrick Nürnberger, Robert Wolf
Di-tert-butyldiphosphatetrahedrane (tBuCP)2 (1) is a mixed carbon- and phosphorus-based tetrahedral molecule, isolobal to white phosphorus (P4). However, despite the fundamental significance and well-explored reactivity of the latter molecule, the precise structure of the free (tBuCP)2 molecule (1) and a detailed analysis of its electronic properties have remained elusive. Here, single-crystal X-ray
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Shape Memory and Self-Healing in a Molecular Crystal with Inverse Temperature Symmetry Breaking Chem. Sci. (IF 8.4) Pub Date : 2024-03-08 Jiantao Meng, Yuan Su, Hang Zhu, Ting Cai
Mechanically responsive molecular crystals have attracted increasing attention for their potential as actuators, sensors, and switches. However, their inherent structural rigidity usually makes them vulnerable to external stimuli, limiting their usage in many applications. Here, we present the mechanically compliant single crystals of penciclovir, a first-line antiviral drug, achieved through an unconventional
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Electrosynthesis of Iminophosphoranes and Applications in Nickel Catalysis Chem. Sci. (IF 8.4) Pub Date : 2024-03-08 Velabo Mdluli, Dan Lehnherr, Yu-Hong Lam, Mohammad T. Chaudhry, Justin A Newman, Jimmy DaSilva, Erik Luis Regalado
P(V) iminophosphorane compounds are accessed via electrochemical oxidation of commercially available P(III) phosphines, including mono-, di- and tri-dentate phosphines, as well as chiral phosphines. The reaction uses inexpensive bis(trimethylsilyl)carbodiimide as an efficient and safe aminating reagent. DFT calculations, cyclic voltammetry, and NMR studies provide insight into the reaction mechanism
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How the AI-assisted discovery and synthesis of a ternary oxide highlights capability gaps in materials science Chem. Sci. (IF 8.4) Pub Date : 2024-03-07 Joseph Harold Montoya, Carolyn Grimley, Muratahan Aykol, Colin Ophus, Hadas Sternlicht, Benjamin H Savitzky, Andrew Minor, Steven Bartholomew Torrisi, Jackson Goedjen, Ching-Chang Chung, Andrew Comstock, Shijing Sun
Exploratory synthesis has been the main generator of new inorganic materials for decades. However, our Edisonian processes of synthetic exploration alone are no longer sufficient in an age that demands rapid advances in materials development. In this work, we demonstrate one of the first end-to-end attempts towards systematic, computer-aided discovery and laboratory synthesis of inorganic crystalline
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From propenolysis to enyne metathesis: tools for expedited assembly to 4a,8a-azaboranaphthalene and extended embedded BN-polycycles Chem. Sci. (IF 8.4) Pub Date : 2024-03-07 Federica Rulli, Guillem Sanz-Liarte, Pol Roca, Nina Martínez, Víctor Medina, Raimon Puig de la Bellacasa, Alexandr Shafir, Ana Belén Cuenca
The synthesis of BN-containing molecules, with an interesting isosteric relationship to their parent all-C cores, has drawn a great deal of attention as an avenue to alter and tune molecular function. Nevertheless, many BN-embedded cores are still hard to synthesize, and so sustained effort is required in that direction. Here, we present an integrated approach to BN-embedded polycycles rooted in an
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Laser capture microdissection and native mass spectrometry for spatially-resolved analysis of intact protein assemblies in tissue Chem. Sci. (IF 8.4) Pub Date : 2024-03-07 James Hughes, Emma Sisley, Oliver Hale, Helen J. Cooper
Previously, we have shown that native ambient mass spectrometry imaging allows the spatial mapping of folded proteins and their complexes in thin tissue sections. Subsequent top-down native ambient mass spectrometry of adjacent tissue section enables protein identification. The challenges associated with protein identification by this approach are i) the low abundance of proteins in tissue and associated
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Revealing the Role of Bridging Oxygen in Carbon Shell Coated Ni Interface for Enhanced Alkaline Hydrogen Oxidation Reaction Chem. Sci. (IF 8.4) Pub Date : 2024-03-06 Wei Luo, Pengyu Han, Xinyi Yang, Liqing Wu, Hongnan Jia
Encapsulating metal nanoparticles inside carbon layers is a promising approach to simultaneously improve the activity and stability of electrocatalysts. The role of carbon layer shells, however, is not fully understood. Herein, we study boron doped carbon layers coated nickel nanoparticles (Ni@BC) as a model catalyst to understand the role of bridging oxygen in carbon shell coated Ni interface for
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The superiority of Pd2+ in CO2 hydrogenation to formic acid Chem. Sci. (IF 8.4) Pub Date : 2024-03-06 Yanyan Wang, Minghua Dong, Shaopeng Li, Bingfeng Chen, Huizhen Liu, Buxing Han
The hydrogenation of CO2 to formic acid is an essential subject since formic acid is a promising hydrogen storage material and valuable commodity chemical. In this work, we firstly reported the hydrogenation of CO2 to formic acid catalyzed by Pd2+ catalyst Pd-V/AC-air. The catalyst exhibited extraordinary catalytic activity toward the hydrogenation of CO2 to formic acid. The TON and TOF are up to 4790
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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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Electrocatalytic CO2 Reduction to Formate by a Cobalt Phosphino-Thiolate Complex Chem. Sci. (IF 8.4) Pub Date : 2024-02-12 Jeremy A Intrator, David A Velazquez, Sicheng Fan, Ellie Mastrobattista, Christine J. Yu, Smaranda C Marinescu
Electrochemical conversion of CO2 to value-added products serves as an attractive method to store renewable energy as energy-dense fuels. Selectivity in this type of conversion can be limited, often leading to the formation of side products such as H2. The activity of a cobalt phosphino-thiolate complex ([Co(triphos)(bdt)]+) towards the selective reduction of CO2 to formate is explored in this report
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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