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A DASA Displaying Highly Efficient and Rapid Reversible Isomerization within Sustainable Nano/Micro Capsules: One Step Closer to Sustainability Chem. Sci. (IF 7.6) Pub Date : 2024-09-25 Baoshuo Liu, Xinnian Fan, Jun Xiang, Hao Ma, Yutong Xie, Haojun Fan, Qiang Yan
Donor-acceptor Stenhouse adducts (DASAs) are photochromic molecules derived from furfural that exhibit reversible isomerization under visible light and thermal stimuli. Achieving efficient and rapid reversible isomerization of DASAs within solid matrices under mild conditions is crucial for their practical application. However, such examples remain scarce, posing significant challenges related to the
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Probing Substrate Binding inside a Paramagnetic Cavity: A NMR Spectroscopy Toolbox for Combined Experimental and Theoretical Investigation Chem. Sci. (IF 7.6) Pub Date : 2024-09-24 Sabyasachi Sarkar, Chang-Quan Wu, Santanu Manna, Deepannita Samanta, Peter Ping-Yu Chen, Sankar Prasad Rath
Protein cavities often rely on the paramagnetic metal present in their active site in order to catalyze various chemical transformations in biology. The selective detection and identification of the substrate is of fundamental importance in environmental monitoring and biological studies. Herein, a covalently linked Fe(III)porphyrin dimer-based paramagnetic sensory cavity has been devised for an accurate
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An alternating copolymer of phenothiazine and ethylenedioxythiophene for perovskite solar cells: effects of flexible and rigid substituent alternation Chem. Sci. (IF 7.6) Pub Date : 2024-09-24 Bing Zhang, Yaohang Cai, Lifei He, Niansheng Xu, Yi Yuan, Jing Zhang, Yuyan Zhang, Peng Wang
Developing p-type polymeric semiconductors with exceptional electrical performance, heat tolerance, and cost-effectiveness is pivotal for advancing the practical application of n-i-p perovskite solar cells. Here, we employed direct arylation polycondensation to synthesize an alternating copolymer of phenothiazine and 3,4-ethylenedioxythiophene, featuring a high glass transition temperature (175 °C)
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Tether-entangled conjugated helices Chem. Sci. (IF 7.6) Pub Date : 2024-09-24 Ke Jin, Zuo Xiao, Huidong Xie, Xingxing Shen, Jizheng Wang, Xiangyu Chen, Zhijie Wang, Zujin Zhao, Keyou Yan, Yong Ding, Liming Ding
A new design concept, tether-entangled conjugated helices (TECHs), is introduced for helical polyaromatic molecules. TECHs consist of a linear polyaromatic ladder backbone and periodically entangling tethers with the same planar chirality. By limiting the length of tether, all tethers synchronously bend and twist the backbone with the same manner, and change it into a helical ribbon with a determinate
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Selective inhibition of cancer cell migration using a pH-responsive nucleobase-modified DNA aptamer Chem. Sci. (IF 7.6) Pub Date : 2024-09-24 Yuyuan Chen, Kunihiko Morihiro, Yui Nemoto, Akito Ichimura, Ryosuke Ueki, Shinsuke Sando, Akimitsu Okamoto
Because of the extracellular acidic microenvironment of cancer cells, many pH-responsive molecules have become indispensable materials for bioanalysis and targeted therapy development. pH-Responsive DNA aptamers, which selectively bind to target proteins in cancer cells, have become a key research target in the therapeutic field. However, conventional pH-responsive aptamers have fatal drawbacks, such
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Discovery of polyketide carboxylate phytotoxin from polyketide glycoside hybrid by β-glucosidase mediated ester bond hydrolysis Chem. Sci. (IF 7.6) Pub Date : 2024-09-24 Xin Wang, Dekun Kong, Hua-Ran Zhang, Yi Zou
Fungal phytotoxins cause significant harm to agricultural production or lead to plant diseases. Discovering new phytotoxins, dissecting their formation mechanism and understanding their action mode are important for controlling the harmful effects of fungal phytopathogens. Here, a long term unsolved cluster (polyketide synthase 16, PKS16 cluster) from Fusarium species has been well investigated and
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Single-Molecule Detection of a Terrylenediimide-Based Near-Infrared Emitter Chem. Sci. (IF 7.6) Pub Date : 2024-09-24 Suvarna Sujilkumar, Philip Daniel Maret, Kavya Vinod, Athira T John, Mahesh Hariharan
Environment-sensitive fluorescent agents with near-infrared (NIR) emission are in great demand owing to their applications in biomedical and quantum technologies. We report a novel NIR absorbing (λmaxAbs = 735 nm) and emitting (λmaxFl = 814 nm) terrylenediimide (TDI) based donor-acceptor chromophore (TDI-TPA4), exhibiting polarity-sensitive single-photon emission. By virtue of the charge transfer (CT)
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Direct Observation of β-Alkynyl Eliminations from Unstrained Propargylic Alkoxide Cu(I) Complexes by C-C Bond Cleavage Chem. Sci. (IF 7.6) Pub Date : 2024-09-23 Ba Tran, Jack Fuller III, Jeremy D. Erickson, Bojana Ginovska, Simone Raugei
β-Carbon eliminations of aryl, allylic, and propargylic alkoxides of Rh(I), Pd(II), and Cu(I) are key elementary reactions in the proposed mechanisms of homogeneously catalysed cross coupling, group transfer, and annulation. Besides the handful of studies with isolable Rh(I)-alkoxides, β-carbon eliminations of Pd(II)- and Cu(I)-alkoxides are less definitive. Herein, we provide a comprehensive synthetic
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Resolving molecular frontier orbitals in molecular junctions with kHz resolution Chem. Sci. (IF 7.6) Pub Date : 2024-09-23 Yuji Isshiki, Enrique Montes, Tomoaki Nishino, Hector Vazquez, Shintaro Fujii
Designing and building single-molecule circuits with tailored functionalities requires a detailed knowledge of the junction electronic structure. The energy of frontier molecular orbitals and their electronic coupling to the electrodes play a key role in determining the conductance of nanoscale molecular circuits. Here, we developed a method for measuring current-voltage (I−V) characteristics of single-molecule
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Visualization of Drug Release in a Chemo-Immunotherapy Nanoplatform via Ratiometric 19F Magnetic Resonance Imaging Chem. Sci. (IF 7.6) Pub Date : 2024-09-23 Fanqi Liu, Xindi Li, Yumin Li, Suying Xu, Chang Guo, Leyu Wang
Visualization of drug release in vivo is crucial for improving therapeutic efficacy and preventing inappropriate medication dosing, yet, challenging. Herein, we report a pH-activated chemo-immunotherapy nanoplatform with visualization of drug release in vivo by ratiometric 19F magnetic resonance imaging (19F MRI). This nanoplatform consists of ultra-small histamine-modified perfluoro-15-crown-5-ether
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AI Empowering Traditional Chinese Medicine? Chem. Sci. (IF 7.6) Pub Date : 2024-09-23 Zhilin Song, Guan-Xing Chen, Calvin Yu-Chian Chen
For centuries, Traditional Chinese Medicine (TCM) has been a prominent treatment method in China, incorporating acupuncture, herbal remedies, massage, and dietary therapy to promote holistic health and healing. TCM has played a major role in drug discovery, with over 60% of small-molecule drugs approved by the FDA from 1981 to 2019 being derived from natural products. However, TCM modernization faces
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Water at electrode-electrolyte interfaces: combining HOD vibrational spectra with ab initio-molecular dynamics simulations Chem. Sci. (IF 7.6) Pub Date : 2024-09-23 Pavithra Gunasekaran, Xianglong Du, Andrew Burley, Jiabo Le, Jun Cheng, Angel Cuesta
We have undertaken a vibrational study of the structure of interfacial water and its potential dependence using H2O:D2O mixtures to explore the O-H and O-D stretching modes of HOD as well as the bending modes of HOD and H2O. Due to the symmetry reduction, some of the complexity characteristic of the vibrational spectrum of water is removed in HOD. Coupled with potential-dependent ab-initio simulations
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Mononuclear Metal Complex Catalysts on Supports:Foundations in Organometallic and Surface Chemistry and Insights into Structure, Reactivity, and Catalysis Chem. Sci. (IF 7.6) Pub Date : 2024-09-20 Bruce C Gates
Catalysts that consist of isolated metal atoms bonded to solid supports have drawn wide attention by researchers, with recent work emphasizing noble metals on metal oxide and zeolite supports. Progress has been facilitated by methods for atomic-scale imaging the metals and spectroscopic characterization of the supported structures and the nature of metal–support bonding, even with catalysts in the
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Facile and scale-up syntheses of high-performance enzyme@meso-HOF biocatalysts Chem. Sci. (IF 7.6) Pub Date : 2024-09-20 Zhengyi Di, Yu Qi, Xin-Xin Yu, Hai-Ruo Li, Meng-Xuan Zuo, Tian-Tian Ren, Cheng-Peng Li, Yanli Zhao
Facile immobilization is essential for the wide application of enzymes in large-scale catalytic processes. However, exploration of suitable enzyme supports poses an unmet challenge, particularly in the context of scale-up biocatalyst fabrication. In this study, we present facile and scale-up syntheses of high-performance enzyme biocatalysts via in situ encapsulation of cytochrome c (Cyt-c) as mono-enzyme
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Facilitating Intrinsic Delayed Fluorescence of Conjugated Emitters by Inter-Chromophore Interaction Chem. Sci. (IF 7.6) Pub Date : 2024-09-20 Yixuan Gao, Yingman Sun, Zilong Guo, Guo Yu, Yaxin Wang, Yan Wan, Yandong Han, Wensheng Yang, Dongbing Zhao, Xiaonan Ma
The delayed fluorescence (DF) is a unique emitting phenomenon and of great interest for important applications in organic optoelectronics. In general, DF requires well-separated frontier orbitals, inherently corresponding to charge transfer (CT) type emitters. However, facilitating intrinsic DF for local excited (LE) type conjugated emitters remains great challenging. Aiming to overcome this obstacle
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Promoting Oxygen Electrode Reaction Kinetics in Photo-Assisted Li-O2 Batteries Through Heterostructure Design and Built-In Electric Field Construction Chem. Sci. (IF 7.6) Pub Date : 2024-09-20 Yinglei Tao, Tao Wang, Xingyu Yu, Ke Gong, Hao GONG, Haixia Chen, Xiaoli Fan, Aidi Zhang, Xianli Huang, Kun Chang, Jianping He
The Li-O2 batteries (LOBs) boast an exceptionally high theoretical energy density; however, the slow kinetics of the oxygen electrode reaction have been a significant hurdle in their advancement and practical application. In this study, a composite of bismuth oxyhalides heterojunction incorporated with metal-organic frameworks (MOFs) was engineered on carbon cloth (Zr-MOF/BiOIBr/CC) as an efficient
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Electron-losing regulation strategy for stripping modulation towards highly reversible Zn Anode Chem. Sci. (IF 7.6) Pub Date : 2024-09-20 Xinyi Wang, Liyang Liu, Zewei Hu, Chao Han, Xun Xu, Shi Xue Dou, Weijie Li
Practical application of aqueous zinc-ion batteries (AZIBs) is hindered by their low Coulombic efficiency (CE) and unstable cycle life. Numerous electrolyte-additive-related studies have been implemented, but most of the focus has been gathered on the Zn plating process. In fact, the practical AZIBs undergo stripping in practice rather than plating in the initial cycle, because the commonly-used cathodes
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The Role of an Intramolecular Hydrogen Bond in the Redox Properties of Carboxylic Acid Naphthoquinones Chem. Sci. (IF 7.6) Pub Date : 2024-09-20 Walter Damian Guerra, Emmanuel Odella, Kai Cui, Maxim Secor, Rodrigo E. Dominguez, Edwin J. Gonzalez, Thomas A. Moore, Sharon Hammes-Schiffer, Ana L Moore
A bioinspired naphthoquinone model of the quinones in photosynthetic reaction centers but bearing an intramolecular hydrogen-bonded carboxylic acid has been synthesized and characterized electrochemically, spectroscopically, and computationally to provide mechanistic insight into the role of proton-coupled electron transfer of quinone reduction in photosynthesis. The reduction potential of this construct
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Plasmon-Powered Chemistry with Visible-Light Active Copper Nanoparticles Chem. Sci. (IF 7.6) Pub Date : 2024-09-20 Shreya Tyagi, Radha Krishna Kashyap, Ankit Dhankhar, Pramod P Pillai
In the quest for affordable materials for doing visible-light driven chemistry, we report here intriguing optical and photothermal properties of plasmonic copper nanoparticles (CuNPs). Precise tuning of reaction conditions and surface functionalization yield stable and monodisperse CuNPs, with a strong localized surface plasmon absorption at ~580 nm. The molar extinction coefficient is estimated to
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Solvation Structures Dependent Ion Transport and Desolvation Mechanism for Fast-Charging Li-Ion Batteries Chem. Sci. (IF 7.6) Pub Date : 2024-09-20 Zhenyu Fan, Jingwei Zhang, Lanqing Wu, Huaqing Yu, Jia Li, Kun Li, Qing Zhao
The solvation structures of Li+ in electrolytes take prominent roles on determining the fast-charging capabilities of lithium-ion batteries (LIBs), which are urgent demand for smart electronic devices and electric vehicles. Nevertheless, a comprehensive understanding on how solvation structures affect ion transport through the electrolyte bulk and interfacial charge transfer reaction remain elusive
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Cooperative intra- and intermolecular hydrogen bonding in scaffolded squaramide arrays Chem. Sci. (IF 7.6) Pub Date : 2024-09-19 Luis Martínez-Crespo, George F. S. Whitehead, Iñigo J. Vitorica Yrezabal, Simon Webb
The structural, self-assembly and binding properties of oligo-(phenylene-ethynylene) (OPE) rigid rods linked to squaramides (SQs) have been studied and correlated with rod length. In the solid-state, OPE-SQ conjugates form indefinite arrays of head-to-tail hydrogen bonded SQs, arrays that include both intra- and intermolecular hydrogen bonds. In dichloromethane solution, intramolecularly hydrogen bonded
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Intermolecular Sulfur Atom Transfer Cascade Enabled Late-Stage Introduction of Sulfilimines into Peptides Chem. Sci. (IF 7.6) Pub Date : 2024-09-19 Zeyuan He, Yuyang Liu, Guangjun Bao, Yiping Li, Xiufang Zhao, Quan Zuo, Kai Li, Wangsheng Sun, Rui Wang
Sulfilimine, a privileged class of −S(IV)=N− functional group found in nature, have been exploited as valuable building blocks in organic synthesis and as pharmacophores in drug discovery, and have aroused significant interests for chemical community. Nevertheless, the strategies for late-stage introduction of sulfilimines into peptides and proteins have still met with limited success. Herein, we have
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Copper Catalyzed Benzylic sp3 C-H Alkenylation Chem. Sci. (IF 7.6) Pub Date : 2024-09-19 Ting-An Chen, Richard J. Staples, Timothy H. Warren
The prenyl group is present in numerous biologically active small molecule drugs and natural products. We introduce benzylic C-H alkenylation of substrates Ar-CH3 with alkenylboronic esters (CH2)3O2B-CH=CMe2 as a pathway to form prenyl functionalized arenes Ar-CH2CH=CMe2. Mechanistic studies of this radical relay catalytic protocol reveal diverse reactivity pathways exhibited by the copper(II) vinyl
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Visible-light induced Mallory reaction of tertiary benzanilides via iminium intermediates Chem. Sci. (IF 7.6) Pub Date : 2024-09-19 Xiaoqiang Ma, Si Wang, Zhanyong Tang, jialin Huang, Tianhao Jia, Xingda Zhao, Depeng Zhao
The Mallory reaction is of significant synthetic importance, involving the photocyclization of stilbenes/diarylethenes and their analogues into polycyclic aromatics. However, the application of the Mallory reaction to tertiary benzanilides has not been explored to date. Besides, most of the reported Mallory reactions require ultraviolet irradiation. In this study, we show the first Mallory reaction
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Electron Transport Chain-Inspired Coordination Polymer for Macroscopic Spatiotemporal Scales of Charge Separation and Transport in Photocatalysis Chem. Sci. (IF 7.6) Pub Date : 2024-09-19 Lin Ma, Tiexin Zhang, Mochen Li, Xu Zhang, Lanqiao Li, Yusheng Shi, Rui Cai, Xueming Yang, Chunying Duan
Classic homogeneous photocatalysis is limited by the temporal transience and the spatial proximity of photoinduced charge separation and transport. The electron transfer chain (ETC) in cellular respiration can mediate unidirectional and long-range electron transfer to isolate the oxidation and reduction centres. Inspired by this, we modified electron-accepting (A) viologen with π-extending thiazolothiazole
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Two-dimensional nanomaterials based on rare earth elements for biomedical applications Chem. Sci. (IF 7.6) Pub Date : 2024-09-19 Mingjun Bai, Hao Wan, Ying Zhang, Siqi Chen, Chunyin Lu, Xiaohe Liu, Gen Chen, Ning Zhang, Renzhi Ma
As a kind of star materials, two-dimensional (2D) nanomaterials have attracted tremendous attention for their unique structures, excellent performance and wide applications. In recent years, layered rare earth-based or doped nanomaterials have become a new important member of the 2D nanomaterials family and have attracted significant interest, especially the layered rare earth hydroxides (LREHs) and
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Designer Pseudopeptides: Autofluorescent Polygonal Tubes via Phe-zipper and Triple Helix Chem. Sci. (IF 7.6) Pub Date : 2024-09-18 V. Haridas, Govind P Maurya, Souvik Dutta
Chemists are increasingly turning to biology for inspiring ideas that can be adopted to develop novel and superior synthetic materials. Here, we present an innovative peptide design strategy for tubular assembly. In this simple design, a phenylene urea unit is introduced as an aglet at the N-terminus of the peptide. When α-amino isobutyric acid (Aib) is the first residue and phenylalanine (Phe) is
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Dual-Emissive Luminescence in OIHMH Single Crystals: Tunable Red-Green Emissions via Mn2+ Doping and Theoretical Insights Chem. Sci. (IF 7.6) Pub Date : 2024-09-18 Qianrong Jin, Rui Wu, Yuexiao Pan, Hongzhou Lian, Yihong Ding, Jun Lin, Liyi Li
The burgeoning demand for materials with tunable photoluminescence properties for applications has necessitated the exploration of novel luminescent materials. This study presents the synthesis and characterization of a novel 0D organic-inorganic hybrid metal halide (OIHMH) single crystal, C6H14N2CdBr4, which exhibits intriguing luminescent properties upon Mn2+ doping. The introduction of single Mn2+
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Synthesis of Chiral α-Amino Acids via Pd(II)-Catalyzed Enantioselective C–H Arylation of α-Aminoisobutyric Acid Chem. Sci. (IF 7.6) Pub Date : 2024-09-18 Zi-Yu Zhang, tao zhang, Yuxin Ouyang, Peng Lu, Jennifer Xiaoxin Qiao, Jin-Quan Yu
Non-natural chiral α,α-disubstituted α-amino acids (α,α-AAs) are attractive Aib (α-aminoisobutyric acid) replacement for improving bioavailability of linear peptides as therapeutics due to their ability to induce helix structure. Enantioselective β-C(sp3)–H arylation of Aib could potentially provide a versatile one-step strategy for accessing diverse α,α-AAs, however, the installation and removal of
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Carbon-Based Bifunctional Heterogeneous Enzyme: Toward Sustainable Pollution Control Chem. Sci. (IF 7.6) Pub Date : 2024-09-18 Yuting Sun, Ming Guo, Shengnan Hu, Yankun Jia, Wenkai Zhu, Yusuke Yamauchi, Chaohai Wang
We present a study on immobilized functional enzyme (IFE), a novel biomaterial with exceptional sustainability in enzyme utility, widely employed across various fields worldwide. However, conventional carriers are prone to eroding the active functional domain of IFE, thereby weakening its intrinsic enzyme activity. Consequently, there is a burgeoning interest in developing next-generation IFEs. In
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Chemical and Redox Non-Innocence in Low‑Valent Molybdenum 𝜷-Diketonate Complexes: Novel Pathways for CO2 and CS2 Activation Chem. Sci. (IF 7.6) Pub Date : 2024-09-18 Fabio Masero, Victor Mougel
The investigation of fundamental properties of low‑valent molybdenum complexes bearing anionic ligands is crucial for elucidating the molybdenum’s role in critical enzymatic systems involved in the transformation of small molecules, including the nitrogenase’s iron molybdenum cofactor, FeMoco. The β-diketonate ligands in [Mo(acac)3] (acac = acetylacetonate), one of the earliest low‑valent Mo complexes
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Making the Inverted Keggin Ion Lacunary Chem. Sci. (IF 7.6) Pub Date : 2024-09-16 Lu-Lu Liu, Zi-Yu Xu, Peng Yi, Chao-Qin Chen, Zhong-Ling Lang, Peng Yang
The century-old inverted Keggin ion has been revisited, in an effort to unearth its potential in the structural engineering and functional development of polyoxomolybdates (POMos). Over the past hundred years, attempts to program the metal-oxo scaffold of inverted Keggin have been conducted continually but without any success. In this work, the structurally inert, inverted Keggin-type POMo finally
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Stereoselective Transition Metal-Catalyzed [(2+2)+1] and [(2+2)+2] Carbocyclization Reactions using 1,6-Enynes with 1,1-Disubstituted Olefins: Construction of Quaternary Centers Chem. Sci. (IF 7.6) Pub Date : 2024-09-12 Ridge Michael P. Ylagan, Yu Zhu, P. Andrew Evans
Transition metal-catalyzed carbocyclization reactions offer a powerful method for the stereoselective assembly of complex, highly substituted (poly)cyclic scaffolds. Although 1,6-enynes are common substrates for these transformations, using polysubstituted alkene derivatives to construct functionalized cyclic products remains challenging due to significantly lower reactivity. This Perspective highlights
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Reconstructing Nearly Isotropic Microstructures to Construct One-dimensional Framework Causing the Record Birefringence in Thiophosphates Chem. Sci. (IF 7.6) Pub Date : 2024-09-12 Lin-Tao Jiang, Xiao-Ming Jiang, yuhang fan, Bin-Wen Liu, Guo-Cong Guo
Infrared birefringent crystal that holds significant importance for optoelectronic application has been rarely reported. Traditional tetrahedral PS4, ethane-like P2S6, and octahedral InS6 units in thiophosphates typically manifest near isotropy, often resulting in extremely small birefringence. However, this study prepares -Rb2InP2S7 (1), -Rb2InP2S7 (3) and Cs2InP2S7 (2), consisting of the aforementioned
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Exploration, expansion and definition of the atropopeptide family of ribosomally synthesized and posttranslationally modified peptides Chem. Sci. (IF 7.6) Pub Date : 2024-09-10 Friederike Biermann, Bin Tan, Milena Breitenbach, Yuya Kakumu, Pakjira Nanudorn, Yoana Dimitrova, Allison Walker, Reiko Ueoka, Eric Helfrich
Ribosomally synthesized and posttranslationally modified peptides (RiPPs) constitute a diverse class of natural products. Atropopeptides are a recent addition to the class. Here we developed AtropoFinder, a genome mining algorithm to chart the biosynthetic landscape of the atropopeptides. AtropoFinder identified more than 650 atropopeptide biosynthetic gene clusters (BGCs). We pinpointed crucial motifs
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Leveraging Ligand-Based Proton and Electron Transfer for Aerobic Reactivity and Catalysis Chem. Sci. (IF 7.6) Pub Date : 2024-09-09 Kate Jesse, John S Anderson
O2 is an abundant, benign, and thermodynamically potent oxidant. However, it is also kinetically inert which frequently limits its use in synthetic transformations. Correspondingly, direct aerobic reactivity with O2 often requires comparatively harsh or forcing conditions to overcome this kinetic barrier. Forcing conditions limit product selectivity and can lead to over oxidation. Alternatively, O2
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Heavy-Atom Tunnelling in Benzene Isomers: How Many Tricyclic Species are Truly Stable? Chem. Sci. (IF 7.6) Pub Date : 2024-09-05 Sindy Julieth Rodríguez, Sebastian Kozuch
The variety of possible benzene isomers may provide a fundamental basis for understanding structural and reactivity patterns in organic chemistry. However, the vast majority of these isomers remain unsynthesized, while most of the experimentally known species are only moderately stable. Consequently, there is a high probability that the theoretically proposed isomers would also be barely metastable
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Cyclic Polymers from Alkynes: A Review Chem. Sci. (IF 7.6) Pub Date : 2024-09-04 Parker T. Boeck, Adam S. Veige
Cyclic polymers have applications across various fields, including material science, biomedicine, and inorganic chemistry. Cyclic polymers derived from alkyne monomers have expanded the application scope to include electronic materials and polyolefins. This review highlights recent advancements in the synthesis of cyclic polymers from both mono- and disubstituted alkynes. The aim is to provide a comprehensive
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Acylhydrazone-based reversibly photoswitchable ion pair transporter with OFF–ON transport activity Chem. Sci. (IF 7.6) Pub Date : 2024-08-30 Sandip Chattopadhayay, Paras Wanjari, Pinaki Talukdar
The cellular membrane transport of physiologically important cations and anions is omnipresent and regulates different physiological functions. Whereas a notable number of cation-anion transporters are being developed to transport salts across the membrane, developing an artificial cation-anion symporter with stimulus-responsive activities is an immense obstacle. Herein, for the first time, we report
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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 Kozlowska
The 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
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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 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 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 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 7.6) 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 7.6) 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 7.6) 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 7.6) 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 7.6) 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 7.6) 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 7.6) 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 7.6) 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 7.6) 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 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 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 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 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 7.6) 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 7.6) 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 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 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 7.6) 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 7.6) 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 7.6) Pub Date : 2019-11-27 Biswajit Pradhan, Christopher Engelhard, Sebastiaan Van Mulken, Xueyan Miao, Gerard W. Canters, Michel Orrit