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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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Polymorphism and flexibility of six-porphyrin nanorings in the solid state Chem. Sci. (IF 7.6) Pub Date : 2024-09-18 Wojciech Stawski, Harry Laurence Anderson
Butadiyne-linked porphyrin nanorings are fascinating nanometer-sized platforms for exploring electronic delocalization and aromaticity, and they mimic ultra-fast photosynthetic energy-transfer phenomena in plants and purple bacteria. However, little is known about how they interact in the solid state. Here, we compare the crystal structures of several polymorphs of a six-porphyrin nanoring template
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Catechol/o-Benzoquinone Exchange at Gold(III) Chem. Sci. (IF 7.6) Pub Date : 2024-09-18 Félix León, Yago García-Rodeja, Sonia Mallet-Ladeira, Karinne Miqueu, György Szalóki, Didier Bourissou
Although gold(III) chemistry has tremendously progressed in the past 2 decades, gold(III) catecholate complexes remain extremely scarce and underdeveloped. Upon preparation and full characterization of P^C-cyclometalated gold(III) complexes, we serendipitously uncovered an intriguing catechol exchange process at gold(III). Electron-rich catecholates turned out to be readily displaced by electron-poor
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Does “Zero-Strain” Lithiated Spinel Serve as a Strain Retardant and Irreversible Phase Transition Regulator for Layered Oxide Cathode? Chem. Sci. (IF 7.6) Pub Date : 2024-09-18 Zixin Wu, Qizheng Zheng, Guiyang Gao, Jianhua Yin, Leiyu Chen, Yonglin Tang, Yawen Yan, Huan Huang, Yaru Qin, Xiaoxiao Kuai, Yu Qiao, Shi-Gang Sun
Layered oxide cathodes encounter structural challenges during cycling, prompting the exploration of an ingenious heterostructure strategy, which incorporates stable components into the layered structure as strain regulators to enhance materials cycle stability. Despite considerable research efforts, identifying suitable, convenient, and cost-effective materials and methods remains elusive. Herein,
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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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Structural basis of Pseudomonas aeruginosa penicillin binding protein 3 inhibition by the siderophore-antibiotic cefiderocol Chem. Sci. (IF 7.6) Pub Date : 2024-09-18 Helen G Smith, Shyam Basak, Victor Aniebok, Matthew J Beech, Faisal M Alshref, Mark D Allen, Alistair Farley, Christopher J Schofield
The breakthrough cephalosporin cefiderocol, approved for clinical use in 2019, has activity against many Gram-negative bacteria. The catechol group of cefiderocol enables it to efficiently enter bacterial cells via the iron/siderophore transport system thereby reducing resistance due to porin channel mutations and efflux pump upregulation. Limited information is reported regarding the binding of cefiderocol
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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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Helically chiral multiresonant thermally activated delayed fluorescent emitters and their use in hyperfluorescent organic light-emitting diodes Chem. Sci. (IF 7.6) Pub Date : 2024-09-18 Jingxiang Wang, Dongyang Chen, Juan Naranjo, Francesco Zinna, Lucas Frédéric, David Bradford Cordes, Aidan P McKay, Matthew Fuchter, Xiaohong Zhang, Eli Zysman-Colman
Chiral multiresonant thermally activated delayed fluorescence (MR-TADF) materials show great potential as emitters in circularly polarized (CP) organic light-emitting diodes (CP-OLEDs) owing to their bright and narrowband CP emission. Here, two new chiral MR-TADF emitters tBuPh-BN and DPA-tBuPh-BN possessing intrinsically helical chirality have been synthesized and studied. The large steric interactions
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Bucking the trend: understanding lipopolysaccharide structure and outer membrane dynamics in cold-adapted Pseudomonas isolated from Enigma Lake, Antarctica Chem. Sci. (IF 7.6) Pub Date : 2024-09-18 Marcello Mercogliano, Stefania De Chiara, Antonio De Nicola, Jacopo Cardellini, Costanza Montis, Mikhail M Yakimov, Violetta La Cono, Francesca Crisafi, Alba Silipo, Debora Berti, Giuseppe Milano, Antonio Molinaro, Flaviana Di Lorenzo
Cold environments are predominant over the Earth and are inhabited by bacteria able to cope with a series of simultaneous environmental pressures. Gram-negative species of the Pseudomonas genus are the predominant ones isolated from cold habitats, making them an excellent model for studying the mechanisms of bacterial adaptation to the most extreme habitats on our planet. Here we focused on the lipopolysaccharide
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Thiol-selective native grafting from polymerization for the generation of protein-polymer conjugates Chem. Sci. (IF 7.6) Pub Date : 2024-09-18 Melina Feldhof, Sandro Sperzel, Lorand Bonda, Susanne Boye, Adam Braunschweig, Ulla I.M. Gerling-Driessen, Laura Hartmann
Protein-polymer conjugates combine properties of biopolymers and synthetic polymers, such as specific bioactivity and increased stability, with great benefits for various applications from catalysis to biomedicine. Furthermore, polymer conjugation can mimic important posttranslational modifications of proteins such as glycosylation. There are typically two approaches to create protein-polymer conjugates:
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Introducing chirality in porous organic cages through solid-state interactions Chem. Sci. (IF 7.6) Pub Date : 2024-09-18 Emma Helen Wolpert, Kim E. Jelfs
Molecular cages contain an internal cavity designed to encapsulate other molecules, resulting in applications in molecular separation, gas storage, and catalysis. Introducing chirality in cage molecules can improve the selective separation of chiral molecules and add new functionalities due to the realisation of chiral photophysical properties. It has recently been shown that solid-state supramolecular
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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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Highly Efficient Circularly Polarized Electroluminescence Based on Chiral Manganese (II) Complexes Chem. Sci. (IF 7.6) Pub Date : 2024-09-18 De-Hao Kong, Yue Wu, Cui-Mi Shi, Hao Zeng, Liang-Jin Xu, Zhong-Ning Chen
Currently reported circularly polarized luminescent devices concentrate on rare earth and noble metal complexes or lead perovskite materials. Reports on electroluminescent devices employing eco-friendly luminescent materials are notably scarce. In this study, we strategically designed and synthesized manganese complexes featuring Binapo as the chiral ligand. The complex structure reveals a tetrahedral
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A Structurally Conserved Helix Enables Leader-Independent Tyramine Splicing of Proteins Chem. Sci. (IF 7.6) Pub Date : 2024-09-18 Daniel Richter, Alicia Courvoisier-Clément, Anna Lisa Vagstad, Sarolt Magyari, Joern Piel
Ribosomally synthesized and post-translationally modified peptides (RiPPs) are natural products that feature diverse modifications. They show a wide range of biological activities and are therefore of great interest for drug discovery and protein engineering. An unusual modification found in spliceotide RiPPs is the installation of β-amino acid residues with diverse side chains, generated by backbone
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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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Robust Inorganic Binder Against Corrosion and Peel-Off Stress in Electrocatalysis Chem. Sci. (IF 7.6) Pub Date : 2024-09-18 Joey Andrew Arquisola Valinton, Meng-Yu Lin, Cheng-Han Tsai, Cheng-Te Tsai, Ming-Jia Chiu, Cheng-chau Chiu, Chun-Hu Chen
Electrochemical binders used to immobilize electrocatalysts on electrodes are essential in all fields of electrochemistry. Yet conventional organic-based binders like Nafion generally suffer from oxidative decomposition at high potential on anodic electrodes, as well as from a high charge transport resistivity. This work proposes the acidic redox-assisted deposition of cobalt manganese oxyhydroxides
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Surface Reconstruction Route for Increasingly Improved Photocatalytic H2O2 Production Using Sr2Bi3Ta2O11Cl Chem. Sci. (IF 7.6) Pub Date : 2024-09-18 Maqsuma Banoo, Arjun Kumar Sah, Raj Sekhar Roy, Komalpreet Kaur, Bramhaiah Kommula, Dirtha Sanyal, Ujjal K. Gautam
Photocatalytic hydrogen peroxide (H2O2) generation is attractive for the chemical industry and energy production. However, photocatalysts generally deteriorate significantly during use to limit their application. Here we present the highly active, Sr2Bi3Ta2O11Cl single-crystal nanoplates for conversion of O2 to H2O2 using ambient air with a production rate of ~3 mmol/h/g (maximum 17.5% photon conversion)
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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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Photobiocatalytic CO2 reduction into CO by organic nanorods-carbon monoxide dehydrogenase assemblies: surfactant matters Chem. Sci. (IF 7.6) Pub Date : 2024-09-18 Mariia V. Pavliuk, Maximilian Böhm, Janna Wilhelmsen, Henrik Land, Steffen Hardt, Haining Tian
Photobiocatalytic CO2 reduction represents an attractive approach for conversion of solar light and abundant resources to value-added chemicals. However, the design of suitable systems requires a detailed understanding of the interaction between artificial photosensitizer and biocatalyst interface. In this work, we investigate the effect of surfactant charge utilized in the preparation of a phenoxazine-based
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Optical Activity Levels of Metal Centers Controlling Multi-Mode Emissions in Low-Dimensional Hybrid Metal Halides for Anti-Counterfeiting and Information Encryption Chem. Sci. (IF 7.6) Pub Date : 2024-09-16 Qiqiong Ren, Guojun Zhou, Yilin Mao, Nan Zhang, Jian Zhang, Xian-Ming Zhang
In-depth insight into the the electronic competition principles between inorganic units and organic ligands proves to be extremely challenging for controlling multi-mode emissions in low-dimensional hybrid metal halides (LHMHs). Herein, an efficient blue emission from organic ligand was engineered in (DppyH)2MCl4 (Dppy = diphenyl-2-pyridylphosphine, M = Zn2+, Cd2+) due to the reverse type I band alignment
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A Stereodivergent Multicomponent Approach for the Synthesis of C–N Atropisomeric Peptide Analogues Chem. Sci. (IF 7.6) Pub Date : 2024-09-16 Natalie J. Roper, Aaron D. G. Campbell, Paul G Waddell, Alistair K. Brown, Kristaps Ermanis, Roly J. Armstrong
A four-component Ugi reaction is described for the stereoselective synthesis of novel C–N atropisomeric peptide analogues. Using this approach, a combination of simple, readily available starting materials (ortho-substituted anilines, aldehydes, carboxylic acids and isocyanides) could be combined to access complex products possessing both central and axial chirality in up to 92% yield and >95:5 d.r
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Bifunctional PdMoPt Trimetallene Boosts Alcohol-water Electrolysis Chem. Sci. (IF 7.6) Pub Date : 2024-09-16 Junfeng Liu, Tong Li, Qiuxia Wang, Haiting Liu, Jingjing Wu, Ping Yan Sui, Huaming Li, Pengyi Tang, Yong Wang
Substituting oxygen evolution with alcohol oxidation is crucial for enhancing cathodic hydrogen evolution reaction (HER) at low voltages. However, the development of high-performance bifunctional catalysts remains a challenge. In this study, an ultrathin and porous PdMoPt trimetallene is developed using a wet-chemical strategy. The synergetic effect between alloying metals regulates the adsorption
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π-Extended Pyrenes: From Antiaromatic Buckybowl to Doubly Curved Nanocarbons with Gulf Architectures Chem. Sci. (IF 7.6) Pub Date : 2024-09-16 Binbin Liu, Zhengxiong Jin, Xinyue Liu, Lanfei Sun, cao Yang, Lei Zhang
The synthesis of π-extended pyrenes keeps attracting considerable attention. In particular, frameworks containing nonbenzenoid rings might display intriguing properties. Here, we report a practical synthetic pathway to access a new buckybowl (1) with a central pyrene core. The newly synthesized buckybowl 1 containing four five-membered rings externally fused to a pyrene core, exhibits antiaromaticity
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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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Electron Diffraction and Solid-state NMR Reveals Structure and Exciton Coupling in a Eumelanin Precursor Chem. Sci. (IF 7.6) Pub Date : 2024-09-16 Kavya Vinod, Renny Mathew, Christian Jandl, Brijith Thomas, Mahesh Hariharan
Eumelanin, a versatile biomaterial found throughout animal kingdom, performs essential functions like photoprotection and radical scavenging. The diverse properties of eumelanin are attributed to its elusive and heterogenous structure with DHI (5,6-dihydroxyindole) and DHICA (5,6-dihydroxyindole-2-carboxylic acid) precursors as the main constituents. Despite DHICA being recognized as the key eumelanin
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Simultaneous modulation of cathode/anode and electrolyte interfaces via a nitrile additive for high-energy-density lithium-metal batteries Chem. Sci. (IF 7.6) Pub Date : 2024-09-13 Ziye Wang, Yingshuai Wang, Yuhang Xin, Qingbo Zhou, Xiangyu Ding, Lei Liu, Tinglu Song, Feng Wu, Zhongbao Wei, Hongcai Gao
Nickel-rich layered oxides have great potential for commercial development applications, so it is critical to address their stability over long cycles. Ensuring long-term cycle stability relies heavily on the stability of the interface between the electrode and electrolyte in Li|LiNi0.8Co0.1Mn0.1O2 (NCM811) batteries. In this work, a denser, more stable and thinner nickel-rich cathode/electrolyte interface
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Metal-Free Site-Selective Functionalization with Cyclic Diaryl λ3-Chloranes: Suppression of Benzyne Formation for Ligand-Coupling Reactions Chem. Sci. (IF 7.6) Pub Date : 2024-09-13 Koushik Patra, Manas Pratim Dey, Mahiuddin Baidya
While hypervalent halogens are versatile reagents enabling diverse reactions in organic synthesis, the utility of hypervalent chlorine compounds, particularly cyclic λ3-chloranes, remains underdeveloped despite their unique electronic properties and innate enhanced reactivity. Herein, we illustrate the elusive ligand coupling reaction of cyclic λ3-chloranes that suppresses the more facile competing
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Supramolecular interaction of molecular catalyst on a polymeric carbon nitride photoanode enhances photoelectrochemical activity and stability at neutral pH Chem. Sci. (IF 7.6) Pub Date : 2024-09-13 Sanjit Mondal, Martina Salati, Marco Nicaso, Josep Albero, Mireia Segado-Centellas, Michael Volokh, Carles Bo, Hermenegildo Garcia, Marcos Gil-Sepulcre, Antoni Llobet, Menny Shalom
Polymeric carbon nitride (CN) emerged as an alternative, metal-free photoanode material in water-splitting photoelectrochemical cells (PEC). However, the performance of CN photoanodes is limited due to the slow charge separation and water oxidation kinetics due to poor interaction with water oxidation catalysts (WOCs). Moreover, operation under benign, neutral pH conditions is rarely reported. Here
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Dual active site-mediated Ir single-atom-doped RuO2 catalysts for highly efficient and stable water splitting Chem. Sci. (IF 7.6) Pub Date : 2024-09-13 Zhenhua Tao, Ning Lv, Hongyu Zhao, Xu Luo, Zilan Li, Jun Yu, Lei Chen, Xupo Liu, Shichun Mu
The electronic structure modulation through heterogeneous single-atom doping is an effective strategy to improve electrocatalysis performance of catalysts. Here, Ir single-atom doped RuO2 (IrSA/RuO2) are constructed by substituting Ru sites with mono-disperse Ir atoms in RuO2 crystals. The catalyst shows excellent activity for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in
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H/F Substitution Strategy Can Achieve Large Spontaneous Polarization in 1D Hybrid Perovskite Ferroelectric Chem. Sci. (IF 7.6) Pub Date : 2024-09-13 Jiu-Yang Liu, Meng-Meng Lun, Zhi-Jie Wang, Jun-Yi Li, Kun Ding, Da-Wei Fu, Hai-Feng Lu, Yi Zhang
Hybrid organic-inorganic perovskite (HOIP) ferroelectrics exhibit polarization reversibility and have a wide range of applications in the fields of smart switches, memorizers, sensors, etc. However, the inherent limitations of small spontaneous polarization (Ps) and large coercive field (Ec) in ferroelectrics have impeded their broader utilization in electronic and data storages. Molecular ferroelectrics
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Chemical Diversity of Reagents that Modify RNA 2'-OH in Water: a Review Chem. Sci. (IF 7.6) Pub Date : 2024-09-12 Ryuta R.S. Shioi, Eric Kool
Electrophilic water-soluble compounds have proven versatile in reacting selectively with 2'-OH groups in RNA, enabling structure mapping, probing, caging, labeling, crosslinking, and conjugation of RNAs in vitro and in living cells. While early work focused on one or two types of reagents with limited properties, recent studies have greatly diversified the structure, properties, and applications of
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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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Navigation through High-dimensional Chemical Space: Discovery of Ba5Y13[SiO4]8O8.5 and Ba3Y2[Si2O7]2 Chem. Sci. (IF 7.6) Pub Date : 2024-09-12 Nataliia Hulai, Marco Zanella, Craig Robertson, Daniel Ritchie, Manel Sonni, Matthew A Wright, Jon Alexander Newnham, Cara J. Hawkins, Jayne Whitworth, Bhupendra Mali, Hongjun Niu, Matthew Stephen Dyer, Christopher M Collins, Luke M. Daniels, John B Claridge, Matthew J. Rosseinsky
Two compounds were discovered in the well-studied BaO-Y2O3-SiO2 phase field. Two different experimental routines were used for the exploration of this system due to the differences of synthetic conditions and competition with a glass field. The first phase Ba5Y13[SiO4]8O8.5 was isolated through a combination of energy dispersive X-ray spectroscopy analysis and diffraction techniques which guided the
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Consecutive Chirality Transfer: Efficient Synthesis of Chiral C,O-Chelated BINOL/Gold(III) Complexes for Asymmetric Catalysis and Chiral Resolution of Disubstituted BINOLs Chem. Sci. (IF 7.6) Pub Date : 2024-09-12 Kwok-Heung Aries Chan, Wa-Yi O, Jia-Jun Jiang, Jian-Fang Cui, Man Kin Wong
A novel approach for efficient synthesis of chiral C,O-chelated BINOL/gold(III) complexes by diastereomeric resolution using enantiopure BINOL as chiral resolving agent was demonstrated. The BINOL/gold(III) diastereomers with different solubility were separated by simple filtration, providing optically pure BINOL/gold(III) complexes with up to >99:1 dr. Combining with the efficient BINOL ligand dissociation
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Incorporation of 2D Pyreneammonium Iodide for Enhancing Efficiency and Stability of Perovskite Solar Cells Chem. Sci. (IF 7.6) Pub Date : 2024-09-11 Zhongquan Wan, Yuanxi Wang, Hui Lu, Ruiming Wei, Haomiao Yin, Huaibiao Zeng, Muhammad Azam, Junsheng Luo, Chunyang Jia
Despite the excellent performance of three-dimensional (3D) perovskite-based solar cells (PSCs), their poor stability under moisture and heating conditions limits their commercial application. To address the issue, a new pyreneammonium iodide (named as TAPPyI), in which pyrene-based compound 4,4',4'',4'''-(1,8-dihydropyrene-1,3,6,8-tetrayl)tetraaniline (named as TAPPy) acts as the 2D cation, is introduced
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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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Highly Enhanced Chiroptical Effect from Self-Inclusion Helical Nanocrystals of Tetraphenylethylene Bimacrocycles Chem. Sci. (IF 7.6) Pub Date : 2024-09-10 Ming Hu, Fengying Ye, Wei Yu, Kang Sheng, Zhi-Rong Xu, Jin-Jin Fu, Xin Wen, Hai-Tao Feng, Minghua Liu, Yan-Song Zheng
The helical structure is often the key factor for forming and enhancing chiroptical properties such as circular dichroism (CD) and circular polarized luminescence (CPL) effects. However, no matter whether helical molecules or helical aggregates, they usually display modest chiroptical signals, which limit their practical applications. Herein, chiral tetraphenylethylene (TPE) bimacrocycles that are
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Dynamic Handedness Inversion of Self-organized Helical Superstructures Enabled by Novel Thermally Stable Light-driven Chiral Hydrazone Switches Chem. Sci. (IF 7.6) Pub Date : 2024-09-10 Jingyu Chen, Zichen Wang, Yuexin Yu, Jun Huang, Xinyu Chen, Tongji DU, Xinyue Song, Haiyang Yuan, Shuai Zhou, Xiang-Guo Hu, Xing-Ping Zeng, Shengliang Zhong, Ruochen Lan
Chiral hydrazone photoswitch features as its high thermal stability and negative photochromy, making it desirable in fabrication of thermally stable optical device. However, chiral hydrazone capable of reversibly inversing chirality is scarcely reported. Herein, a series of new chiral hydrazone switches HI-1, HI-2 and HI-3 were designed and synthesized. Due to the photoinduced configuration changes
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Stabilizing ultra-close Pt clusters on all-in-one CeO2/Al2O3 fibril-in-tubes against sintering Chem. Sci. (IF 7.6) Pub Date : 2024-09-10 Wanlin Fu, Kuibo Yin, Zhihui Li, Jun Wang, Mingyu Tang, Jilan Tian, Litao Sun, Yueming Sun, Yunqian Dai
Metal sintering poses significant challenges for developing reliable catalytic systems toward high-temperature reactions, particularly those based on metal clusters with sizes below 3 nm. In this work, electrospun dual-oxide fibril-in-tubes consisting of CeO2 and Al2O3 are rationally designed in an all-in-one manner, to stabilize 2.3-nm Pt clusters with a Tammann temperature (sintering onset temperature)
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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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2D Compounds with Heterolayered Architecture for Infrared Photodetectors Chem. Sci. (IF 7.6) Pub Date : 2024-09-09 Hao Gu, Tianshuo Zhang, Yunluo Wang, Tianrui Zhou, Haijie Chen
Compounds with heterolayered architecture, as a family of the two-dimensional (2D) materials, are composed of alternating positive and negative layers. Their physical properties are determined not only by the charged constituents, but also by the interaction between the two layers. This kind of materials has been widely used for superconductivity, thermoelectricity, energy storage, etc. In recent years
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Tumor oxygen microenvironments-tailored electron transfer-type photosensitizers for precise cancer therapy Chem. Sci. (IF 7.6) Pub Date : 2024-09-07 Yiting Yang, Yafu Wang, Yang Liu, Kui Wang, Ge Wang, Yonggang Yang, Won Jun Jang, Tony D. James, Juyoung Yoon, Hua Zhang
The oxygen levels in a tumor typically exhibits complex characteristics, ranging from mild hypoxia to moderate and even severe hypoxia. This poses significant challenges for the efficacy of photodynamic therapy, where oxygen is an essential element. Herein, we propose a novel therapeutic strategy and developed a series of lipid droplet-targeting photosensitive dyes (Ser-TPAs), i.e., in situ synergistic
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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