-
Photocatalytic NOx removal and recovery: progresses, challenges and future perspectives Chem. Sci. (IF 8.4) Pub Date : 2024-05-20 Ting Xue, Jing Li, Lvcun Chen, Kanglu Li, Ying Hua, Yan Yang, Fan Dong
The excessive production of nitrogen oxides (NOx) from energy production, agricultural activities, transportation, and other human activities remains a pressing issue in atmospheric environment management. NOx serves both as a significant pollutant and a potential feedstock for energy carriers. Photocatalytic technology for NOx removal and recovery has received widespread attention and has experienced
-
Simultaneous Detection of 5-Methylcytosine and 5-Hydroxymethylcytosine at Specific Genomic Loci by Engineered Deaminase-Assisted Sequencing Chem. Sci. (IF 8.4) Pub Date : 2024-05-20 Neng-Bin Xie, Min Wang, Tong-Tong Ji, Xia Guo, Fang-Yin Gang, Ying Hao, Li Zeng, Yafen Wang, Yu-Qi Feng, Bi-Feng Yuan
Cytosine modifications, particularly 5-methylcytosine (5mC) and 5-hydroxymethylcytosine (5hmC), play crucial roles in numerous biological processes. Current analytical methods are often constrained to the separate detection of either 5mC or 5hmC, or the combination of both modifications. The ability to simultaneously detect C, 5mC, and 5hmC at the same genomic locations with precise stoichiometry is
-
Selectively “Size-Excluding” Water Molecules to Enable Highly Reversible Zinc Metal Anode Chem. Sci. (IF 8.4) Pub Date : 2024-05-17 Xiaowei Shen, Wanhao Chen, Haocong Wang, Lifang Zhang, Baojiu Hao, Changhao Zhu, Xiuzhen Yang, Meizhu Sun, Jinqiu Zhou, Xue jun Liu, Chenglin Yan, Tao Qian
Significant water-related side reactions hinder the development of highly safe, low-cost aqueous zinc metal batteries (AZMBs) for grid-scale energy storage. Herein, by regulating the length of alkyl chains, we successfully adjust the interstitial voids between the polymer chains of metal soap interface between 1.48 Å (size of zinc ion) and 4.0 Å (size of water molecule). Therefore, water molecules
-
2D arrays of hollow carbon nanoboxes: outward contraction-induced hollowing mechanism in Fe−N−C catalysts Chem. Sci. (IF 8.4) Pub Date : 2024-05-17 Xiaokai Song, Xiaoke Wang, Jiamin Wei, Shenghua Zhou, Haifeng Wang, Jiali Lou, Yaqi Zhang, Yuhai Liu, Luyao Zou, Yingji Zhao, Xiaoqian Wei, Sameh M Osman, Xiaopeng Li, Yusuke Yamauchi
Maximizing the utilization efficiency of monatomic Fe sites in Fe−N−C catalysts poses a significant challenge for their commercial applications. Herein, a structural and electronic dual-modulation is achieved on a Fe−N−C catalyst to substantially enhance its catalytic performance. We develop a facile multi-component ice-templating co-assembly (MIC) strategy to construct two-dimensional (2D) arrays
-
Efficient Cytosolic Delivery of Luminescent Lanthanide Bioprobes in Live Cells for Two-Photon Microscopy Chem. Sci. (IF 8.4) Pub Date : 2024-05-17 Kyangwi Patrick Malikidogo, Thibault Charnay, Daouda Ndiaye, Ji-Hyung Choi, Lucile Bridou, Baptiste Chartier, Sule Erbek, Guillaume Micouin, Akos Banyasz, Olivier Maury, Veronique Martel-Frachet, Alexei Grichine, Olivier Sénèque
Lanthanide(III) (Ln3+) complexes have desirable photophysical properties for optical bioimaging. However, despite their advantage over organic dyes, their use for microscopy imaging is limited by the high-energy UV excitation they require and their poor ability to cross the cell membrane and reach the cytosol. Here we describe a novel family of lanthanide-based luminescent probes, termed dTAT[Ln·L]
-
Facile synthesis of hydrazone-based zinc(II) complex for ferroptosis-augmented sonodynamic therapy Chem. Sci. (IF 8.4) Pub Date : 2024-05-17 Dan Li, Minghui Fan, Haobing Wang, Yongjie Zhu, Bole Yu, Pingyu Zhang, Huaiyi Huang
Sonodynamic therapy (SDT), as a novel non-invasive cancer treatment modality derived from photodynamic therapy (PDT), has drawn much attention due to its unique advantages for the treatment of deep tumors. Zinc-based complexes have shown great clinical prospect in PDT due to their excellent photodynamic activity and biosafety. However, their application in SDT has been seriously lagging behind. Exploring
-
Palladium-Catalyzed Asymmetric [4+3] Cycloaddition of Methylene-Trimethylenemethane: Access to Seven-Membered Exocyclic Axially Chiral Allenes Chem. Sci. (IF 8.4) Pub Date : 2024-05-17 Yafei Wu, Zhuo Wang, Yuqian Shan, Yukun Ma, Teng Li, Chunhao Yuan, Hongchao Guo, Biming Mao
A palladium-catalyzed asymmetric [4+3] cycloaddition of methylene-trimethylenemethane donor with an azadiene has been developed, affording benzofuro[3,2-b]azepine-derived exocyclic chiral allene with control of axial and point chirality. The target compounds were generated in good to excellent yields and with high diastereoselectivities and enantioselectivities (up to >20:1 dr, 99% ee). Furthermore
-
Increased CO2/N2 selectivity by stepwise fluorination in isoreticular ultramicroporous metal-organic frameworks Chem. Sci. (IF 8.4) Pub Date : 2024-05-16 Tuo Di, Yukihiro Yoshida, Ken-ichi Otake, Susumu Kitagawa, Hiroshi Kitagawa
Exploration of porous adsorbents with high CO2/N2 selectivity is of great significance for reducing CO2 content in the atmosphere. In this study, a series of isoreticular ultramicroporous fluorinated metal-organic frameworks (MOFs) were prepared to explore the benefits of fluorinated ultramicropores in improving CO2/N2 selectivity. Gas adsorption measurements revealed that the increase in the number
-
Carboxylate ester-based electrolytes for Na-ion batteries Chem. Sci. (IF 8.4) Pub Date : 2024-05-16 Yunan Qin, Seong-Gyu Choi, Lucia Mason, Jing Liu, Zongjian Li, Tao Gao
Sodium-ion batteries (SIBs) are promising technology for next-generation energy storage. However, their performance is limited at low temperatures due to the inferior bulk and interfacial resistance of current electrolytes. Here we present a systematic study to evaluate carboxylate ester-based electrolytes for SIB applications, due to their favorable properties (i.e., low melting point, low viscosity
-
Copper/Ruthenium Relay Catalysis Enables 1,6-Double Chiral Inductions with Stereodivergence Chem. Sci. (IF 8.4) Pub Date : 2024-05-16 Hao-Ran Yang, Xiang Cheng, Xin Chang, Zo-Fei Wang, Xiu-Qin Dong, Chun-Jiang Wang
Dual catalysis strategy is an efficient and powerful tool to fulfill the stereodivergent synthesis of all stereoisomeric products from the same set of the starting materials, and great attentions have been paid on the construction of chiral compounds bearing two contiguous stereocenters. However, the more challenging synthesis of remote two noncontiguous stereocenters have been less developed and in
-
Re-assessing viologens for modern bio-electrocatalysis Chem. Sci. (IF 8.4) Pub Date : 2024-05-16 Desmond A. Koomson, Jake Nicholson, Alex Brogan, Leigh Aldous
Viologens, 1,1′-disubstituted-4,4′-bipyridinium salts, are organic redox species that can be used in place of NADPH as mediators for redox enzymes. In this study, using the reduction of oxidized glutathione by glutathione reductase as a model system, a rationally designed library of viologens covering a range of polarities and functional groups were explored as electron transfer mediators for bio-electrocatalysis
-
Formation and Reactivity of a Unique M…C–H Interaction Stabilized by Carborane Cages Chem. Sci. (IF 8.4) Pub Date : 2024-05-16 Guo-Xin Jin, Xin-Ran Liu, Peng-Fei Cui, Yago García-Rodeja, Miquel Solà
Broadening carborane applications has consistently been the goal of chemists in this field. Herein, compared to alkyl or aryl groups, a carborane cage demonstrates an advantage in stabilizing a unique bonding interaction: M…C–H interaction. Experimental results and theoretical calculations have revealed the characteristic of this two-center, two-electron bonding interaction, in which the carbon atom
-
Boosting Degradation of Antibiotics via Peroxymonosulfate Activation with a Cu-based Metal-Organic Framework Chem. Sci. (IF 8.4) Pub Date : 2024-05-16 Ying Wu, Gang Liang, Wen-Bin Li, Xiao-Feng Zhong, Yang-Yang Zhang, Jia-Wen Ye, Tao Yang, Zong-Wen Mo, Xiao-Ming Chen
Highly efficient degradation of antibiotics is a huge challenge due to the extremely stable molecules and the potential for biological resistance. However, conventional degradation methods are limited to lower degradation rate, higher energy consumption and secondary pollution. Herein, we report a new Cu-based metal-organic framework (MOF), featuring classical planar trinuclear [Cu3(µ3-O)]4+ clusters
-
Surface Coating Induced Room-temperature Phosphorescence in Flexible Organic Single Crystals Chem. Sci. (IF 8.4) Pub Date : 2024-05-16 Prodipta Samadder, Khalid Naim, Subash Chandra Sahoo, Prakash P. Neelakandan
Materials exhibiting room temperature phosphorescence (RTP) are in high demand for signage, information encryption, sensing, and biological imaging. Due to weak spin-orbit coupling and other non-radiative processes that effectively quench the triplet excited states, RTP is sparsely observed in organic materials. Although the incorporation of a heavy atom through covalent or non-covalent modification
-
Self-assembled molecular hybrids comprising lacunary polyoxometalates and multidentate imidazole ligands Chem. Sci. (IF 8.4) Pub Date : 2024-05-16 Haoran Sun, Atsuhiro Jimbo, Chifeng Li, Kentaro Yonesato, Kazuya Yamaguchi, Kosuke Suzuki
Self-assembly via coordination bonding facilitates the creation of diverse inorganic–organic molecular hybrids with distinct structures and properties. Recent advances in this field have been driven by the versatility of organic ligands and inorganic units. Lacunary polyoxometalates are a class of well-defined metal-oxide clusters with a customizable number of reactive sites and bond directions, which
-
The photoactivated dynamics of dGpdC and dCpdG sequences in DNA: a comprehensive quantum mechanical study. Chem. Sci. (IF 8.4) Pub Date : 2024-05-16 Lara Martinez-Fernandez, James Alexander Green, Luciana Esposito, Martha Yaghoubi Jouybari, Yuyuan Zhang, Fabrizio Santoro, Bern Kohler, Roberto Improta
Study of alternating DNA GC sequences by different time-resolved spectroscopies has provided fundamental information on the interaction between UV light and DNA, a process of great biological importance. Multiple decay paths have been identified, but their interplay is still poorly understood. Here, we characterize the photophysics of GC-DNA by integrating different computational approaches, to study
-
Copper-Catalysed Perarylation of Cyclopentadiene: Synthesis of Hexaarylcyclopentadienes Chem. Sci. (IF 8.4) Pub Date : 2024-05-16 Yohan Gisbert, Pablo Simon-Marques, Caterina Baccini, Seifallah Abid, Nathalie Saffon-Merceron, Gwenael Rapenne, Claire Kammerer
While hexaphenylsilacyclopentadiene (hexaphenylsilole) is viewed as an archetypal Aggregation-Induced Emission (AIE) luminogen, its isostructural hydrocarbon surrogate hexaphenylcyclopentadiene has strikingly never been investigated in this context, most probably due to a lack of synthetic availability. Herein, we report a straightforward synthesis of hexaphenylcyclopentadiene, via the direct perarylation
-
Development of an inhibitor of the mutagenic SOS response that suppresses the evolution of quinolone antibiotic resistance Chem. Sci. (IF 8.4) Pub Date : 2024-05-16 Thomas Lanyon-Hogg, Jacob D. Bradbury, Thomas Hodgkinson, Adam M. Thomas, Omprakash Tanwar, Gabriele La Monica, Vanessa V. Rogga, Luke J. MacKay, Emilia K. Taylor, Kiera Gilbert, Yihua Zhu, Amber Y. Sefton, Andrew M Edwards, Charlotte Gray-Hammerton, Gerald R. Smith, Paul Roberts, Timothy R. Walsh
Antimicrobial resistance (AMR) is a growing threat to health globally, with the potential to render numerous medical procedures so dangerous as to be impractical. There is therefore an urgent need for new molecules that function through novel mechanisms of action to combat AMR. The bacterial DNA-repair and SOS-response pathways promote survival of pathogens in infection settings and also activate hypermutation
-
Re-pairing DNA: Binding of a ruthenium phi complex to a double mismatch Chem. Sci. (IF 8.4) Pub Date : 2024-05-16 Christine Cardin, Tayler D. Prieto Otoya, Kane T. McQuaid, Neil G. Paterson, D. J. Cardin, Andrew Kellett
We report a crystal structure at atomic resolution (0.9 Å) of a ruthenium complex bound to a consecutive DNA double mismatch, which results in a TA basepair with flipped out thymine, together with the formation of an adenine bulge. The structure shows a form of metalloinsertion interaction of the Λ-[Ru(phen)2phi]2+ (phi= 9,10-phenanthrenediimine) complex at the bulge site. The metal complex interacts
-
'Visualizing' the partially reversible conversion of gold nanoclusters via Au23(S-c-C6H11)17 intermediate Chem. Sci. (IF 8.4) Pub Date : 2024-05-16 Sukhendu Mandal, SANIYA GRATIOUS, Afreen Afreen, Eti Mahal, Jibin Thomas, Shubhadeep Saha, Akhil S Nair, K. V. Adarsh, Biswarup Pathak
Transformation chemistry of atomically precise metal nanoclusters has emerged as a novel strategy for the fundamental research on structure-property correlations of nanomaterials. However, a thorough understanding of the transformation mechanism is indeed necessary to understand the structural growth patterns and corresponding property evolutions in nanoclusters. Herein, we present the ligand-exchange-induced
-
Dual-strategy engineered nickel phosphide for achieving efficient hydrazine-assisted hydrogen production in seawater Chem. Sci. (IF 8.4) Pub Date : 2024-05-16 Rui-Qing Li, Songyun Guo, Xiaojun Wang, Xiaoyu Wan, Shuixiang Xie, Yu Liu, Changming Wang, Guangyu Zhang, Jun Cao, Jiamu Dai, Mingzheng Ge, Wei Zhang
The electrocatalytic hydrogen production in seawater without freshwater shortage pressure is promising, but hindered by tardy oxygen evolution reaction and detrimental chloride electrochemistry. Herein, dual-strategy of Fe-doping and CeO2-decorating into nickel phosphide (Fe-Ni2P/CeO2) is rationally designed to achieve eminently bifunctional catalytic performances for hydrogen evolution reaction (HER)
-
Low-temperature synthesis of cation-ordered bulk Zn3WN4 semiconductor via heterovalent solid-state metathesis Chem. Sci. (IF 8.4) Pub Date : 2024-05-15 Christopher L Rom, Shaun O'Donnell, Kayla Huang, Ryan A. Klein, Morgan J Kramer, Rebecca W Smaha, Andriy Zakutayev
Metathesis reactions are widely used in synthetic chemistry. While the state-of-the-art organic metathesis are highly controlled processes where specific bonds are broken and formed, inorganic metathesis reactions are often highly exothermic and, consequently, poorly controlled. Ternary nitrides offer a technologically relevant platform for expanding synthetic control of inorganic metathesis reactions
-
Characterization of a LanC-free pathway for the formation of an LL-MeLan residue and an alloAviMeCys residue in the newly identified class V lanthipeptide triantimycins Chem. Sci. (IF 8.4) Pub Date : 2024-05-15 Weizhong Ding, Xiaofeng Wang, Yu Yin, J. Tao, Yanqing Xue, Wen Liu
The thioether-connected bis-amino acid lanthionine (Lan) residues are class-defining residues of lanthipeptides. Typically, the cyclization step of lanthionine formation, which relies on the addition of a cysteine to an unsaturated dehydroamino acid, is directed either by a standalone cyclase LanC (class I) or by a cyclase domain (class II-IV). However, the pathways of characterized class V members
-
Transition Metal-Free Decarboxylative Olefination of Carboxylic Acid Salts Chem. Sci. (IF 8.4) Pub Date : 2024-05-15 Ebbin Joseph, Deshkanwar S. Brar, Gaven Stuhlsatz, Jon Tunge
The cost-effective and efficient synthesis of alkenes is highly significant due to their extensive applications in both synthetic and polymer industries. A transition metal-free approach has been devised for the chemoselective olefination of carboxylic acid salts. This modular approach provides direct access to valuable electron-deficient styrenes in moderate to good yields. Detailed mechanistic studies
-
G-Quadruplex-Guided Cisplatin Triggers Multiple Pathways in Targeted Chemotherapy and Immunotherapy Chem. Sci. (IF 8.4) Pub Date : 2024-05-15 Tian-Zhu Ma, Liu-Yi Liu, You-Liang Zeng, Ke Ding, Hang Zhang, Wenting Liu, Qian Cao, Wei Xia, Xushen Xiong, Chao Wu, Zong-Wan Mao
G-quadruplexes (G4s) are atypical nucleic acid structures involved in basic human biological processes and are regulated by small molecules. To date, pyridostatin and its derivatives [e.g., PyPDS (4-(2-aminoethoxy)-N2, N6-bis(4-(2-(pyrrolidin-1-yl) ethoxy) quinolin-2-yl) pyridine-2,6-dicarboxamide)] are the most widely used G4-binding small molecules and considered to have the best G4 specificity,
-
α-Phenylthioaldehydes for the effective generation of acyl azolium and azolium enolate intermediates Chem. Sci. (IF 8.4) Pub Date : 2024-05-14 Paul Ewing, Pankaj Mahji, Callum Prentice, Claire M Young, Karlotta van Rees, Polly Louise Arnold, Eli Zysman-Colman, Andrew D Smith
a-Thiophenylaldehydes are readily prepared using a simple multi-step procedure and herein are introduced as a new precursor for the NHC-catalysed generation of acyl azolium and azolium enolate intermediates that are of widespread synthetic interest and utility. Treatment of a-thiophenylaldehydes with an NHC precatalyst and base produces an efficient redox rearrangement via a Breslow intermediate, elimination
-
Bidirectional photomagnetism, exciplex fluorescence and dielectric anomaly in a spin crossover Hofmann-type coordination polymer Chem. Sci. (IF 8.4) Pub Date : 2024-05-14 Yan-Ru Chen, Ting-Ting Ying, Yan-Cong Chen, Pei-Yu Liao, Zhao-Ping Ni, Ming-Liang Tong
Stepped spin crossover (SCO) complexes with three or more spin states have promising applications in high-order data storage, multi-switches and multi-sensors. Further synergy with other functionalities, such as luminescence and dielectric properties, will provide a good chance to develop novel multifunctional SCO materials. Here, the bent pillar ligand and luminescent pyrene guest are integrated into
-
Enhancing corannulene chemiluminescence, electrochemiluminescence and photoluminescence by means of an azabora-helicene to slow down its bowl inversion Chem. Sci. (IF 8.4) Pub Date : 2024-05-14 Xiaoli Qin, Lin Huang, Ziying Zhan, Peng Fu, Qing Wang, Congyang Zhang, Jianhui Huang, Zhifeng Ding
Aromatic system extension of corannulene (Cor) is a synthetic challenge to access non-planar polyaromatic hydrocarbons (PAHs). Herein, we report the design and synthesis of azaborahelicene corannulene 1 through hybridization of an azabora[5] helical structure and subsequent luminescence studies. Significant enhancement in chemiluminescence (CL), electroluminescence (ECL) and photoluminescence (PL)
-
Protein-based layer-by-layer films for biomedical applications Chem. Sci. (IF 8.4) Pub Date : 2024-05-14 Muhammad Haseeb Iqbal, Halima Kerdjoudj, Fouzia Boulmedais
The surface engineering of biomaterials is crucial for their successful (bio)integration by the body, i.e. the colonization by the tissue-specific cell, and the prevention of fibrosis and/or bacterial colonization. Performed at room temperature in an aqueous medium, the layer-by-layer (LbL) coating method is based on the alternating deposition of macromolecules. Versatile and simple, this method allows
-
Peptide Macrocyclisation via Intramolecular Interception of Visible-Light-Mediated Desulfurisation Chem. Sci. (IF 8.4) Pub Date : 2024-05-14 Frances R. Smith, Declan Meehan, Rhys C. Griffiths, Harriet J. Knowles, Peiyu Zhang, Huw Williams, Andrew Wilson, Nicholas J. Mitchell
Synthetic methods that enable the macrocyclisation of peptides facilitate the development of more effective therapeutic and diagnostic tools. Herein we report a peptide cyclisation strategy based on intramolecular interception of visible-light-mediated cysteine desulfurisation. This method allows cyclisation of unprotected peptides in an aqueous solution via the installation of a hydrocarbon linkage
-
Cross-linked K0.5MnO2 Nanoflower Composites for High Rate and Low Overpotential Li–CO2 Batteries Chem. Sci. (IF 8.4) Pub Date : 2024-05-14 Jiawei Wu, Jian Chen, Xiaoyang Chen, Yang Liu, Zhe Hu, Feijian Lou, Shulei Chou, Yun Qiao
Rechargeable Li-CO2 batteries are deemed to be an attractive energy storage system, as they can effectively inhale and fix carbon dioxide and possess an extremely high energy density. Unfortunately, the irreversible decomposition of the insoluble and insulating Li2CO3 results in awful electrochemical performance and inferior energy efficiency of Li-CO2 batteries. Furthermore, the low energy efficiency
-
Atomically dispersed dinuclear iridium active sites for efficient and stable electrocatalytic chlorine evolution reaction Chem. Sci. (IF 8.4) Pub Date : 2024-05-14 Zhipeng Yu, Guang-Jie XIA, Vlad Martin-Diaconescu, Laura Simonelli, Alec P LaGrow, Zhixin Tai, Xinyi Xiang, Dehua Xiong, Lifeng Liu
The electrochemical chlorine evolution reaction (CER) is a critical anode reaction in chlor-alkali electrolysis. Although precious metal-based mixed metal oxides (MMOs) have long been used as CER catalysts, they suffer from high cost and poor selectivity due to the competing oxygen evolution reaction (OER). Single-atom catalysts (SACs), featuring high atom utilization, have captured widespread interest
-
Exceptional Three- to Six-Photon Absorption at Organometallic Dendrimers Chem. Sci. (IF 8.4) Pub Date : 2024-05-14 Ling Zhang, Mahbod Morshedi, Torsten Schwich, Rika Kobayashi, Mark G Humphrey
The light-intensity dependence of multi-photon absorption (MPA) affords outstanding spatial control. Furthermore, compared to the higher-energy photons needed for analogous linear absorption, the lower-energy photons involved in MPA often correspond to important wavelengths, such as those of the biological and telecommunications “windows”. It is therefore of crucial importance to develop molecules
-
Identification of two-dimensional covalent organic frameworks with mcm topology and their application in photocatalytic hydrogen evolution Chem. Sci. (IF 8.4) Pub Date : 2024-05-13 Xin Zhao, Fengju Tian, Xianghao Han, Qiao-Yan Qi
Covalent organic frameworks have attracted considerable attention in recent years as a distinct class of crystalline porous organic materials. Their functional properties are inherently linked to their structural characteristics. Although hundreds of COFs have been reported so far, the types of their topologic structure are still limited. In this article, we report the identification of mcm topology
-
Copper-oxygen adducts: new trends in characterization and properties towards C−H activation Chem. Sci. (IF 8.4) Pub Date : 2024-05-13 Catherine Belle, Jonathan De Tovar, Rébecca Leblay, Yongxing Wang, Laurianne Wojcik, Aurore Thibon-Pourret, Marius Reglier, A. Jalila Simaan, Nicolas Le Poul
This review summarizes the latest discoveries in the field of C−H activation by copper monoxygenases and more particularly by their bioinspired systems. This work first describes recent background on copper-containing enzymes along with additional interpretations about the nature of the active copper-oxygen intermediates. It then focuses on relevant examples of bioinorganic synthetic copper-oxygen
-
Trimodal Operation of a Robust Smart Organic Crystal Chem. Sci. (IF 8.4) Pub Date : 2024-05-13 Kui Chen, Wenbo Wu, Hui Yu, Jiaxuan Zhu, Yaoguang Feng, Jingkang Wang, Xin Huang, Liang Li, Ting Wang, Na Wang, Pance Naumov, Hongxun Hao
We describe a dynamic crystalline material that integrates mechanical, thermal, and light modes of operation, with unusual robustness and resilience and a variety of both slow and fast kinematic effects that occur on very different time scales. In the mechanical mode of operation, crystals of this material are amenable to elastic deformation, and they can be reversibly morphed and even closed into
-
Neutral Inverse-Sandwich Rare-Earth Metal Complexes of the Benzene Tetraanion Chem. Sci. (IF 8.4) Pub Date : 2024-05-13 Yi Wang, Yurou Zhang, Jiefeng Liang, Bowen Tan, Chong Deng, Wenliang Huang
Rare-earth metal complexes of the parent benzene tetraanion and neutral inverse-sandwich rare-earth metal arene complexes have remained elusive. Here, we report the first neutral inverse-sandwich rare-earth metal complexes of the parent benzene tetraanion supported by a monoanionic β-diketiminate (BDI) ligand. Reduction of the trivalent rare-earth metal diiodide precursors (BDI)MI2(THF) (BDI = HC(
-
Stabilization of Ni-containing Keggin-type Polyoxometalates with Variable Oxidation States as Novel Catalysts for Electrochemical Water Oxidation Chem. Sci. (IF 8.4) Pub Date : 2024-05-13 Edman Tsang, Xiang Li, Bryan K Y Ng, Baron Ho, Chunbo Jia, Jining Shang, Tatchamapan Yoskamtorn, Xuelei Pan, Yiyang Li, guangchao Li, Tai-Sing Wu, Yun-Liang Soo, Heyong He, Bin Yue
The development of new recyclable and inexpensive electrochemically active species for water oxidation catalysis is the most crucial step for future utilization of renewables. Particularly, transition metal complexes containing internal multiple, cooperative metal centers to couple with redox catalysis in the inorganic Keggin-type polyoxometalate (POM) framework at high potential or under extreme pH
-
Conformational Flexibility Driving Charge-Selective Substrate Translocation Across Bacterial Transporter Chem. Sci. (IF 8.4) Pub Date : 2024-05-13 Devika Vikraman, Bibhab Bandhu Majumdar, S. K. Sharavanakkumar, Conrad Weichbrodt, Niels Fertig, Mathias Winterhalter, Jagannath Mondal, Mahendran R. Kozhinjampara
Bacterial membrane porins facilitate the translocation of small molecules while restricting large molecules, and this mechanism remains elusive at the molecular level. Here, we investigate the selective uptake of large cyclic sugars across an unusual passive membrane transporter CymA, comprising a charged zone and a constricting N terminus segment. Using a combination of electrical recordings, protein
-
Rapidly Solar-driven Atmospheric Water Harvesting with MAF-4 Derived Nitrogen-doped Nanoporous Carbon Chem. Sci. (IF 8.4) Pub Date : 2024-05-11 MING XUE, Jinhua Feng, Feng Lu, Zhen Chen, Miaomiao Jia, Yi-Le Chen, Wei-Hai Lin, Qing-Yun Wu, Yi Li, Xiao-Ming Chen
Sorption-based atmospheric water harvesting (AWH) technology is a powerful approach for solving global fresh water scarcity. In this field, an upsurge in searching adsorbents with high water uptake capacity at low relative humidity, rapid adsorption-desorption kinetics and high thermal conductivity, which have been considered to be critical challenges in the AWH process. Herein, we report a MAF-4 (aka
-
Sulphur-Atom Positional Engineering in Perylenimide: Structure-Property Relationships and H-aggregation Directed Type-I Photodynamic Therapy Chem. Sci. (IF 8.4) Pub Date : 2024-05-10 Mst Nasima Khatun, Satyendu Nandi, Hirakjyoti Roy, Siddhartha Sankar Ghosh, Sachin Kumar, Parameswar K. Iyer
An innovative design strategy of placing sulfur (S)-atoms within the pendant functional groups and at carbonyl positions in conventional perylenimide (PNI-O) has been demonstrated to investigate the condensed state structure-property relationship and potential photodynamic therapy (PDT) application. Incorporation of simply S-atoms at the peri-functionalized perylenimide (RPNI-O) leads to aggregation-induced
-
Future Prospects of High-Entropy Alloys as Next-Generation Industrial Electrode Materials Chem. Sci. (IF 8.4) Pub Date : 2024-05-08 Saikat Bolar, Yoshikazu Ito, Takeshi Fujita
The rapid advancement of electrochemical processes in industrial applications has increased the demand for high-performance electrode materials. High-entropy alloys (HEAs), a class of multicomponent alloys with unique properties, have emerged as potential electrode materials owing to their enhanced catalytic activity, superior stability, and tunable electronic structures. This review explores contemporary
-
Mechanistic investigations of the Fe(II) mediated synthesis of squaraines Chem. Sci. (IF 8.4) Pub Date : 2024-05-07 Yu Liu, Nathan Thomas Coles, Nathalia Cajiao, Laurence John Taylor, Edward Stephen Davies, Alistair Barbour, Patrick Morgan, Kevin Butler, Ben Pointer-Gleadhill, Stephen Argent, Jonathan McMaster, Michael L. Neidig, David Robinson, Deborah Lorraine Kays
The scission and homologation of CO is a fundamental process in the Fischer-Tropsch reaction. However, given the heterogeneous nature of the catalyst and forcing reaction conditions, it is difficult to determine the intermediates of this reaction. Here we report detailed mechanistic insight into the scission/homologation of CO by two-coordinate iron terphenyl complexes. Mechanistic investigations,
-
Nanoscale and Chiral Metal–Organic Framework for Asymmetric Reactions in Water: Bridging Lewis Acid Catalysis to Biological Systems Chem. Sci. (IF 8.4) Pub Date : 2024-05-06 Watchara Srimontree, Taku Kitanosono, Yasuhiro Yamashita, Shu Kobayashi
Nowadays, stereoselective control over the sheer variety of chemical transformations benefits from the multipotency of chiral Lewis acids. Their use under biocompatible conditions has long posed a challenge because profuse amounts of biogenic nucleophiles readily deactivate them. To bridge a gap between chiral Lewis acid catalysis and biocompatible chemistry, the conversion of UiO(BPY)-type nanosized
-
AN ANTHROPOCENE-FRAMED TRANSDISCIPLINARY DIALOG AT THE CHEMISTRY-ENERGY NEXUS Chem. Sci. (IF 8.4) Pub Date : 2024-05-02 mathieu prevot, Valeria Finelli, Xavier Carrier, Gabriele Deplano, Margherita Cavallo, Elsje Alessandra Alessandra Quadrelli, Juliette Michel, Marie-Hélène Pietraru, Clément Camp, Giulia Forghieri, Anna Gagliardi, Sebastian Seidel, Antoine Missemer, Bertrand Reuillard, Barbara Centrella, Silvia Bordiga, Maria Grace Salamanca González, Vincent Artero, Keanu V. A. Bierkelbach, Niklas Von Wolff
At the energy-chemistry nexus, key molecules include carbon dioxide (CO2), hydrogen (H2), methane (CH4), and ammonia (NH3). The position of these four molecules and that of the more general family of synthetic macromolecular polymer blends (found in plastics) were cross-analyzed with the Planetary Boundary framework, and as part of five scientific policy roadmaps for the energy transition. According
-
Adamantane-Type Clusters: Compounds with a Ubiquitous Architecture but a Wide Variety of Compositions and Unexpected Materials Properties Chem. Sci. (IF 8.4) Pub Date : 2024-05-02 Stephanie Dehnen, Niklas Rinn, Irán Rojas-León, Benjamin Peerless, Saravanan Gowrisankar, Ferdinand Ziese, Nils Wilhelm Rosemann, Wolf-Christian Pilgrim, Simone Sanna, Peter R Schreiner
The research of adamantane-type compounds has gained momentum in recent years, yielding remarkable new applications for this class of materials. In particular, organic adamantane derivatives (AdR4) or inorganic adamantane-type compounds of the general formula [(RT)4E6] (R: organic substituent; T: group 14 atom C, Si, Ge, Sn; E: chalcogenide atom S, Se, Te or CH2) were shown to exhibit strong non-linear
-
Carbonyl Mediated Fluorescence in Aceno[n]helicenones and Fluoreno[n]helicenes Chem. Sci. (IF 8.4) Pub Date : 2024-05-01 Michal Šámal, Ludmilla Sturm, Marzena Banasiewicz, Irena Deperasińska, Boleslaw Kozankiewicz, Olaf Morawski, Yuuya Nagata, Pierre Dechambenoit, Harald Bock, Amandine Rossel, Milos Budesinsky, Anthony Boudier, Andrej Jancarik
Helicenes are very attractive chiral non-planar polycyclic aromatic hydrocarbons possessing strong chiroptical properties. However, most of the helicenes absorb light mainly in the ultraviolet region, with only a small segment in the blue part of the visible spectrum. Furthermore, carbo[n]helicenes exhibit only weak luminescence that limits their utilization. Herein, we demonstrate that peripheral
-
Emerging high voltage V4+/V5+ redox reaction in Na3V2(PO4)3-based cathode for sodium-ion batteries Chem. Sci. (IF 8.4) Pub Date : 2024-05-01 Meng Zhou, Xunzhu Zhou, Lin Li, Xiang Chen, Zhen-An Qiao, Shulei Chou
Na3V2(PO4)3 (NVP) cathode materials with the advantages of long cycle life and superior thermal stability have been considered promising cathode candidates for SIBs. However, the unsatisfied energy density derived from low theoretical capacity and operating voltage (3.35 V vs. Na+/Na, based on V3+/V4+ redox couple) inevitably limits their practical application. Therefore, the activation of V4+/V5+
-
Near-Infrared Photocatalysis with Cyanines: Synthesis, Applications and Perspectives Chem. Sci. (IF 8.4) Pub Date : 2024-05-01 Jean-Philippe Goddard, Nicolas Sellet, Johanna Frey, Morgan Cormier
Cyanine are organic dyes bearing two Aza-heterocycles linked by a polymethine chain. Excited states, fluorescence, redox activity, and energy transfer are interesting properties which have been used by chemists. Moreover, they are easily accessible and highly tunable. For all these reasons, cyanines are often selected for applications like fluorescent probes, phototherapy and photovoltaic. However
-
¬The impact of earth-abundant metals as a replacement for Pd in cross coupling reactions Chem. Sci. (IF 8.4) Pub Date : 2024-04-16 Michael U. Luescher, Fabrice Gallou, Bruce H. Lipshutz
Substitution of one metal catalyst for another is not straightforward as simply justifying this change based on the availability and/or cost of the metals. A life cycle-like assessment was performed leading to the conclusion that the commonly held view that use of earth-abundant metals (and in this case study, Ni) are replacements for palladium most notably in cross coupling reactions, and Suzuki-Miyaura
-
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
-
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
-
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
-
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
-
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
-
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
-
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
-
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
-
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
-
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