Chemistry - A European Journal最新文献

{"title":"Developing High-Rate Aqueous Zinc-Ion Batteries with Zn-Doped V₁₀O₂₄·12H₂O Cathode.","authors":"Prahlada Thippeswamy, Suman Kalyan Sahoo, Hemavathi Nj, Soumen Giri, Debasis Ghosh","doi":"10.1002/chem.202502204","DOIUrl":"https://doi.org/10.1002/chem.202502204","url":null,"abstract":"<p><p>Aqueous zinc-ion batteries (AZIBs) have garnered attention as a cost-effective and safer alternative to lithium-ion batteries (LIBs). However, developing suitable cathode materials which can reversibly host Zn2 + ions remains a challenge. Herein we explore the effect of zinc doping into hydrothermally synthesized V₁₀O₂₄.12H₂O (ZVO) and demonstrate that such doping enhances electronic conductivity and structural stability, leading to improved rate capability and cycling performance of ZVO as a cathode material for AZIBs. The effect of zinc doping in the V₁₀O₂₄.12H₂O as a ZIB cathode has not been previously explored. The ZVO materials had a bundled rod-like morphology with a zinc content of 1.3% and an average oxidation state of 4.86 for the vanadium. DFT calculations further validate that Zn doping to the pristine V₁₀O₂₄ is thermodynamically favorable, which also improves the electronic conductivity of the ZVO. As a result, the Zn//ZVO cell exhibited superior specific capacity and improved rate performance over the pristine V₁₀O₂₄.12H₂O (VO) electrode, with a high specific capacity of 359 mAh/g at 0.1 A/g and sustained 121 mAh/g at 5 A/g. The Zn//ZVO cell also showed commendable cycle stability with 90 mAh/g capacity retention over 1110 cycles, which was equivalent to the starting capacity of the pristine VO cathode.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02204"},"PeriodicalIF":3.7,"publicationDate":"2025-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145038919","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nickel-Doped Copper Oxide Nanorods for Efficient Biomass Electro-Oxidation.","authors":"Xinru Yu, Yue Zhao, Kaiyue Yan, Yiming Zhao, Min Ma, Ziqi Tian, Ruixiang Ge","doi":"10.1002/chem.202502192","DOIUrl":"https://doi.org/10.1002/chem.202502192","url":null,"abstract":"<p><p>Cu-based catalysts are regarded as promising materials for the electro-oxidation of biomass. However, developing effective strategies to improve the intrinsic activity of Cu-based catalysts is still challenging and rarely reported. Herein, we synthesized a nickel-doped copper oxide catalyst (Ni-CuO_x) for 5-hydroxymethylfurfural (HMF) electro-oxidation to 2,5-furandicarboxylic acid (FDCA). The Ni-CuO_x exhibited a large current density of 199.7 mA cm^-2 at 1.4 V, which is 2.8-fold higher than that of pure CuO_x, and exceeds most of the reported Cu-based catalysts. Moreover, the Ni-CuO_x also showed high FDCA yield (90.1%) and Faradaic efficiency (98.5%). Physical characterizations and electrochemical analyses demonstrated that Ni doping optimizes the electronic structure of Cu sites, and promoting the adsorption of HMF, contributing to enhanced electrocatalytic activity. This work provides insights into the rational design of copper-based catalysts for biomass electro-oxidation.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02192"},"PeriodicalIF":3.7,"publicationDate":"2025-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145038892","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cage Amine Superbases: Synthesis and Studies of Nona(ethylene)Hexamine and Dodeka(ethylene)Octamine.","authors":"Kel Vin Tan, Dat Quoc Duong, Keith F White, Brian J Smith, Peter J Barnard","doi":"10.1002/chem.202502448","DOIUrl":"https://doi.org/10.1002/chem.202502448","url":null,"abstract":"<p><p>The cage-amine molecules nona(ethylene)hexamine and dodeka(ethylene)octamine, have been prepared by coupling 1,4,7-triazacyclononane (tacn) or 1,4,7,10-tetraazacyclododecane (cyclen) to the corresponding α-chloroacetamide derivatives of these macrocycles. The formed tri- or tetra-amide cryptands were then reduced to the corresponding hexamine and octamine with borane. In all cases, the amide and amine cryptands were isolated as protonated ammonium salts, with the proton oriented to the inside of the cage molecules (i.e., endohedral). Deprotonation studies on the hexamine and octamine showed the encapsulated protons are highly inert, with no evidence of deprotonation or deuterium exchange. Detailed theoretical studies predict very high proton affinity and basicity of 1118.7 and 1086.7 kJ mol^-1, respectively, for dodeka(ethylene)octamine, and 1108.3 and 1083.7 kJ mol^-1, respectively, for nona(ethylene)hexamine, placing them among the strongest amine bases ever prepared and firmly within the realm of \"superbases\".</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02448"},"PeriodicalIF":3.7,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145032464","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Coordination-Driven Orthogonal Ligand Pairings through Dual Hydrogen-Bonding/π-π Interaction Complementarity.","authors":"Jordan N Smith, Yolanda Yau, Nina R Lawson, Rosemary J Goodwin, Dan Preston","doi":"10.1002/chem.202502411","DOIUrl":"https://doi.org/10.1002/chem.202502411","url":null,"abstract":"<p><p>Multi-layered and orthogonal recognition is an excellent route to controlled molecular complexity. Here we report a series of heteroleptic complexes where two ligands pair together at a palladium(II) metal centre in complementary fashion and with orthogonality to others pairs. This complementarity is driven in part through hydrogen-bonding acceptor or donor sites proximal to the coordination domain (either DD:AA or AD:DA). These interactions alone are insufficient to control ligand pairing identity and/or orientation-secondary π-π interactions between electron-rich and electron-poor aromatic groups in the recognition domain combine with the hydrogen bonding to give high levels of complementarity. Importantly, the different heteroleptic complexes can be combined without significant scrambling or mismatching.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02411"},"PeriodicalIF":3.7,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145028610","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"LMCT-Driven Iron Photocatalysis: Mechanistic Insights and Synthetic Applications.","authors":"Amrita Chaudhuri, Luca Mareen Denkler, Qing Zhuo, Anup Mandal, Ala Bunescu","doi":"10.1002/chem.202502185","DOIUrl":"https://doi.org/10.1002/chem.202502185","url":null,"abstract":"<p><p>Iron-based photocatalysis has emerged as a sustainable and versatile platform for facilitating a wide range of chemical transformations, offering an appealing alternative to precious metal photocatalysts. Among the various activation modes, ligand-to-metal charge transfer (LMCT)-driven homolysis of Fe(III)-L(ligand) bonds has garnered considerable attention due to its ability to generate reactive radical species under mild conditions, without requiring the matching of substrates' redox potentials. In this review, we present a comprehensive overview of recent developments in LMCT-driven iron photocatalysis, with a particular focus on both mechanistic insights and synthetic applications published in the last five years. We classify Fe(III)-L homolysis into four major categories based on the nature of the coordinated ligand: halides, carboxylates, alkoxides, and azide. For a few cases, mechanistic understanding derived from spectroscopic studies, computational modeling, and kinetic investigations is discussed in more detail. We further highlight the expanding repertoire of synthetic transformations enabled by LMCT-driven iron photocatalysis, including C─H functionalization, alkene functionalization, cross-coupling, oxidation, and radical-mediated bond formation. Finally, we provide future perspectives on the continued development of LMCT-based iron photocatalysis as a broadly applicable platform for sustainable organic synthesis. This review aims to serve as a valuable resource for researchers interested in leveraging the full potential of LMCT-mediated iron photocatalysis in modern organic chemistry.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02185"},"PeriodicalIF":3.7,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145028604","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"High Shear Conversion of Elemental Bismuth in Water Under Air to 2D Bismuth Oxycarbonate.","authors":"Fayed Abdullah Alrashaidi, Jason R Gascooke, Mohammed Z Asiri, Abigail K Mann, Ashley Slattery, Jonathan A Campbell, Youhong Tang, Colin L Raston","doi":"10.1002/chem.202502202","DOIUrl":"https://doi.org/10.1002/chem.202502202","url":null,"abstract":"<p><p>2D Bismuth oxycarbonate (2D BOC) nanosheets have a unique layered structure with many applications, including capture and reduction of carbon dioxide. Processing powdered elemental bismuth in water under ambient air conditions using a vortex fluidic device (VFD) results in the formation of 2D BOC without the need of surfactants or other excipients. The induced high shear mechanical energy in the form of micron/submicron topological typhoon like spinning top (ST) fluid flow drives the conversion, which we propose initially melts the metal particles which are spontaneously oxidised at the liquid-quartz tube interface to form 2D bismuth oxide (Bi₂O₃). Then it reacts with atmospheric CO₂ to form 2D BOC. These sheets, ≤ 15.7 nm thick, are in the orthorhombic phase with a lattice spacing of 0.29 nm, which is converted to Bi₂O₃ monoclinic phase as an exothermic process at 269 °C.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02202"},"PeriodicalIF":3.7,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145032528","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"An Amino Acid-Based Self-Shrinking Supramolecular Bioactive Hydrogel - A Sustainable Platform for Wastewater Treatment and Water Purification.","authors":"Swaraj Ganesh Gaonkar, Pandey Priya Arun, S Daisy Precilla, Hirak Kumar Basak, Meenakshi Singh, B Agiesh Kumar, Sudipta Bhowmik, Biswarup Chakraborty, Mayank Varshney, Biplab Mondal, Subhasish Roy","doi":"10.1002/chem.202501895","DOIUrl":"https://doi.org/10.1002/chem.202501895","url":null,"abstract":"<p><p>This study investigates the unique syneresis (self-shrinking) behavior of N-Terminally Fmoc-protected amino acid, Fmoc-hPhe-OH (Fmoc-homo-L-phenylalanine, abbreviated in this work as hF)-based hydrogel, and its potential in environmental remediation applications. Fmoc-hPhe-OH (hF) forms a hydrogel in 50 mM phosphate buffer (PB) of pH 7.4. Interestingly, hF-based hydrogel shows syneresis behavior with controlled release of residual water from the hydrogel matrix. Moreover, this hydrogelator can form co-assembled hydrogels with various dyes, including Congo Red and Rhodamine B; natural water samples, including natural mud water and sea water; and heavy metal ions aqueous solutions, including Cd^II, Pb^II, and Hg^II separately in 50 mM PB of pH 7.4. Interestingly, after 2 to 3 hours for shake gel and 5-6 hours for nonshake gel, the released waters have been tested and it has been found that these co-assembled hydrogels are capable of retaining almost all the contaminants within the shrink hydrogels matrix and releasing almost pure water along with the presence of hydrogel nanofibers. Syneresis is augmented to purify the contaminated water with dyes, mud, dissolved salts, and toxic heavy metal ions. These co-assembled hydrogels, leading to distinct structural and functional changes, which have been characterized by using Fourier-Transform Infrared Spectroscopy (FTIR), X-ray Diffraction (XRD), and Field Emission Scanning Electron Microscopy (FE-SEM), suggesting various supramolecular interactions including π-π stacking, hydrogen bonding, and electrostatic interactions are responsible for stable hydrogelations. The rheological study evaluates the hydrogel's mechanical and thixotropic properties and spectroscopic techniques, including UV-visible spectroscopy and fluorescence spectroscopy, to monitor structural transition. This novel class of amino acid-based hydrogel shows antibacterial activity against both Gram-positive and Gram-negative bacteria, likely through membrane-disruptive mechanisms, and also shows promising antioxidant properties. The native hF hydrogel is biocompatible and shows anticancer activity toward the pancreatic cancer cell line. The research finding bestows the biomedically relevant hydrogel's potential use in green and sustainable environmental remediation.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e01895"},"PeriodicalIF":3.7,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145032457","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Palladium-Catalyzed Coupling of Aryl Iodides with Sulfinamide Reagents for the Construction of Sulfinamides.","authors":"Rutian Sun, Daming Zeng, Ming Wang, Xuefeng Jiang","doi":"10.1002/chem.202502496","DOIUrl":"https://doi.org/10.1002/chem.202502496","url":null,"abstract":"<p><p>A novel sulfinamide reagent was developed that enables the one-step installation of sulfinamides through palladium-catalyzed coupling with aryl iodides. This method offers distinct advantages, including the use of readily available starting materials and broad substrate compatibility. Moreover, the strategy was successfully extended to the synthesis of complex functional molecules. Mechanistic investigations reveal that the key intermediate undergoes base-promoted retro-Michael addition to afford the target product.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02496"},"PeriodicalIF":3.7,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145028639","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Optimization of CEST MRI Reporter Protein Design Using Cation-Pi Networks.","authors":"David E Korenchan, Ethan J French, Emerenziana Runco, Chetan B Dhakan, Jinwu Yan, Hiroshi Nakashima, Michael T McMahon, Assaf A Gilad, Christian T Farrar","doi":"10.1002/chem.202501638","DOIUrl":"https://doi.org/10.1002/chem.202501638","url":null,"abstract":"<p><p>Nucleic acid-based therapeutics, such as oncolytic virotherapy or gene therapy, would benefit greatly from a reporter gene that induces endogenous production of a protein biomarker to noninvasively track the delivery, persistence, and spread with imaging. Several chemical exchange saturation transfer (CEST) reporter proteins detectable by magnetic resonance imaging (MRI) have been demonstrated to have high sensitivity. However, to date none can provide strong CEST contrast at a distinct resonance from that of endogenous proteins, limiting their specificity. We investigated proteins and peptides containing tyrosine (Tyr), tryptophan (Trp), and lysine (Lys) residues that demonstrate CEST contrast shifted far downfield (4-10 ppm) from water. Although Tyr, Trp, and Lys exchangeable protons are typically not detectable under physiological conditions, those in our tested molecules are, having exchange rates of 400-2500 s^-1. The large chemical shift dispersion and rapid exchange rates are attributed to unique hydrogen bonding and cation-π network interactions. These discoveries set the stage for designing a stable reporter protein with high detection specificity and sensitivity that can facilitate the in vivo monitoring of viral and gene therapies using MRI.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e01638"},"PeriodicalIF":3.7,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145028667","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Corrigendum: New Tripod Amphiphiles for Membrane Protein Analysis.","authors":"","doi":"10.1002/chem.202502700","DOIUrl":"https://doi.org/10.1002/chem.202502700","url":null,"abstract":"","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02700"},"PeriodicalIF":3.7,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145032582","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}