{"title":"Asymmetric 1,4-Addition and Functionalization Strategy in Total Synthesis.","authors":"Shaowei Wang, Ping Lu","doi":"10.1002/chem.202501269","DOIUrl":"https://doi.org/10.1002/chem.202501269","url":null,"abstract":"<p><p>The transition-metal catalyzed enantioselective 1,4-addition and subsequent functionalization strategy provides a powerful approach to construct 2,3-disubstituted cycloalkanones, which are further utilized as important intermediates in the total synthesis of natural products. This concept article highlights recent advances in the methodology development and related synthetic application.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202501269"},"PeriodicalIF":3.9,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144075149","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":"Porous Nitrogen-doped Nb2C Nanosheets for Electrocatalytic ORR to Selectively Produce H2O2.","authors":"Meixuan Li, Xinyao Zhang, Bing Ni, Wenbo Yue","doi":"10.1002/chem.202500758","DOIUrl":"https://doi.org/10.1002/chem.202500758","url":null,"abstract":"<p><p>The two-electron pathway in the oxygen reduction reaction (ORR) represents an efficient and environmentally friendly approach for H2O2 production. Among various types of potential catalysts, MXene have garnered significant attention due to their outstanding electrical conductivity, abundant edge active sites, and low costs. In this study, we successfully synthesize porous N-doped Nb2C nanosheets (N-Nb2C) via a room-temperature ammonia etching method and investigate their ORR performance toward the formation of H2O2. The doping of nitrogen effectively modulates the electronic structure of Nb2C nanosheets, while the abundant surface pores formed during ammonia etching facilitate the ORR process. Hence, the electrocatalytic performance of N-Nb2C nanosheets is significantly improved, demonstrating excellent long-term stability and durability. Notably, in rotating ring-disk electrode (RRDE) tests, the N-Nb2C catalyst achieves a remarkable H2O2 yield of 86.8%, highlighting its potential for selective H2O2 production through electrocatalytic ORR. Our findings suggest that N-doped Nb2C holds great promise for applications in two-electron oxygen reduction for H2O2 synthesis.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500758"},"PeriodicalIF":3.9,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144075158","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":"Flexible cyclotriphosphonitrile-based covalent organic frameworks for the capture of iodine.","authors":"Zhaoqi Zheng, Hong Yang, Peixu Zheng, Wei Luo, Jianhua Qiu, Liping Jiang","doi":"10.1002/chem.202500546","DOIUrl":"https://doi.org/10.1002/chem.202500546","url":null,"abstract":"<p><p>The development of highly efficient materials for trapping radioactive iodine is essential for the safe use of nuclear energy. Herein, we present a strategy to synergistically enhance iodine capture by exploiting the flexible building blocks with the affinity properties of electrically rich heteroatoms by combining the cyclic triphosphonitrile derivative, with amine linkers of different molecular lengths, and constructing triangular pore-structured flexible cyclotriphosphonitrile-based covalent organic frameworks. A series of cyclotriphosphonitrile-based COFs (CTP-X-COF, X=PDA, ODA, BPY, DPT) with triangular pore topology were synthesized usingCTP-6 as the node and connection point of p-phenylenediamine (PDA), 4,4-diaminodiphenyl ether (ODA), 5,5-diamino2,2-bipyridine (BPY), and 4,4-diaminotribiphenyl (DPT) with different molecular lengths. It was found that the adsorption capacities of CTP-PDA-COF, CTP-ODA-COF, CTP-BPY-COF, and CTP-DPT-COF for iodine vapor were 4.65 g g-1, 4.18 g g-1, 2.38 g g-1 and 3.57 g g-1, respectively. The results showed that the adsorption capacities of CTP-PDA-COF, CTP-ODA-COF, CTP-BPY-COF, and CTP-DPT-COF for iodine in cyclohexane were 281.50 mg g-1, 221.67 mg g-1, 161.14 mg g-1, and 222.67 mg g-1, respectively. It was found that the four COFs adsorbed iodine in cyclohexane solution was a mixed adsorption process with chemical adsorption playing a predominant role and physical adsorption as an auxiliary mechanism.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500546"},"PeriodicalIF":3.9,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144075151","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}
Karolina Gutmańska, Agnieszka Podborska, Andrzej Sławek, Ramesh Sivasamy, Lulu Alluhaibi, Alexey Maximenko, Anna Ordyszewska, Konrad Szaciłowski, Anna Dołęga, Tomasz Mazur
{"title":"Structural Insights and Advanced Spectroscopic Characterization of Thiazolothiazoles: Unveiling Potential for Optoelectronic and Sensing Applications.","authors":"Karolina Gutmańska, Agnieszka Podborska, Andrzej Sławek, Ramesh Sivasamy, Lulu Alluhaibi, Alexey Maximenko, Anna Ordyszewska, Konrad Szaciłowski, Anna Dołęga, Tomasz Mazur","doi":"10.1002/chem.202501664","DOIUrl":"https://doi.org/10.1002/chem.202501664","url":null,"abstract":"<p><p>Thiazolothiazoles (TzTzs) are planar, π-conjugated heterocyclic compounds exhibiting unique structural and optoelectronic properties. In this study, a series of symmetrically substituted TzTz derivatives including imidazolyl, o-vanillyl, p-vanillyl, phenyl, thiazolyl, cinnamoyl, and trifluoromethylphenyl were synthesized and extensively characterized using X-ray crystallography (XRD), Fourier-transformed infrared (FTIR), nuclear magnetic resonance (NMR) and ultraviolet-visible (UV-Vis) spectroscopies, photoluminescence, X-ray absorption near edge structure (XANES, S K-edge), and density functional calculations. The compounds demonstrated diverse intermolecular interactions, including π×××π stacking and chalcogen bonding, which directly influenced their optical properties and electronic band structures. Several derivatives displayed promising features such as large Stokes shifts over 0.4 eV in solution and up to 1 eV in solid state, and reversible resistive switching behavior, positioning them as attractive candidates for use in optoelectronic devices and emerging memristive technologies.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202501664"},"PeriodicalIF":3.9,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144075171","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}
Naveen S Reddy, Chirodeep Bakli, Vinay Arya, Debasis Ghosh
{"title":"ENHANCED POLYSULFIDE REGULATION IN RECHARGEABLE LI-S BATTERIES WITH ZnS AS ELECTROCATALYST: EXPERIMENTAL VALIDATION AND INTERFACIAL INSIGHTS FROM SIMULATIONS.","authors":"Naveen S Reddy, Chirodeep Bakli, Vinay Arya, Debasis Ghosh","doi":"10.1002/chem.202501030","DOIUrl":"https://doi.org/10.1002/chem.202501030","url":null,"abstract":"<p><p>We present a high-performance lithium-sulfur (Li-S) battery cathode based on a reduced graphene oxide (rGO)-decorated ZnS nanosphere structure, which serves as a multifunctional sulfur host. The rGO framework provides a high-surface-area conductive network for enhanced sulfur loading, while ZnS acts as an electrocatalyst to accelerate polysulfide conversion. Fabricated via a one-step hydrothermal method, the composite achieves a high sulfur content (~80%) with efficient polysulfide confinement and catalytic conversion as a Li-S battery cathode. As a result, it delivers an initial capacity of 1014 mAh/g at 0.1 C and retains 592 mAh/g at 1C, demonstrating excellent rate capability and cycling stability (479 mAh/g over 200 cycles at 1C). To further understand the interfacial interactions, molecular dynamics simulations were conducted, revealing the role of ZnS in accelerating lithium polysulfide (LiPS) conversion, particularly from Li₂S₄ to Li₂S. The study analyzed LiPS diffusion coefficients and potential energy across different sulfur species, confirming the superior efficiency of the rGO@ZnS host. These findings highlight the potential of ZnS-decorated rGO structures as a promising approach to improving Li-S battery performance through enhanced sulfur utilization and polysulfide regulation.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202501030"},"PeriodicalIF":3.9,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144075150","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}
Riccardo Bellan, David Attia, Marcel H P van Genderen, Patricia Y W Dankers
{"title":"Hybrid pH Responsive Supramolecular Polymers Through the Combination of the Ureido-Pyrimidinone Motif with β-Sheet Peptide Sequences.","authors":"Riccardo Bellan, David Attia, Marcel H P van Genderen, Patricia Y W Dankers","doi":"10.1002/chem.202500429","DOIUrl":"https://doi.org/10.1002/chem.202500429","url":null,"abstract":"<p><p>Supramolecular biomaterials based on 1D supramolecular polymers in water replicate the fibrous and dynamic structures of natural architectures. Peptides, valued for their biocompatibility, are commonly employed as building blocks for supramolecular biomaterials, often in combination with large aromatic or hydrogen-bonding groups at the N-terminus to improve their structural stability. Herein, the self-assembly properties of two β-sheet peptides combined with the ureido-pyrimidinone self-dimerizing motif in aqueous solution are investigated in detail. The assembly of the resulting molecules is demonstrated to be intimately dependent on the β-sheet sequence, while the incorporation of a hydrophobic spacer enhances the assembly of the monomers, irrespective of the peptide sequence employed. Furthermore, the assembly of each monomer is significantly enhanced at pH = 3.0 while being stable between pH = 5.0 and 9.0. Only at pH = 12, upon enolate formation, the transition to random coil conformation is observed for all the monomers. The supramolecular polymers developed hereby point to fundamental design principle toward the development of UPy-peptide based materials with tuneable properties and potential applications in the biomedical fields of research.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500429"},"PeriodicalIF":3.9,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144075153","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":"Photocatalytic Oxidation of Alcohols with Organic Dyes: from Homogeneous Systems to Sensitized Materials.","authors":"Elena Tacchi, Greta Rossi, Andrea Sartorel","doi":"10.1002/chem.202501124","DOIUrl":"https://doi.org/10.1002/chem.202501124","url":null,"abstract":"<p><p>The oxidation of alcohols retains an enormous importance in industry and in synthetic organic chemistry. The renaissance in photocatalysis is offering new routes to conduct this class of transformations under benign and sustainable conditions. In this concept article, we highlight the efforts that have been conducted in light driven oxidation of alcohols using organic photocatalysts. After an overview of relevant industrial processes, we will discuss relevant examples of organic photocatalysts employed in solution, or when integrated in photosynthetic schemes within semiconductor slides or nanoparticles. The combination of the photochemical systems with electrochemical routes or their engineering in flow will be considered. Where possible, we highlight also mechanistic aspects that reveal the key steps involved and contribute to improve the performance of the process. We finally present an outlook on the future perspectives and developments in the field.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202501124"},"PeriodicalIF":3.9,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144075156","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":"Real-Time Monitoring of Wheel Movement in a [2]Rotaxane Using a Competing Kinetic Pathway.","authors":"Shogo Azuma, Keisuke Wada, Kazuma Yasuhara, Kenichi Kato, Shunsuke Ohtani, Tomoki Ogoshi","doi":"10.1002/chem.202501151","DOIUrl":"https://doi.org/10.1002/chem.202501151","url":null,"abstract":"<p><p>Wheel movement of rotaxanes is typically fast in solution. Therefore, real-time monitoring of such movement is one of the challenging topics. Herein, we report real-time monitoring of wheel movement in a [2]rotaxane (comprising hydrophilic pillar[5]arene as a wheel and hydrophobic π-conjugated moiety with hydrophilic tetra(ethylene oxide) ends as an axle) via a competing kinetic pathway, i.e., aggregation/dissociation equilibrium. In non-aqueous solvent, the [2]rotaxane shows blue-purple locally excited emission from the π-conjugated moiety because the pillar[5]arene wheel shuttles over the whole axle. In aqueous solvent, the [2]rotaxane forms aggregates owing to its amphiphilic nature. Because the [2]rotaxane forms the kinetically stable aggregates, location of the pillar[5]arene wheel on the axle is maintained, resulting in the locally excited emission even in the polar conditions. Surprisingly, the emission color gradually changes from blue-purple to light-blue over 720 h because exposure of the monomeric [2]rotaxane generated by dissociation of the kinetically stable aggregates, to the polar environment triggers movement of the hydrophilic wheel to the hydrophobic π-conjugated moiety by hydrophobic effect. After this movement, the monomeric [2]rotaxane forms the thermodynamically stable aggregates, which exhibit light-blue emission from charge-transfer complex between the electron-donating pillar[5]arene wheel and the electron-accepting π-conjugated moiety.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202501151"},"PeriodicalIF":3.9,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144075159","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}
Lilian S. Szych, Daniel S. Frost, Moritz J. Ernst, Jonas Bresien, Manuela Weber, Annelie Puhlmann, Luise Sander, Christian Müller
{"title":"Cover Feature: On the Facile Synthesis of Triazaarsoles Using Acyclic Precursors","authors":"Lilian S. Szych, Daniel S. Frost, Moritz J. Ernst, Jonas Bresien, Manuela Weber, Annelie Puhlmann, Luise Sander, Christian Müller","doi":"10.1002/chem.202582702","DOIUrl":"https://doi.org/10.1002/chem.202582702","url":null,"abstract":"<p><b>A new portal has opened to aromatic triazaarsoles</b>. In their Research Article (DOI: 10.1002/chem.202500514), C. Müller and co-workers demonstrate that novel triazaarsoles, the arsenic analogues of tetrazoles and triazaphospholes can be synthesized from easily accessible dichloroarsanes, organic azides and a suitable base. Their findings pave the way to access and fully investigate these aromatic arsenic heterocycles.\u0000\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"31 27","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chem.202582702","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143949841","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nikita Ostrovitsa, Conor Williams, Konstantin Raabe, Joshua McLean, Markus Muttenthaler, Eoin Scanlan
{"title":"An Efficient Thiol-ene Mediated Protocol for Thiolated Peptide Synthesis and On-Resin Diversification.","authors":"Nikita Ostrovitsa, Conor Williams, Konstantin Raabe, Joshua McLean, Markus Muttenthaler, Eoin Scanlan","doi":"10.1002/chem.202501372","DOIUrl":"https://doi.org/10.1002/chem.202501372","url":null,"abstract":"<p><p>The sulfhydryl groups unique nucleophilic and redox properties render it highly useful as a synthetic handle for the diversification of peptide structure, including macrocyclization, ligation, and bioconjugation. Herein, we demonstrated a sequential acyl-thiol-ene/S-deacetylation protocol for selectively installing thiol residues onto bioactive peptides on-resin. Through judicious placement of appropriate unsaturated residues, the hydrothiolation/S-deacetylation protocol offers a novel synthetic tool to investigate the structure-activity relationship of disulfide-containing peptides displaying different ring sizes. Furthermore, a new and generally applicable fluorescent labeling strategy is introduced to facilitate direct on-resin conjugation without intermediate purification steps. These new methods provide a robust and versatile platform for peptide macrocyclization and bioconjugation, with broad applications in peptide synthesis and chemical biology.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202501372"},"PeriodicalIF":3.9,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144075148","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}