{"title":"A Singlet Oxygen-Mediated Route to O,O-Bidentate BF<sub>2</sub> Complexes via Visible-Light-Driven Ring Opening of Isoxazoles.","authors":"Pritishree Panigrahi, Subhendu Ghosh, Dinabandhu Barik, Manjunath Ningapur, Bhisma K Patel","doi":"10.1002/chem.71144","DOIUrl":"10.1002/chem.71144","url":null,"abstract":"<p><p>A strategy for the O,O-bidentate BF<sub>2</sub> complexation from isoxazole via N─O bond cleavage, N→O replacement, followed by BF<sub>2</sub> insertion, accompanied by ring closing, is accomplished. This non-hydrolytic path proceeds through a sequence involving isoxazole ring opening via N─O bond cleavage, generating an azirine intermediate, which then reacts with the in situ generated singlet oxygen (<sup>1</sup>O<sub>2</sub>). Subsequent elimination of nitric oxide (NO) and BF<sub>2</sub> insertion affords a highly luminogenic borylated product.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71144"},"PeriodicalIF":3.6,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13532125/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147968956","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}
Hanan Al Hamwi, Mirko Rippke, Anke Spannenberg, Michal Horáček, Jiří Pinkas, Vojtěch Varga, Martin Lamač, Fabian Reiß, Torsten Beweries
{"title":"Dinuclear Group 4 Metallocene Catalysts of the Type [(Cp<sub>2</sub>M)<sub>2</sub>(μ-Me)(μ-C<sub>2</sub>R)]: Structure-Activity Relationships in Ethylene Polymerization.","authors":"Hanan Al Hamwi, Mirko Rippke, Anke Spannenberg, Michal Horáček, Jiří Pinkas, Vojtěch Varga, Martin Lamač, Fabian Reiß, Torsten Beweries","doi":"10.1002/chem.71125","DOIUrl":"10.1002/chem.71125","url":null,"abstract":"<p><p>The heterodinuclear zirconocene/titanocene complexes, [Cp<sub>2</sub>Zr(μ-Me)(μ-C<sub>2</sub>R)(TiCp<sub>2</sub>)] where R = SiMe<sub>3</sub> and R = Ph, were prepared using the previously reported comproportion reaction of the zirconocene alkynyl methyl complex with Rosenthal's zirconocene source. Examination of the molecular structure revealed alkynyl group migration from Zr to Ti, as confirmed by single-crystal x-ray analysis, nuclear magnetic resonance spectroscopy, and quantum chemical calculations. The homodinuclear (Zr/Zr) and heterodinuclear (Ti/Zr) complexes were activated with [Ph<sub>3</sub>C][B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>], B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>, and a mixture of B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub> with excess Et<sub>3</sub>SiH (SiHB system) as aluminium-free activators and tested in ethylene polymerization. Depending on the type of activator, unique reactivity was observed, resulting in either electron or methyl abstraction and the formation of cationic species. The catalytically active species are proposed to have dinuclear character, forming linear polyethylenes with unsaturated groups predominantly on the Zr cationic center. In contrast, the Ti cationic center generated by a SiHB system only in dichloromethane produced silicon-terminated polyethylenes.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71125"},"PeriodicalIF":3.6,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13532123/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147985948","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}
Qingxin Ma, Zhanyu Su, Peng Zhang, Yize Zuo, Yiqun Cao, Tianzeng Chen, Yonghong Wang, Biwu Chu, Hao Li, Joseph S. Francisco, Hong He
{"title":"pH-Dependent Photosensitized Generation of Multiphase •OH Radicals: Unravelling the Catalytic Mechanism","authors":"Qingxin Ma, Zhanyu Su, Peng Zhang, Yize Zuo, Yiqun Cao, Tianzeng Chen, Yonghong Wang, Biwu Chu, Hao Li, Joseph S. Francisco, Hong He","doi":"10.1002/chem.71228","DOIUrl":"10.1002/chem.71228","url":null,"abstract":"<div>\u0000 \u0000 <p>Photosensitized reactions at aerosol interfaces are pivotal to regional atmospheric oxidizing capacity, but the complex physicochemical architecture of atmospheric particles severely impedes mechanistic elucidation of photochemical pollution. We report that polycyclic aromatic hydrocarbons (PAHs) in soot photosensitization processes can function as critical catalysts driving hydroxyl radicals (•OH) formation. Photochemical experiments and quantum-chemical calculations reveal that photoexcited PAHs activate two distinct •OH generation channels. On the one hand, the conversion of excited-state PAHs to •PAH<sup>+</sup> triggers the generation of •OH radicals through a proton-coupled electron-transfer (PCET) sequence. Meanwhile, the direct electron transfer between hydroxide ions (OH<sup>−</sup>) and •PAH<sup>+</sup> can also produce additional •OH radicals and reduce •PAH<sup>+</sup> to reform PAHs. Further pH-dependent experiments support that the relative dominance of two different channels in aqueous microenvironments depends on the interfacial acidity. These findings deepen our understanding of aerosol photosensitization and reveal that particulate acidity, beyond modulating the surface uptake of pollutants, can also control their secondary conversion by regulating interfacial oxidation capacity.</p>\u0000 </div>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"32 33","pages":""},"PeriodicalIF":3.6,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148161202","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}
Moritz Schmidt, Alexander Virovets, Eugenia Peresypkina, Hans-Wolfram Lerner, Matthias Wagner
{"title":"Polarity on Demand: Nucleophilic, Electrophilic, and Ambiphilic Reactivity at a 9,10-Dihydro-9,10-Disilaanthracene Platform.","authors":"Moritz Schmidt, Alexander Virovets, Eugenia Peresypkina, Hans-Wolfram Lerner, Matthias Wagner","doi":"10.1002/chem.71100","DOIUrl":"10.1002/chem.71100","url":null,"abstract":"<p><p>9,10-Dihydro-9,10-diheteroanthracenes constitute rigid molecular entities that enable cooperative reactivity between two proximal heteroatoms. While diboraanthracenes act as ditopic Lewis acids and diphosphaanthracenes as ditopic Lewis bases, ambiphilic behavior has so far largely relied on the incorporation of two different heteroelements. Herein, we demonstrate ambiphilicity within a homo-heteroelement framework based on 9,10-dihydro-9,10-disilaanthracene (DSA). Efficient cyclocondensation of 1,2-disilyl-4,5-dimethylbenzene, promoted by substoichiometric amounts of MeLi, affords DSA 1<sup>2H</sup> featuring two SiH<sub>2</sub> groups. Compound 1<sup>2H</sup> exhibits electrophilic reactivity toward magnesium anthracene, affording a double 'butterfly'-type framework 13 reminiscent of the anthracene photodimer. Selective reductive Si-H bond cleavage using 2 equiv. KC<sub>8</sub> or excess elemental K enables controlled, stepwise access to the monosilanide [1<sup>H</sup>]<sup>-</sup> or the disilanide [1]<sup>2-</sup>, respectively. The disilanide [1]<sup>2-</sup>, which was structurally characterized by SCXRD, behaves as a ditopic Lewis base toward 9,10-dihydro-9,10-diboraanthracene, forming a cyclic, 13-type double adduct K<sub>2</sub>[10]. Notably, [1<sup>H</sup>]<sup>-</sup> displays ambiphilic reactivity toward pTolC≡CpTol to furnish a tricyclic product containing a deprotonated 1,2-ethylenediyl bridge between the Si centers. These findings establish that controlled reduction within a homo-heteroelement platform enables polarity switching, thereby providing a versatile strategy for the design of cooperative main-group reactivity.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71100"},"PeriodicalIF":3.6,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13532117/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147968948","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}
Shuya Miao, Shuang Tang, Xiaoda Pan, Xi Zhang, Xianze Yin, Zongmin Zhu, Long Zheng
{"title":"Natural Rubber Latex-Reinforced Polyacrylamide Hydrogels With Enhanced Mechanical Performance.","authors":"Shuya Miao, Shuang Tang, Xiaoda Pan, Xi Zhang, Xianze Yin, Zongmin Zhu, Long Zheng","doi":"10.1002/chem.71652","DOIUrl":"https://doi.org/10.1002/chem.71652","url":null,"abstract":"<p><p>Polyacrylamide (PAM) hydrogels are attractive soft materials owing to their high-water content and tunable network structure. However, their limited strength and toughness restrict practical use. Here, prevulcanized natural rubber (NR) latex was incorporated into an acrylamide precursor before polymerization to prepare NR latex-reinforced PAM (PAM@NR) hydrogels. The PAM matrix served as a continuous hydrophilic network, while NR latex particles served as flexible biobased dispersed domains. NR incorporation produced a denser freeze-dried surface morphology with NR-rich domains and increased the storage and loss moduli, indicating enhanced network stiffness and a stronger dissipative response. At a PAM-to-dry-NR mass ratio of 5:5 (PAM@NR-5:5), the hydrogel achieved a tensile strength of 255.0 kPa, elongation at break of 401%, and toughness of 809.1 kJ m<sup>-</sup> <sup>3</sup>, representing increases of 278.3%, 165.6%, and 1207.1% compared with PAM, respectively. NR incorporation also suppressed swelling and slowed water loss under ambient conditions. These results suggest that prevulcanized NR latex can serve as a biobased reinforcing phase to improve the mechanical performance of PAM hydrogels.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71652"},"PeriodicalIF":3.6,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148872331","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":"Gold Redox Catalysis Enabled by Cyclic Diacyl Peroxides for Homocoupling and Cross-Coupling of Terminal Alkynes","authors":"Haowei Gao, Jiale Yan, Chao Zeng, Lei Shi","doi":"10.1002/chem.71175","DOIUrl":"10.1002/chem.71175","url":null,"abstract":"<div>\u0000 \u0000 <p>Conjugated 1,3-diynes are valuable scaffolds, yet their selective assembly via cross-coupling of terminal alkynes remains challenging. In this study, we report a gold redox catalytic system employing cyclic diacyl peroxides as dual-function oxidants that enable both homocoupling and cross-coupling of terminal alkynes without exogenous ligands. This operationally simple protocol proceeds under mild conditions, exhibits broad substrate scope, and delivers symmetrical and unsymmetrical 1,3-diynes in moderate to good yields. The tether-guided redox platform facilitates efficient Au(I)/Au(III) redox cycling, offering a previously unrecognized catalytic paradigm to ligand-free gold catalysis for selective C(sp)─C(sp) bond formation.</p>\u0000 </div>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"32 33","pages":""},"PeriodicalIF":3.6,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148012431","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":"Bioinspired Design and Synthesis of Polyphenolic Star-Like and Hyperbranched Polyester Models","authors":"Guanfei Shen, Laurent Pouységu, Christophe Schatz, Etienne Grau, Stéphane Quideau","doi":"10.1002/chem.71120","DOIUrl":"10.1002/chem.71120","url":null,"abstract":"<p>Inspired by the structure of natural gallotannins, which feature polyphenolic galloyl ester chains grafted onto a glucopyranose core, we report the design and synthesis of star-like and dendritic hyperbranched aromatic polyester model compounds. Using penta-<i>O</i>-acylated-<i>D</i>-glucopyranose core molecules made from D-glucose and <i>AB</i><sub>n</sub>-type phenolic acid monomers, such as vanillic, protocatechuic, ferulic, and caffeic acids, we developed a modular strategy to access core-arm architectures through stepwise esterification reactions under mild Steglich conditions. Oligomeric model compounds were synthesized to validate this strategy and assess the solubility and structural features of the resulting materials. Direct polyesterification attempts yielded partially grafted analogues, and protocatechuic acid-derived polymers spontaneously formed stable aqueous dispersions with nanoparticulate structures (∼400 nm). These glycopolymeric nanoparticles were successfully loaded with the hydrophobic dye nile red, demonstrating their potential as bioinspired encapsulation systems. This work opens new perspectives for the development of functional biobased aromatic polyesters derived from renewable phenolics.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"32 33","pages":""},"PeriodicalIF":3.6,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chem.71120","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147985936","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}
{"title":"Polylactic Acid-Based Biodegradable Room-Temperature Phosphorescent Materials: A Review","authors":"Nianshuang Zhang, Yujing Qin, Haoyi Ma, Jinbin Liu, Minghui Lu, Shanfeng Xue, Qikun Sun, Wenjun Yang","doi":"10.1002/chem.71162","DOIUrl":"10.1002/chem.71162","url":null,"abstract":"<div>\u0000 \u0000 <p>Polylactic acid (PLA) is an ideal matrix for constructing pure organic room-temperature phosphorescence (RTP) materials due to its renewability, biodegradability, and excellent biocompatibility. This study investigates the preparation, luminescence mechanisms, and application potential of PLA-based RTP materials. By evaluating both chemical grafting and physical doping strategies, we highlight the distinct advantages of PLA-based systems. Our findings demonstrate that the unique properties of the PLA matrix are pivotal in activating and enhancing RTP performance. These materials hold significant promise for bioimaging, information encryption, and 3D printing, effectively overcoming the degradation of RTP properties typically encountered in photocuring processes. Finally, we discuss the future prospects for PLA-based room-temperature phosphorescent materials.</p>\u0000 </div>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"32 33","pages":""},"PeriodicalIF":3.6,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148004050","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}
Yuxin Liu, Gyunhee Lee, Curt M Wong, Elizabeth J Vrana, Christo S Sevov
{"title":"Redox-Targeting Reactions of Viologen-Based Shuttles and Polymers Translated From Nonaqueous to Aqueous Electrolyte.","authors":"Yuxin Liu, Gyunhee Lee, Curt M Wong, Elizabeth J Vrana, Christo S Sevov","doi":"10.1002/chem.71148","DOIUrl":"10.1002/chem.71148","url":null,"abstract":"<p><p>Redox-targeting flow batteries (RTFBs) present an attractive strategy for enhancing the energy density of conventional redox flow batteries (RFBs) by integrating heterogeneous energy storage materials as capacity boosters. However, nearly all RTFB systems have been developed with nonaqueous redox chemistries, while capacity boosters in aqueous storage systems are limited to anthraquinone chemistries. In this work, we expand the chemistry of aqueous RTFBs to viologen-based compounds by translating a nonaqueous RTFB into an aqueous platform. All redox chemistries of the prior nonaqueous RTFB-redox shuttles and solids-required a synthetic redesign to address challenges associated with promoting fast redox targeting reactions of organic solids and shuttles in aqueous media. The effects of molecular structure, ion pairing, and supporting electrolytes on RTFB performance are detailed in this report to provide a case study for developing future aqueous organic RTFBs. The redesigned RTFBs achieve 50% utilization of the aqueous capacity booster for charge storage.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71148"},"PeriodicalIF":3.6,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13532144/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147968932","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}
Patrycja Lenartowicz, Jan-Willem H Langenbach, Nataliia Voloshyna, David Aidukas, Arwin J Brouwer, John A W Kruijtzer, Geert-Jan Boons
{"title":"Synthesis and Biological Evaluation of Well-Defined M6P(n)-Modified Glycopeptides for Targeted Protein Degradation.","authors":"Patrycja Lenartowicz, Jan-Willem H Langenbach, Nataliia Voloshyna, David Aidukas, Arwin J Brouwer, John A W Kruijtzer, Geert-Jan Boons","doi":"10.1002/chem.71147","DOIUrl":"10.1002/chem.71147","url":null,"abstract":"<p><p>Lysosome-targeting chimeras (LYTACs) is an emerging therapeutic strategy to deplete circulating and cell-surface proteins. It harnesses endocytic receptors, such as the cation-independent mannose-6-phosphate receptor (CI-M6PR), to direct a protein of interest for lysosomal degradation. We have developed a synthetic methodology to prepare multifunctional M6PR-targeting glycopeptides of varying valency using common building blocks. Peptides were prepared having one to six 4-methyltrityl (Mtt)-protected lysine moieties that could selectively be removed to give amines that were coupled with mannose-6-phosphate (M6P), mannose-6-phosphonate (M6Pn) and mannosyl building blocks having an α-configured anomeric 2-(2-(2-(2-hydroxyethoxy)ethoxy)ethoxy)acetic acid. The hydroxyls, phosphate and phosphonate of the building blocks were protected as p-methylbenzyl, which exhibited excellent stability during synthesis but could be removed under mild conditions without affecting sensitive functionalities. The glycopeptides have an azido lysine moiety for functionalization by strain-promoted azide-alkyne cycloaddition (SPAAC). Cetuximab (Ctx) was functionalized with bicyclo[6.1.0]non-4-yne for conjugation to M6P and M6Pn containing peptides via SPAAC. The resulting mAbs were examined for cellular uptake of soluble Epidermal Growth Factor Receptor (EGFR). Only mABs modified by glycopeptides carrying three or six M6P or M6Pn residues significantly increased uptake. Phosphonates were more efficient in removing cell surface EGFR by Ctx modified by tri- or hexavalent M6P or M6Pn ligand.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71147"},"PeriodicalIF":3.6,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13532108/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147979794","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}