Mohamed I Gadallah, Kate A McConnell, Kelli M Hager, Virginia K James, Annalee W Nguyen, Jennifer A Maynard, Jennifer S Brodbelt
Structural characterization of antigen-antibody interactions is critical for understanding protective vaccine responses and development of therapeutic monoclonal antibodies (mAb). Traditional biophysical and biochemical techniques often require the immobilization of one binding partner or provide ensemble-averaged measurements, constraints which may limit the ability to probe multiple facets of antigen-antibody interactions. Native mass spectrometry (nMS) offers a versatile alternative, providing a comprehensive view of antigen-antibody complexes. Here, we utilized native MS to screen the interactions between a small panel of monoclonal antibodies (mAbs) and the Bordetella pertussis vaccine antigen mature pertactin (Prn), offering in-depth characterization of binding affinity, stoichiometry, and competition. We implemented variable temperature electrospray ionization to evaluate thermally induced unfolding and stability of different mAb·Prn complexes, while biolayer interferometry (BLI) and competition experiments were employed to provide complementary information about binding kinetics and mapping of distinct epitopes on Prn. Finally, we used nMS to evaluate the interactions of individual mAbs with Prn variants as a predictor for therapeutic action. Our results demonstrate the utility of nMS in combination with other techniques as a powerful approach for understanding the interactions of protective mAb binding to Prn, providing insight into mechanisms of vaccine-induced protection.
{"title":"Screening pertactin-specific antibodies and evaluating competitive epitope recognition by native mass spectrometry.","authors":"Mohamed I Gadallah, Kate A McConnell, Kelli M Hager, Virginia K James, Annalee W Nguyen, Jennifer A Maynard, Jennifer S Brodbelt","doi":"10.1039/d5sc09702a","DOIUrl":"https://doi.org/10.1039/d5sc09702a","url":null,"abstract":"<p><p>Structural characterization of antigen-antibody interactions is critical for understanding protective vaccine responses and development of therapeutic monoclonal antibodies (mAb). Traditional biophysical and biochemical techniques often require the immobilization of one binding partner or provide ensemble-averaged measurements, constraints which may limit the ability to probe multiple facets of antigen-antibody interactions. Native mass spectrometry (nMS) offers a versatile alternative, providing a comprehensive view of antigen-antibody complexes. Here, we utilized native MS to screen the interactions between a small panel of monoclonal antibodies (mAbs) and the <i>Bordetella pertussis</i> vaccine antigen mature pertactin (Prn), offering in-depth characterization of binding affinity, stoichiometry, and competition. We implemented variable temperature electrospray ionization to evaluate thermally induced unfolding and stability of different mAb·Prn complexes, while biolayer interferometry (BLI) and competition experiments were employed to provide complementary information about binding kinetics and mapping of distinct epitopes on Prn. Finally, we used nMS to evaluate the interactions of individual mAbs with Prn variants as a predictor for therapeutic action. Our results demonstrate the utility of nMS in combination with other techniques as a powerful approach for understanding the interactions of protective mAb binding to Prn, providing insight into mechanisms of vaccine-induced protection.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12994607/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147479937","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Subir Panja, Tuan Anh Trinh, Ethan M. Warrington, Derek B. Hu, Leah C. Garman, Ilia Guzei, Jennifer Schomaker
Transition metal-catalyzed C-H functionalization is a powerful strategy to upgrade simple hydrocarbons to versatile synthetic building blocks and is a useful tool for the late-stage functionalization of complex molecules. In this study, we report an intermolecular, non-directed amidation of benzylic C-H bonds via a nitrene transfer pathway. This operationally simple method uses inexpensive silver-based catalysts, only a small excess of substrate and displays broad substrate scope that includes arenes, biaryls, heteroarenes, and complex molecules. Changes to the AgNTf2:tert-butylterpyridine ligand ratio furnish dimeric or trimeric Ag complexes as the proposed active catalysts; these show differing reactivity and selectivity dependent on the nature of the substrate’s benzylic C–H bond.
{"title":"Silver-Catalysed Intermolecular Benzylic-Selective C–H Amidation via Nitrene Transfer","authors":"Subir Panja, Tuan Anh Trinh, Ethan M. Warrington, Derek B. Hu, Leah C. Garman, Ilia Guzei, Jennifer Schomaker","doi":"10.1039/d5sc10184k","DOIUrl":"https://doi.org/10.1039/d5sc10184k","url":null,"abstract":"Transition metal-catalyzed C-H functionalization is a powerful strategy to upgrade simple hydrocarbons to versatile synthetic building blocks and is a useful tool for the late-stage functionalization of complex molecules. In this study, we report an intermolecular, non-directed amidation of benzylic C-H bonds via a nitrene transfer pathway. This operationally simple method uses inexpensive silver-based catalysts, only a small excess of substrate and displays broad substrate scope that includes arenes, biaryls, heteroarenes, and complex molecules. Changes to the AgNTf2:tert-butylterpyridine ligand ratio furnish dimeric or trimeric Ag complexes as the proposed active catalysts; these show differing reactivity and selectivity dependent on the nature of the substrate’s benzylic C–H bond.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"92 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147466172","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This review provides an overview of recent advances in CO2 electrocatalysis, starting with the development of homogeneous electrocatalytic systems. We focused on porphyrin and phthalocyanine based molecular catalysts where different chemical strategies have been implemented drawing inspiration from natural enzyme systems that process CO2, such as hydrogen bonding, proton relay, bimetallic cooperative action, electrostatic interactions and structural dynamics to help enhancing the selectivity and efficiency of electrochemical CO2 reduction. The discussion then expands to heterogeneous processes in traditional H-cells, and more relevant flow-cell setups integrated with gas diffusion electrodes. A special focus is given to the growing trend of hybrid molecular-metallic co-catalyst systems, which are driving significant progress in heterogeneous CO2 electrocatalysis.
{"title":"Molecular Engineering of Metalloporphyrins and Phthalocycanines for Homogeneous and Heterogeneous CO 2 Electroreduction","authors":"Aakash Santra, Joost Helsen, Ally Aukauloo, Chanjuan Zhang, Arnab Ghatak, Zhiyuan Chen, Jing Shen, Yuvraj Y. Birdja","doi":"10.1039/d5sc07983g","DOIUrl":"https://doi.org/10.1039/d5sc07983g","url":null,"abstract":"This review provides an overview of recent advances in CO2 electrocatalysis, starting with the development of homogeneous electrocatalytic systems. We focused on porphyrin and phthalocyanine based molecular catalysts where different chemical strategies have been implemented drawing inspiration from natural enzyme systems that process CO2, such as hydrogen bonding, proton relay, bimetallic cooperative action, electrostatic interactions and structural dynamics to help enhancing the selectivity and efficiency of electrochemical CO2 reduction. The discussion then expands to heterogeneous processes in traditional H-cells, and more relevant flow-cell setups integrated with gas diffusion electrodes. A special focus is given to the growing trend of hybrid molecular-metallic co-catalyst systems, which are driving significant progress in heterogeneous CO2 electrocatalysis.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"17 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147466175","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
High-nuclearity indium-oxo clusters (InOCs) represent critical molecular models for understanding indium oxide (In2O3) nanoparticles, yet their rational synthesis remains a formidable challenge. Herein, we report a dual-ligand strategy to access bixbyite-type In15-oxo clusters—the largest discrete indium-oxo cores reported to date. Their strategically labile carboxylate sites enable facile functionalization to generate InOC-38, InOC-39, and InOC-40. Notably, the In15 core serves as the highest-nuclearity secondary building unit (SBU) within the InOCs family, which can be extended into an In30 dimer (InOC-41) via a cluster-docking strategy or hierarchically assembled into one-dimensional chains (InOC-42) using multidentate 6-hydroxynicotinate linkers. These architectures, featuring π-conjugated ligands, heavy metals, and dense intermolecular interactions, exhibit exceptional optical limiting (OL) performance. InOC-38 and InOC-41 demonstrate record metrics (Tmin = 0.11 and 0.17; FOL = 0.275 and 0.408 J/cm2), surpassing state-of-the-art cluster-based materials. Furthermore, their processability into flexible transparent films underscores significant practical potential for optical applications.
{"title":"Record-Large Indium-Oxo Clusters: Synthesis, Hierarchical Assembly, and Efficient Optical Limiting","authors":"Xiuzhen Wang, Yian Chen, Xiaofeng Yi, Shumei Chen, Jian Zhang","doi":"10.1039/d6sc00913a","DOIUrl":"https://doi.org/10.1039/d6sc00913a","url":null,"abstract":"High-nuclearity indium-oxo clusters (InOCs) represent critical molecular models for understanding indium oxide (In2O3) nanoparticles, yet their rational synthesis remains a formidable challenge. Herein, we report a dual-ligand strategy to access bixbyite-type In15-oxo clusters—the largest discrete indium-oxo cores reported to date. Their strategically labile carboxylate sites enable facile functionalization to generate InOC-38, InOC-39, and InOC-40. Notably, the In15 core serves as the highest-nuclearity secondary building unit (SBU) within the InOCs family, which can be extended into an In30 dimer (InOC-41) via a cluster-docking strategy or hierarchically assembled into one-dimensional chains (InOC-42) using multidentate 6-hydroxynicotinate linkers. These architectures, featuring π-conjugated ligands, heavy metals, and dense intermolecular interactions, exhibit exceptional optical limiting (OL) performance. InOC-38 and InOC-41 demonstrate record metrics (Tmin = 0.11 and 0.17; FOL = 0.275 and 0.408 J/cm2), surpassing state-of-the-art cluster-based materials. Furthermore, their processability into flexible transparent films underscores significant practical potential for optical applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"11 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147466177","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hongmin Yu, Thomas Golin Almeida, Samir P. Rezgui, Vili-Taneli Salo, John D. Crounse, Brian M. Stoltz, Henrik G. Kjaergaard, Paul O. Wennberg
Gas-phase autoxidation is an atmospheric chemistry reaction mechanism capable of transforming volatile organic compounds (VOCs) into highly oxygenated organic molecules (HOMs) that contribute to secondary organic aerosol (SOA) formation and growth. The key steps in this mechanism are intramolecular hydrogen shift (H-shift) reactions in organic peroxy radicals (RO2). For acyclic saturated molecules, these H-shift reactions are generally sufficiently slow that they cannot compete with atmospheric bimolecular reactions with NOx species, except for the 1,5 and 1,6 H-shifts, occurring via transition states (TS) of six- and seven-membered rings. Here, we report a surprisingly fast long-range H-shift reaction in a RO2 formed in the photo-oxidation of a volatile diether. In 1,2-diethoxyethane (1,2-DEE), we observe experimentally a 1,8 H-shift reaction that occurs with a rate coefficient on the order of ∼1 s−1 at 294 K – a rate that outcompetes all other RO2 unimolecular chemistry in the system and will, under most atmospheric conditions, outcompete bimolecular processes as well. Theoretical calculations indicate that activation of the C–H bond by an α-oxyl substituent and weaker transannular strain in the 1,8 H-shift transition state, combined with inductive deactivation of C–H bonds by a β-oxyl group at the abstraction site of competing 1,5 and 1,6 H-shifts, enable the longer-span 1,8 H-shift to be competitive. Our findings broaden the recognized reactivity of functionalized RO2 and highlight the potential for structurally diverse VOCs to undergo unexpected autoxidation pathways, producing HOMs at greater yield and with higher molecular complexity than previously anticipated.
气相自氧化是一种大气化学反应机制，能够将挥发性有机化合物（VOCs）转化为高氧有机分子（HOMs），从而促进二次有机气溶胶（SOA）的形成和生长。该机理的关键步骤是有机过氧自由基（RO2）中的分子内氢移（H-shift）反应。对于无环饱和分子，这些h移反应通常足够缓慢，以至于它们无法与大气中与NOx物种的双分子反应竞争，除了通过六元环和七元环的过渡态（TS）发生的1,5和1,6 h移。在这里，我们报道了在挥发性醚的光氧化形成的RO2中令人惊讶的快速远程h移位反应。在1,2-二氧乙烷（1,2- dee）中，我们在实验中观察到一个1,8 h移位反应，在294 K下发生的速率系数为~ 1 s−1，这一速率优于系统中所有其他RO2单分子化学反应，并且在大多数大气条件下，也将优于双分子过程。理论计算表明，α-羟基取代基的激活和1,8 h -移位过渡态中较弱的跨环应变，再加上β-羟基在1,5和1,6 h -移位的抽象位置诱导失活，使得长跨度1,8 h -移位具有竞争性。我们的发现拓宽了功能化RO2的公认反应性，并强调了结构多样的VOCs经历意想不到的自氧化途径的潜力，以更高的产量和更高的分子复杂性生产HOMs。
{"title":"Stealing from a distant neighbor: an unexpectedly fast long-span peroxy radical hydrogen-shift reaction in a long-chain diether","authors":"Hongmin Yu, Thomas Golin Almeida, Samir P. Rezgui, Vili-Taneli Salo, John D. Crounse, Brian M. Stoltz, Henrik G. Kjaergaard, Paul O. Wennberg","doi":"10.1039/d5sc10150f","DOIUrl":"https://doi.org/10.1039/d5sc10150f","url":null,"abstract":"Gas-phase autoxidation is an atmospheric chemistry reaction mechanism capable of transforming volatile organic compounds (VOCs) into highly oxygenated organic molecules (HOMs) that contribute to secondary organic aerosol (SOA) formation and growth. The key steps in this mechanism are intramolecular hydrogen shift (H-shift) reactions in organic peroxy radicals (RO<small><sub>2</sub></small>). For acyclic saturated molecules, these H-shift reactions are generally sufficiently slow that they cannot compete with atmospheric bimolecular reactions with NO<small><sub><em>x</em></sub></small> species, except for the 1,5 and 1,6 H-shifts, occurring <em>via</em> transition states (TS) of six- and seven-membered rings. Here, we report a surprisingly fast long-range H-shift reaction in a RO<small><sub>2</sub></small> formed in the photo-oxidation of a volatile diether. In 1,2-diethoxyethane (1,2-DEE), we observe experimentally a 1,8 H-shift reaction that occurs with a rate coefficient on the order of ∼1 s<small><sup>−1</sup></small> at 294 K – a rate that outcompetes all other RO<small><sub>2</sub></small> unimolecular chemistry in the system and will, under most atmospheric conditions, outcompete bimolecular processes as well. Theoretical calculations indicate that activation of the C–H bond by an α-oxyl substituent and weaker transannular strain in the 1,8 H-shift transition state, combined with inductive deactivation of C–H bonds by a β-oxyl group at the abstraction site of competing 1,5 and 1,6 H-shifts, enable the longer-span 1,8 H-shift to be competitive. Our findings broaden the recognized reactivity of functionalized RO<small><sub>2</sub></small> and highlight the potential for structurally diverse VOCs to undergo unexpected autoxidation pathways, producing HOMs at greater yield and with higher molecular complexity than previously anticipated.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"176 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147461933","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Per- and polyfluoroalkyl substances (PFAS) are a class of man-made chemicals extensively employed in industrial processes, with their strong C-F bond energy conferring exceptional stability. However, this stability also leads to bioaccumulation and environmental persistence, posing threats to ecosystems and human health. Conventional physical separation technologies can only concentrate PFAS without completely destroying them. Against this backdrop, electrochemical technology has emerged as one of the most promising strategies for complete PFAS destruction, benefiting from its mild reaction conditions and controllable electron transfer. This review systematically summarizes the research progress on electrochemical PFAS degradation, comprehensively examining the degradation mechanisms and key influencing factors in electrochemical oxidation, reduction, and combined processes. It highlights the crucial roles of density functional theory (DFT) and molecular dynamics (MD) calculations in elucidating interfacial behaviors and atomic-scale C–F bond activation mechanisms. Addressing the bottlenecks of mass transfer limitations and incomplete defluorination encountered in practical applications, this paper prospectively points out the potential of microenvironmental regulation and the development of bifunctional materials for achieving in-situ deep mineralization. Furthermore, it briefly explores the application prospects of artificial intelligence (AI)-enabled high-throughput screening technologies in accelerating the development of multi-objective electrode materials. Overall, this review constructs a comprehensive research framework spanning from fundamental bond cleavage mechanisms to macroscopic processes and data-driven optimization. It provides systematic strategies for the complete destruction of PFAS and offers theoretical references for the rational design of advanced environmental functional materials.
{"title":"Advances in Electrochemical Technologies for PFAS Destruction","authors":"Yuqing Dong, Shuaiyu Gao, Yuelin Zhao, Genban Sun, Jihong Yu","doi":"10.1039/d5sc09459c","DOIUrl":"https://doi.org/10.1039/d5sc09459c","url":null,"abstract":"Per- and polyfluoroalkyl substances (PFAS) are a class of man-made chemicals extensively employed in industrial processes, with their strong C-F bond energy conferring exceptional stability. However, this stability also leads to bioaccumulation and environmental persistence, posing threats to ecosystems and human health. Conventional physical separation technologies can only concentrate PFAS without completely destroying them. Against this backdrop, electrochemical technology has emerged as one of the most promising strategies for complete PFAS destruction, benefiting from its mild reaction conditions and controllable electron transfer. This review systematically summarizes the research progress on electrochemical PFAS degradation, comprehensively examining the degradation mechanisms and key influencing factors in electrochemical oxidation, reduction, and combined processes. It highlights the crucial roles of density functional theory (DFT) and molecular dynamics (MD) calculations in elucidating interfacial behaviors and atomic-scale C–F bond activation mechanisms. Addressing the bottlenecks of mass transfer limitations and incomplete defluorination encountered in practical applications, this paper prospectively points out the potential of microenvironmental regulation and the development of bifunctional materials for achieving in-situ deep mineralization. Furthermore, it briefly explores the application prospects of artificial intelligence (AI)-enabled high-throughput screening technologies in accelerating the development of multi-objective electrode materials. Overall, this review constructs a comprehensive research framework spanning from fundamental bond cleavage mechanisms to macroscopic processes and data-driven optimization. It provides systematic strategies for the complete destruction of PFAS and offers theoretical references for the rational design of advanced environmental functional materials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"5 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147462062","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Simon B. H. Karnbrock, Jan F. Köster, Isabelle Becker, Christopher Golz, Franc Meyer, Martí Gimferrer, Manuel Alcarazo
Correction for “Bis(amidophenolate)-supported pnictoranides: Lewis acid-induced electromerism in a bismuth complex” by Simon B. H. Karnbrock et al., Chem. Sci., 2025, 16, 14178–14185, https://doi.org/10.1039/D5SC03374H.
{"title":"Correction: Bis(amidophenolate)-supported pnictoranides: Lewis acid-induced electromerism in a bismuth complex","authors":"Simon B. H. Karnbrock, Jan F. Köster, Isabelle Becker, Christopher Golz, Franc Meyer, Martí Gimferrer, Manuel Alcarazo","doi":"10.1039/d6sc90049f","DOIUrl":"https://doi.org/10.1039/d6sc90049f","url":null,"abstract":"Correction for “Bis(amidophenolate)-supported pnictoranides: Lewis acid-induced electromerism in a bismuth complex” by Simon B. H. Karnbrock <em>et al.</em>, <em>Chem. Sci.</em>, 2025, <strong>16</strong>, 14178–14185, https://doi.org/10.1039/D5SC03374H.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"78 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147461934","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xiaoyu Li, Rui Liu, Han Cao, Chuanyin Tang, Guancheng Hua, Yingxu Hu, Xiangjiang Fan, Yongqing Xia, Shengjie Wang
Conjugated covalent organic frameworks (COFs) integrating different aromatic building units into extended π-conjugated backbones through imine linkages exhibit great potential in photocatalysis but suffer from lower efficiency of intramolecular electron transfer. Herein, we present a new strategy for the reversible activation of imine-linked COFs by triethanolamine (TEOA) under light irradiation. The activated COFs exhibit expanded solar light absorption, elevated reduction potential, decreased chemical impedance, suppressed recombination of charges, and significantly enhanced photocatalytic performance in the generation of nicotinamide adenine dinucleotide (NADH) without any metal cocatalysts. Experimental and theoretical results indicate that the fascinating photocatalytic performance originates from the protonation of imine bonds in the COFs, in which TEOA provides protons in addition to electrons, while light irradiation provides the driving force to overcome the energy barriers. This breaks through the traditional views that imine bonds can only be protonated under acidic conditions and provides new perspectives for the design of metal-free photocatalysts for highly efficient energy conversion.
{"title":"Triethanolamine-activated imine-linked covalent organic frameworks for highly efficient NADH generation","authors":"Xiaoyu Li, Rui Liu, Han Cao, Chuanyin Tang, Guancheng Hua, Yingxu Hu, Xiangjiang Fan, Yongqing Xia, Shengjie Wang","doi":"10.1039/d6sc01309k","DOIUrl":"https://doi.org/10.1039/d6sc01309k","url":null,"abstract":"Conjugated covalent organic frameworks (COFs) integrating different aromatic building units into extended π-conjugated backbones through imine linkages exhibit great potential in photocatalysis but suffer from lower efficiency of intramolecular electron transfer. Herein, we present a new strategy for the reversible activation of imine-linked COFs by triethanolamine (TEOA) under light irradiation. The activated COFs exhibit expanded solar light absorption, elevated reduction potential, decreased chemical impedance, suppressed recombination of charges, and significantly enhanced photocatalytic performance in the generation of nicotinamide adenine dinucleotide (NADH) without any metal cocatalysts. Experimental and theoretical results indicate that the fascinating photocatalytic performance originates from the protonation of imine bonds in the COFs, in which TEOA provides protons in addition to electrons, while light irradiation provides the driving force to overcome the energy barriers. This breaks through the traditional views that imine bonds can only be protonated under acidic conditions and provides new perspectives for the design of metal-free photocatalysts for highly efficient energy conversion.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"233 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147462063","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Efficient and color-tunable organic persistent room-temperature phosphorescence (p-RTP) is highly attractive for applications in colorful displays, advanced information encryption, and sensing. However, achieving such p-RTP remains challenging due to the lack of effective design strategies. Here, we introduce a synergistic chromophore-engineering approach that couples conventional and nonconventional luminophores to construct donor–acceptor adducts. These adducts exhibit dual fluorescence/p-RTP with pronounced excitation-dependent color tunability, even in crystals. Anthracene bromination (BAN/DBAN-MI) enhances SOC via the heavy-atom effect and increases Φp to 21.5% (DBAN-MI). By contrast, maleimide bromination (AN-BMI/AN-DBMI) reorganizes packing and redistributes through-space conjugation (TSC), enabling single-component white emission. Single-crystal analysis, femtosecond transient absorption spectroscopy, and theoretical calculations reveal how site-specific halogenation governs ISC and clustering-triggered emission (CTE) behaviors. This work establishes a general design principle for efficient and color-tunable organic p-RTP materials combining both aromatic and nonaromatic moieties through the CTE mechanism, highlighting their potential in multicolor displays and white-light illumination.
{"title":"Site-selective bromination of anthracene–maleimide Diels–Alder crystals for tunable afterglow and white light emission","authors":"Guangxin Yang, Tianwen Zhu, Xiang Chen, Junhao Duan, Zhipeng Zhao, Wang Zhang Yuan","doi":"10.1039/d6sc00542j","DOIUrl":"https://doi.org/10.1039/d6sc00542j","url":null,"abstract":"Efficient and color-tunable organic persistent room-temperature phosphorescence (p-RTP) is highly attractive for applications in colorful displays, advanced information encryption, and sensing. However, achieving such p-RTP remains challenging due to the lack of effective design strategies. Here, we introduce a synergistic chromophore-engineering approach that couples conventional and nonconventional luminophores to construct donor–acceptor adducts. These adducts exhibit dual fluorescence/p-RTP with pronounced excitation-dependent color tunability, even in crystals. Anthracene bromination (BAN/DBAN-MI) enhances SOC <em>via</em> the heavy-atom effect and increases <em>Φ</em><small><sub>p</sub></small> to 21.5% (DBAN-MI). By contrast, maleimide bromination (AN-BMI/AN-DBMI) reorganizes packing and redistributes through-space conjugation (TSC), enabling single-component white emission. Single-crystal analysis, femtosecond transient absorption spectroscopy, and theoretical calculations reveal how site-specific halogenation governs ISC and clustering-triggered emission (CTE) behaviors. This work establishes a general design principle for efficient and color-tunable organic p-RTP materials combining both aromatic and nonaromatic moieties through the CTE mechanism, highlighting their potential in multicolor displays and white-light illumination.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"83 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147466176","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yang Li, Zhixuan Liu, Haoji Wang, Jun Chen, Zebo Gu, Junyong Deng, Guorong Liu, Kun Huang, Siyao Zhang, Hao Feng, Hao Chen, Hongxin He, Fuliang Zhu, Lina Hu, Hongshuai Hou, Xiaobo Ji
Ni-rich cathodes have revolutionized lithium-ion batteries by delivering high energy density. However, achieving a durable trade-off between capacity and long life remains a formidable challenge, hindered by oxygen loss, irreversible phase transformation, and structural degradation during repeated cycles. Herein, we propose a synchronous bulk-to-surface full-scale modification strategy by integrating multi-site B/Ce bulk doping with a conformal CeO2 surface coating. Boron atoms are successfully incorporated into transition metal (TM) tetrahedral interstitial sites as a covalent "rivet" to suppress detrimental H2-H3 phase transitions and anisotropic strain, thereby effectively inhibiting the intra-particle crack propagation. Concurrently, cerium ions are located at TM octahedral sites, acting as an electron buffer to decrease the concentration of reactive Ni4+ species and stabilize the oxygen lattice. Furthermore, the uniform CeO2 protective layer serves as a robust physical barrier against electrolyte corrosion while effectively scavenging acidic species, reducing TM dissolution, and mitigating interfacial side reactions. The comprehensively regulated NCM83 cathode exhibits exceptional electrochemical performance, maintaining 94.4% capacity retention after 1000 cycles at 1 C in a pouch-type full cell. This study presents an innovative approach that combines an internal multi-site lattice with an external surface structure for developing advanced Ni-rich cathodes.
{"title":"Holistic Bulk-to-Surface Tailoring of Ni-Rich Cathodes for Unlocking Superior Electrochemical Stability","authors":"Yang Li, Zhixuan Liu, Haoji Wang, Jun Chen, Zebo Gu, Junyong Deng, Guorong Liu, Kun Huang, Siyao Zhang, Hao Feng, Hao Chen, Hongxin He, Fuliang Zhu, Lina Hu, Hongshuai Hou, Xiaobo Ji","doi":"10.1039/d6sc01562j","DOIUrl":"https://doi.org/10.1039/d6sc01562j","url":null,"abstract":"Ni-rich cathodes have revolutionized lithium-ion batteries by delivering high energy density. However, achieving a durable trade-off between capacity and long life remains a formidable challenge, hindered by oxygen loss, irreversible phase transformation, and structural degradation during repeated cycles. Herein, we propose a synchronous bulk-to-surface full-scale modification strategy by integrating multi-site B/Ce bulk doping with a conformal CeO2 surface coating. Boron atoms are successfully incorporated into transition metal (TM) tetrahedral interstitial sites as a covalent \"rivet\" to suppress detrimental H2-H3 phase transitions and anisotropic strain, thereby effectively inhibiting the intra-particle crack propagation. Concurrently, cerium ions are located at TM octahedral sites, acting as an electron buffer to decrease the concentration of reactive Ni4+ species and stabilize the oxygen lattice. Furthermore, the uniform CeO2 protective layer serves as a robust physical barrier against electrolyte corrosion while effectively scavenging acidic species, reducing TM dissolution, and mitigating interfacial side reactions. The comprehensively regulated NCM83 cathode exhibits exceptional electrochemical performance, maintaining 94.4% capacity retention after 1000 cycles at 1 C in a pouch-type full cell. This study presents an innovative approach that combines an internal multi-site lattice with an external surface structure for developing advanced Ni-rich cathodes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"33 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147466179","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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