The number and functionality of substituents, as well as the stereochemistry of conjugated dienes, play an essential role in their synthetic utility and biological activity. This has prompted tremendous efforts aimed at the stereoselective synthesis of functionalized 1,3-dienyl molecules. However, the stereoselective synthesis of multisubstituted nonterminal 1,3-dienes with heteroatom substituents remains elusive and represents a daunting synthetic challenge. We herein disclose the first palladium-catalyzed redox-neutral dienylation of internal aliphatic-substituted propargylic esters with broad nucleophiles that deliver diversely functionalized 1,2,4-trisubstituted 1,3-dienes with excellent chemo-, regio-, and stereoselectivity. The key success of this protocol lies in the nucleophilic addition to regioselectively form trisubstituted palladacyclobutene intermediate. Notably, this reaction proceeds through chemo- and stereoselective β–H elimination of sterically congested π-allyl palladium complex to produce 1,2,4-trisubstituted 1,3-dienes. Unlike the conventional catalytic Lewis acid pathway, this redox-neutral dienylation omnipotently couples with a broad range of nucleophiles, including fluoride, phenols, alkanols, carboxylic acids, and amides. It provides a modular strategy for constructing high value-added trisubstituted 1,3-dienes with a remarkable stereoselectivity, which remains unaddressed by other methods. Numerous practical transformations of functionalized 1,3-dienes and late-stage diversifications of natural products and bioactive molecules further demonstrate the utility of this reaction.
{"title":"Palladium-Catalyzed Regio-, Chemo-, and Stereoselective Access to Multisubstituted 1,3-Dienes via Redox-Neutral Dienylation Pathway","authors":"Mengfu Dai, Jianchao Chang, Zhimin Sun, Guorong Wu, Liangliang Song, Liang-An Chen","doi":"10.31635/ccschem.025.202505704","DOIUrl":"https://doi.org/10.31635/ccschem.025.202505704","url":null,"abstract":"The number and functionality of substituents, as well as the stereochemistry of conjugated dienes, play an essential role in their synthetic utility and biological activity. This has prompted tremendous efforts aimed at the stereoselective synthesis of functionalized 1,3-dienyl molecules. However, the stereoselective synthesis of multisubstituted nonterminal 1,3-dienes with heteroatom substituents remains elusive and represents a daunting synthetic challenge. We herein disclose the first palladium-catalyzed redox-neutral dienylation of internal aliphatic-substituted propargylic esters with broad nucleophiles that deliver diversely functionalized 1,2,4-trisubstituted 1,3-dienes with excellent chemo-, regio-, and stereoselectivity. The key success of this protocol lies in the nucleophilic addition to regioselectively form trisubstituted palladacyclobutene intermediate. Notably, this reaction proceeds through chemo- and stereoselective β–H elimination of sterically congested π-allyl palladium complex to produce 1,2,4-trisubstituted 1,3-dienes. Unlike the conventional catalytic Lewis acid pathway, this redox-neutral dienylation omnipotently couples with a broad range of nucleophiles, including fluoride, phenols, alkanols, carboxylic acids, and amides. It provides a modular strategy for constructing high value-added trisubstituted 1,3-dienes with a remarkable stereoselectivity, which remains unaddressed by other methods. Numerous practical transformations of functionalized 1,3-dienes and late-stage diversifications of natural products and bioactive molecules further demonstrate the utility of this reaction.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"200 1","pages":"1-13"},"PeriodicalIF":11.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147358823","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}
Pub Date : 2026-03-01DOI: 10.31635/ccschem.025.202505861
Nan Cao, Wenchao Zhao, Kaifeng Niu, Chenqi Zhao, Kaiwei Wang, Felix Haag, Francesco Allegretti, Johanna Rosen, Jonas Björk, Lifeng Chi, Johannes V. Barth, Biao Yang
Aromatic amines (AAs) are widely used in manufacturing industries, where their oxidation plays a crucial role in direct applications and the synthesis of nitrogen-containing compounds. Understanding their reactivity is a prerequisite for their use in various fields. Given their chemical diversity and significance, the behavior of AAs on surfaces is of considerable interest for potential applications. Herein, we combined scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) to explore the reactivity of AAs on silver (Ag) and gold (Au) surfaces using a gas-mediated reaction strategy. Our results revealed that oxidative dehydrogenation was readily achieved after O2-mediated treatment on Ag surfaces, leading to the formation of organometallic nanopores, while AAs remained unperturbed on Au(111), indicating a substrate-dependent behavior. Density functional theory (DFT) calculations corroborate the experimental observations, by simulated core-level shifts and microscopy images, and demonstrate how the choice of substrate dictates the thermodynamics of the overall reactions. These findings emphasize the importance of substrate selection in modulating the surface chemistry of AAs, paving the way for more efficient catalytic processes and material design.
{"title":"Reactivity of Aromatic Amines Under O2 Exposure on Metal Surfaces","authors":"Nan Cao, Wenchao Zhao, Kaifeng Niu, Chenqi Zhao, Kaiwei Wang, Felix Haag, Francesco Allegretti, Johanna Rosen, Jonas Björk, Lifeng Chi, Johannes V. Barth, Biao Yang","doi":"10.31635/ccschem.025.202505861","DOIUrl":"https://doi.org/10.31635/ccschem.025.202505861","url":null,"abstract":"Aromatic amines (AAs) are widely used in manufacturing industries, where their oxidation plays a crucial role in direct applications and the synthesis of nitrogen-containing compounds. Understanding their reactivity is a prerequisite for their use in various fields. Given their chemical diversity and significance, the behavior of AAs on surfaces is of considerable interest for potential applications. Herein, we combined scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) to explore the reactivity of AAs on silver (Ag) and gold (Au) surfaces using a gas-mediated reaction strategy. Our results revealed that oxidative dehydrogenation was readily achieved after O<sub>2</sub>-mediated treatment on Ag surfaces, leading to the formation of organometallic nanopores, while AAs remained unperturbed on Au(111), indicating a substrate-dependent behavior. Density functional theory (DFT) calculations corroborate the experimental observations, by simulated core-level shifts and microscopy images, and demonstrate how the choice of substrate dictates the thermodynamics of the overall reactions. These findings emphasize the importance of substrate selection in modulating the surface chemistry of AAs, paving the way for more efficient catalytic processes and material design.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"6 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147314907","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}
The selection of suitable ionic liquids (ILs) is critical for CO2 capture and electrocatalytic conversion into valuable chemical products. The screening process can be enhanced with theoretical simulations that reveal the property-performance relationship of ILs, accelerating the identification of optimal candidates. However, anhydrous ILs exhibit low dielectric constants and high ion concentrations, challenging traditional first-principles calculations. Additionally, the spatial distribution of CO2 in the electric double layer plays a crucial role in determining the electrocatalytic activity. This work proposes a solution-corrected constant potential model (CPM-sol) to account for the imbalance between the net charge and the number of electrons on the electrode surface through an implicit consideration of ion distributions. By incorporating solution-phase corrections into the conventional CPM model, we reveal the changes in the Fermi level and charge alongside the reaction process. Furthermore, we systematically investigate the impact of various IL properties on electrode surface charging and CO2 distribution. The theoretical results highlight the critical role of interactions between solution components, forming chain-like structures, in determining their distribution in confined environments and influencing the electrode surface charge. These findings provide insights for mechanism-guided electrolyte design.
{"title":"Solution-Corrected Constant Potential Model for CO2 Electrocatalysis in Ionic Liquids","authors":"Jikai Sun, Alejandro Gallegos, Runtong Pan, Jianzhong Wu","doi":"10.31635/ccschem.025.202506424","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506424","url":null,"abstract":"The selection of suitable ionic liquids (ILs) is critical for CO<sub>2</sub> capture and electrocatalytic conversion into valuable chemical products. The screening process can be enhanced with theoretical simulations that reveal the property-performance relationship of ILs, accelerating the identification of optimal candidates. However, anhydrous ILs exhibit low dielectric constants and high ion concentrations, challenging traditional first-principles calculations. Additionally, the spatial distribution of CO<sub>2</sub> in the electric double layer plays a crucial role in determining the electrocatalytic activity. This work proposes a solution-corrected constant potential model (CPM-sol) to account for the imbalance between the net charge and the number of electrons on the electrode surface through an implicit consideration of ion distributions. By incorporating solution-phase corrections into the conventional CPM model, we reveal the changes in the Fermi level and charge alongside the reaction process. Furthermore, we systematically investigate the impact of various IL properties on electrode surface charging and CO<sub>2</sub> distribution. The theoretical results highlight the critical role of interactions between solution components, forming chain-like structures, in determining their distribution in confined environments and influencing the electrode surface charge. These findings provide insights for mechanism-guided electrolyte design.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"73 1","pages":"1-12"},"PeriodicalIF":11.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147314905","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}
Pub Date : 2026-03-01DOI: 10.31635/ccschem.025.202505901
Xueliang Zhang, Quanzheng Deng, Shuqi Wang, Shunai Che, Lu Han
Crystal structural determination is the foundation for exploring the properties of matter by revealing precise atomic positions and structural arrangements. Although automated methods employing diffraction techniques in reciprocal space have been well-established, there remains no comparable approach in real space. This entails substantial challenges for complex structures, particularly those that cannot be resolved by diffraction methods. Among these, mesostructured materials represent one of the most notable examples. Herein, we developed electron tomographic crystallography (ETC), a universal methodology that integrates advanced electron tomography with crystallographic Fourier analysis, to enable direct determination of electrostatic potential distribution in real space without requiring prior knowledge. ETC employs the three-dimensional (3D) tomogram reconstructed from tilt-series two-dimensional (2D) high-resolution imaging data and introduces two innovative workflows: (1) ETC-2D, which performs Fourier synthesis using high-symmetry reprojections of the tomogram and (2) ETC-3D, which directly extracts crystal structural factors via 3D Fourier transformation to calculate the electrostatic potential map for structural solution. We demonstrate the exceptional capabilities of ETC by successfully solving a highly complex gyroid mesostructure, revealing its accuracy, efficiency, and broad applicability. ETC represents a transformative advance in crystallography, enabling precise exploration of intricate structures with precision and efficiency.
{"title":"Electron Tomographic Crystallography: Integrating Tomography and Fourier Synthesis for Real-Space Structural Analysis","authors":"Xueliang Zhang, Quanzheng Deng, Shuqi Wang, Shunai Che, Lu Han","doi":"10.31635/ccschem.025.202505901","DOIUrl":"https://doi.org/10.31635/ccschem.025.202505901","url":null,"abstract":"Crystal structural determination is the foundation for exploring the properties of matter by revealing precise atomic positions and structural arrangements. Although automated methods employing diffraction techniques in reciprocal space have been well-established, there remains no comparable approach in real space. This entails substantial challenges for complex structures, particularly those that cannot be resolved by diffraction methods. Among these, mesostructured materials represent one of the most notable examples. Herein, we developed electron tomographic crystallography (ETC), a universal methodology that integrates advanced electron tomography with crystallographic Fourier analysis, to enable direct determination of electrostatic potential distribution in real space without requiring prior knowledge. ETC employs the three-dimensional (3D) tomogram reconstructed from tilt-series two-dimensional (2D) high-resolution imaging data and introduces two innovative workflows: (1) ETC-2D, which performs Fourier synthesis using high-symmetry reprojections of the tomogram and (2) ETC-3D, which directly extracts crystal structural factors via 3D Fourier transformation to calculate the electrostatic potential map for structural solution. We demonstrate the exceptional capabilities of ETC by successfully solving a highly complex gyroid mesostructure, revealing its accuracy, efficiency, and broad applicability. ETC represents a transformative advance in crystallography, enabling precise exploration of intricate structures with precision and efficiency.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"55 1","pages":"1-12"},"PeriodicalIF":11.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147358788","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}
Photocatalysis opens unique pathways for reductive hydrogenation under mild conditions. Typically, photocatalytic hydrogenation proceeds via single electron transfer (SET), followed by hydrogen atom transfer. Herein, we elucidate that the deliberate arrangement of an electron reservoir and Ni catalysts enables a transition from photoinduced one- to two-electron transfer, yielding desired products via proton acquisition. Specifically, arranging carbon nitride (CN) that stores multiple photogenerated electrons in proximity to a chemically bonded Ni site accomplishes competitive two-electron/proton hydrogenation of halogenated substrates using water as the hydrogen source, outperforming the SET-mediated process. In contrast, the nonchemically bonded Ni and CN system exhibits poor activity for 2e−/H+ hydrogenation. Mechanistic studies further reveal that the low-valent Ni+ and CN(e−) cooperate to transfer two electrons to the substrate. The catalytic utility of this two-electron mechanism is further underscored by the deuterium labeling of diverse (hetero)arenes and bioactive molecules in D2O, achieving deuterium incorporation of up to 99%. Our work highlights the value of light-driven multiple-electron catalysis that reaches otherwise challenging transformations.
{"title":"Shifting from One- to Two-Electron Transfer Towards Water-Donating Photocatalytic Hydrogenation","authors":"Tongtong Jia, Yufan Zhang, Yu Lei, Bangrong Ming, Ran Duan, Hongwei Ji, Jikun Li, Hua Sheng, Chuncheng Chen, Wenjing Song, Jincai Zhao","doi":"10.31635/ccschem.025.202506308","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506308","url":null,"abstract":"Photocatalysis opens unique pathways for reductive hydrogenation under mild conditions. Typically, photocatalytic hydrogenation proceeds via single electron transfer (SET), followed by hydrogen atom transfer. Herein, we elucidate that the deliberate arrangement of an electron reservoir and Ni catalysts enables a transition from photoinduced one- to two-electron transfer, yielding desired products via proton acquisition. Specifically, arranging carbon nitride (CN) that stores multiple photogenerated electrons in proximity to a chemically bonded Ni site accomplishes competitive two-electron/proton hydrogenation of halogenated substrates using water as the hydrogen source, outperforming the SET-mediated process. In contrast, the nonchemically bonded Ni and CN system exhibits poor activity for 2e<sup>−</sup>/H<sup>+</sup> hydrogenation. Mechanistic studies further reveal that the low-valent Ni<sup>+</sup> and CN(e<sup>−</sup>) cooperate to transfer two electrons to the substrate. The catalytic utility of this two-electron mechanism is further underscored by the deuterium labeling of diverse (hetero)arenes and bioactive molecules in D<sub>2</sub>O, achieving deuterium incorporation of up to 99%. Our work highlights the value of light-driven multiple-electron catalysis that reaches otherwise challenging transformations.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"20 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147358790","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}
Artificial photosynthesis for H2O2 production holds pivotal industrial significance, yet achieving ultrahigh efficiency remains a grand challenge due to limited charge separation efficiency and competing reaction pathways. To this end, this work shows a general atom-level strategy through control on nitrogen number on photocatalyst. Substitution on the 1,3-site by two nitrogen atoms gives the best nitrogen-atom effect, leading to a H2O2 production rate of 8896 μmol h−1 g−1 from pure water under O2 without any sacrificial agent, far exceeding all established photocatalysts, along with the apparent quantum efficiency and solar-to-chemical conversion efficiency of as high as 14.1% and 1.3%, respectively. The catalyst can also run steadily for at least 40 h without any significant decrease in photocatalytic performance. Mechanistic analysis reveals that the atom effect has a great contribution on not only increasing the negative charge distribution and dipole moment, thus creating a built-in electric field for charge separation and transfer, but also enhancing the light absorption and adsorption of reaction intermediates, thus promoting both oxygen reduction for H2O2 generation and water oxidation for O2 production. This study highlights the atom effect on superior photocatalysis and provides big potential for massive H2O2 production.
{"title":"Optimizing Atom Effects via Control on the Nitrogen Number in Material for Efficient H2O2 Photosynthesis","authors":"Liecheng Guo, Yuxuan Liu, Yuanzhe Jia, Zhecheng Huang, Lele Gong, Feng Luo","doi":"10.31635/ccschem.025.202505788","DOIUrl":"https://doi.org/10.31635/ccschem.025.202505788","url":null,"abstract":"Artificial photosynthesis for H<sub>2</sub>O<sub>2</sub> production holds pivotal industrial significance, yet achieving ultrahigh efficiency remains a grand challenge due to limited charge separation efficiency and competing reaction pathways. To this end, this work shows a general atom-level strategy through control on nitrogen number on photocatalyst. Substitution on the 1,3-site by two nitrogen atoms gives the best nitrogen-atom effect, leading to a H<sub>2</sub>O<sub>2</sub> production rate of 8896 μmol h<sup>−1</sup> g<sup>−1</sup> from pure water under O<sub>2</sub> without any sacrificial agent, far exceeding all established photocatalysts, along with the apparent quantum efficiency and solar-to-chemical conversion efficiency of as high as 14.1% and 1.3%, respectively. The catalyst can also run steadily for at least 40 h without any significant decrease in photocatalytic performance. Mechanistic analysis reveals that the atom effect has a great contribution on not only increasing the negative charge distribution and dipole moment, thus creating a built-in electric field for charge separation and transfer, but also enhancing the light absorption and adsorption of reaction intermediates, thus promoting both oxygen reduction for H<sub>2</sub>O<sub>2</sub> generation and water oxidation for O<sub>2</sub> production. This study highlights the atom effect on superior photocatalysis and provides big potential for massive H<sub>2</sub>O<sub>2</sub> production.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"70 1","pages":"1-12"},"PeriodicalIF":11.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147358888","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}
In the quest to enhance the photocatalytic production of hydrogen peroxide (H2O2) using covalent organic frameworks (COFs), key processes such as light absorption, charge separation and transport, and surface redox reactions play a pivotal role. However, the simultaneous optimization of these processes is challenging owing to their intrinsic trade-offs and interdependencies. Drawing inspiration from the “bucket effect,” we propose a mixed-linker strategy that combines two aldehyde monomers, namely terephthalaldehyde (TA) and 2,5-di(thiophen-2-yl)terephthalaldehyde (DTTA) with 2,4,6-trimethyl-1,3,5-triazine (TMT) in a precisely controlled ratio, resulting in the development of a high-performance TA/DTTA-2-TMT photocatalyst. The results revealed that the integration of DTTA units significantly broadened the light absorption range and enhanced the charge carrier separation. Concurrently, the inclusion of TA improved the crystallinity and hydrophilicity of the material, thereby facilitating efficient charge-carrier transport and mass transfer during the reaction. Consequently, the TA/DTTA-2-TMT photocatalyst achieved an exceptional H2O2 yield of 3451 μmol·g−1·h−1 in pure water under an air atmosphere and 100 mW·cm−2 light intensity. This study not only presents a groundbreaking strategy for designing high-performance photocatalysts for H2O2 production but also underscores the transformative potential of mixed-linker COFs for the advancement of photocatalytic technologies.
{"title":"Thiophene-Doped Fully Conjugated Covalent Organic Frameworks for Efficient Photocatalytic Hydrogen Peroxide Generation","authors":"Hailong Lin, Guoying Tan, Yujun Ju, Pingru Su, Fengjuan Chen, Yu Tang","doi":"10.31635/ccschem.025.202506161","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506161","url":null,"abstract":"In the quest to enhance the photocatalytic production of hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) using covalent organic frameworks (COFs), key processes such as light absorption, charge separation and transport, and surface redox reactions play a pivotal role. However, the simultaneous optimization of these processes is challenging owing to their intrinsic trade-offs and interdependencies. Drawing inspiration from the “bucket effect,” we propose a mixed-linker strategy that combines two aldehyde monomers, namely terephthalaldehyde (TA) and 2,5-di(thiophen-2-yl)terephthalaldehyde (DTTA) with 2,4,6-trimethyl-1,3,5-triazine (TMT) in a precisely controlled ratio, resulting in the development of a high-performance TA/DTTA-2-TMT photocatalyst. The results revealed that the integration of DTTA units significantly broadened the light absorption range and enhanced the charge carrier separation. Concurrently, the inclusion of TA improved the crystallinity and hydrophilicity of the material, thereby facilitating efficient charge-carrier transport and mass transfer during the reaction. Consequently, the TA/DTTA-2-TMT photocatalyst achieved an exceptional H<sub>2</sub>O<sub>2</sub> yield of 3451 μmol·g<sup>−1</sup>·h<sup>−1</sup> in pure water under an air atmosphere and 100 mW·cm<sup>−2</sup> light intensity. This study not only presents a groundbreaking strategy for designing high-performance photocatalysts for H<sub>2</sub>O<sub>2</sub> production but also underscores the transformative potential of mixed-linker COFs for the advancement of photocatalytic technologies.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"23 1","pages":"1-14"},"PeriodicalIF":11.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147314904","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}
Pub Date : 2026-03-01DOI: 10.31635/ccschem.026.202507176
Yu Liu, Kun Peng, Qian Cao, Zong-Wan Mao
Ubiquitination modification and its abnormal regulation are closely related to cellular life activities and major diseases such as various malignancies. Transition metal complexes with versatile chemical modifiability and biological activities endow them with tremendous potential for exploring the chemical modification of biomolecules. Herein, a rhenium(I) complex (Re1) was designed by integrating a mitochondrial targeting rhenium(I) tricarbonyl scaffold with a bimetallic chelating moiety, able to simultaneously induce zinc/copper ions overload in mitochondria, thus triggering copper-dependent mitochondrial membrane potential collapse and zinc-dependent upregulation of E3 ubiquitin ligase RNF14. This synergistic effect provoked import stress of mitochondrial proteins and modification of RNF14-mediated ubiquitination of surface-trapped proteins, identified as mitochondrial ribosomal proteins (MtRPs), including MRPL28, MRPL41, MRPS35, and MRPS12. Subsequently, Re1 directly crippled the biogenesis of oxidative phosphorylation (OXPHOS) complexes by degrading MRPs responsible for translating OXPHOS subunits and elicited multiple tumor cell death modes, including pyroptosis, apoptosis, and necroptosis, accompanied by activation of in vitro and in vivo antitumor immunity. Accordingly, for the first time, we report the regulatory role and mechanism of metal complexes on ubiquitination modification and propose a novel anticancer paradigm wherein multimetal (Re, Cu, Zn) cooperation activates MRPs ubiquitination to synergistically enhance chemo-immunotherapy.
{"title":"Triggering Ubiquitin-Mediated Ribosomal Protein Degradation by a Mitochondria-Targeted Re(I) Complex via Intervening Zinc/Copper Ion Homeostasis for Chemo-Immunotherapy","authors":"Yu Liu, Kun Peng, Qian Cao, Zong-Wan Mao","doi":"10.31635/ccschem.026.202507176","DOIUrl":"https://doi.org/10.31635/ccschem.026.202507176","url":null,"abstract":"Ubiquitination modification and its abnormal regulation are closely related to cellular life activities and major diseases such as various malignancies. Transition metal complexes with versatile chemical modifiability and biological activities endow them with tremendous potential for exploring the chemical modification of biomolecules. Herein, a rhenium(I) complex (<b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>Re1</bold></b>) was designed by integrating a mitochondrial targeting rhenium(I) tricarbonyl scaffold with a bimetallic chelating moiety, able to simultaneously induce zinc/copper ions overload in mitochondria, thus triggering copper-dependent mitochondrial membrane potential collapse and zinc-dependent upregulation of E3 ubiquitin ligase RNF14. This synergistic effect provoked import stress of mitochondrial proteins and modification of RNF14-mediated ubiquitination of surface-trapped proteins, identified as mitochondrial ribosomal proteins (MtRPs), including MRPL28, MRPL41, MRPS35, and MRPS12. Subsequently, <b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>Re1</bold></b> directly crippled the biogenesis of oxidative phosphorylation (OXPHOS) complexes by degrading MRPs responsible for translating OXPHOS subunits and elicited multiple tumor cell death modes, including pyroptosis, apoptosis, and necroptosis, accompanied by activation of in vitro and in vivo antitumor immunity. Accordingly, for the first time, we report the regulatory role and mechanism of metal complexes on ubiquitination modification and propose a novel anticancer paradigm wherein multimetal (Re, Cu, Zn) cooperation activates MRPs ubiquitination to synergistically enhance chemo-immunotherapy.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"13 1","pages":"1-15"},"PeriodicalIF":11.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147314910","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}
Brain temperature in different regions plays a crucial role in physiological and pathological processes. However, current techniques face challenges in achieving high spatiotemporal resolution and antifouling properties for long-term in vivo applications. Herein, we develop an implantable iontronic thermometer based on a hydrogel-filled micropipette for real-time and in situ monitoring of brain temperature fluctuations with high spatiotemporal resolution. The hydrogel-filled micropipette was fabricated with highly hydrophilic and narrow-mesh hydrogel with excellent antifouling properties against various proteins. The fabricated micro-thermometer exhibited a sensitivity of 2.81 nA/°C and a detection limit of 0.15 °C. In vivo experiments validated the ability of the micro-thermometer to accurately monitor dynamic temperature changes in rat brains during hyperthermia. Owing to the promising performance of the micro-thermometer, we have, for the first time, uncovered dynamic temperature changes during acute fever. The study paves the way for advancements in brain temperature-related physiological and pathological research.
{"title":"An Implantable Robust Micro-Thermometer Uncovers the Dynamic Change of Brain Temperature","authors":"Yifei Pan, Cong Pan, Guangguo Guo, Yueru Zhao, Wenjie Ma, Lanqun Mao, Ping Yu","doi":"10.31635/ccschem.025.202506041","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506041","url":null,"abstract":"Brain temperature in different regions plays a crucial role in physiological and pathological processes. However, current techniques face challenges in achieving high spatiotemporal resolution and antifouling properties for long-term in vivo applications. Herein, we develop an implantable iontronic thermometer based on a hydrogel-filled micropipette for real-time and in situ monitoring of brain temperature fluctuations with high spatiotemporal resolution. The hydrogel-filled micropipette was fabricated with highly hydrophilic and narrow-mesh hydrogel with excellent antifouling properties against various proteins. The fabricated micro-thermometer exhibited a sensitivity of 2.81 nA/°C and a detection limit of 0.15 °C. In vivo experiments validated the ability of the micro-thermometer to accurately monitor dynamic temperature changes in rat brains during hyperthermia. Owing to the promising performance of the micro-thermometer, we have, for the first time, uncovered dynamic temperature changes during acute fever. The study paves the way for advancements in brain temperature-related physiological and pathological research.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"113 1","pages":"1-12"},"PeriodicalIF":11.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147314903","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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