Norbornene-mediated remote meta-selective C-H functionalizations of arenes have been limited to relatively weakly electronegative and “soft” species, such as aryl, alkyl, and alkylamino moieties. Herein, we describe the first example of the use of a nucleophilic reagent, such as an alcohol or amide, to replace the electrophilic reagent during the palladium-catalyzed meta-C-H alkoxylation or amidation reaction of an arene. The reaction conditions are mild and highly site-selective, thereby facilitating the direct introduction of natural products or drug molecules containing hydroxyl or amido groups at the meta-positions of arenes. In addition, the directing group is rapidly convertible into the corresponding aldehyde, which further enhances the applicability of the reaction. Control experiments and density functional theory (DFT) calculations revealed that alcohol and amide polarity reversal induced by hypervalent iodine reagents and the subsequent formation of a Pd(IV) intermediate via the oxidative addition of the aryl-norbornyl-palladacycle intermediate are crucial for promoting the entire catalytic reaction cycle.
{"title":"Palladium-Catalyzed meta-C-H Alkoxylation and Amidation via the Polarity Reversal of Nucleophilic Reagents","authors":"Xiao-Ping Gong, Heng Yue, Ning Liang, Yu-Yong Luan, Rui-Qiang Jiao, Xi Chen, Yan-Chong Huang, Tian Ding, Bo-Sheng Zhang, Xue-Yuan Liu, Yong-Min Liang","doi":"10.1002/anie.202501648","DOIUrl":"https://doi.org/10.1002/anie.202501648","url":null,"abstract":"Norbornene-mediated remote meta-selective C-H functionalizations of arenes have been limited to relatively weakly electronegative and “soft” species, such as aryl, alkyl, and alkylamino moieties. Herein, we describe the first example of the use of a nucleophilic reagent, such as an alcohol or amide, to replace the electrophilic reagent during the palladium-catalyzed meta-C-H alkoxylation or amidation reaction of an arene. The reaction conditions are mild and highly site-selective, thereby facilitating the direct introduction of natural products or drug molecules containing hydroxyl or amido groups at the meta-positions of arenes. In addition, the directing group is rapidly convertible into the corresponding aldehyde, which further enhances the applicability of the reaction. Control experiments and density functional theory (DFT) calculations revealed that alcohol and amide polarity reversal induced by hypervalent iodine reagents and the subsequent formation of a Pd(IV) intermediate via the oxidative addition of the aryl-norbornyl-palladacycle intermediate are crucial for promoting the entire catalytic reaction cycle.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"34 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143526468","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 operational perovskite/organic tandem solar cells are subjected to light irradiation and driven by a higher bias voltage than single-junction solar cells, posing a severe challenge to their stabilities. Light irradiation can trigger halide phase segregation in the perovskite subcell, exacerbated under higher bias voltage through electron–phonon coupling. To address this, dimethylammonium ion (DMA+) incorporation delays perovskite crystallization by forming an intermediate phase, enhancing crystallinity, and reducing lattice structural defects. DMA+ with a larger ionic radius entering the A-site of lattice tilts the [PbX6]4- (X: I or Br) octahedral, enlarging the perovskite bandgap, shortening Pb–I bonds, and reinforcing the lattice. This mitigates halide escaping from the lattice and subsequent ion migration. Phase segregation in the perovskite subcell is significantly suppressed under high-power irradiation and bias voltage. Consequently, the perovskite subcell exhibits increased and stable quasi-Fermi-level splitting values, delivering a high open-circuit voltage of 1.34 V. Notably, 0.062-cm2 and 1.004-cm2 perovskite/organic tandem solar cells achieved remarkable efficiencies of 26.15% (certified of 25.34%) and 24.87%, respectively, exhibiting excellent operational stability of T90 ~ 1350 h.
{"title":"Retarding Phase Segregation via Lattice Reinforcement for Efficient and Stable Perovskite/Organic Tandem solar cells","authors":"Pengpeng Dong, Zhichao Zhang, Weijie Chen, Jialei Zheng, Jiacheng Xu, Ziyue Wang, Shuaiqing Kang, Haiyang Chen, Xingxing Jiang, Jianlei Cao, Yaowen Li, Yongfang Li","doi":"10.1002/anie.202502391","DOIUrl":"https://doi.org/10.1002/anie.202502391","url":null,"abstract":"The operational perovskite/organic tandem solar cells are subjected to light irradiation and driven by a higher bias voltage than single-junction solar cells, posing a severe challenge to their stabilities. Light irradiation can trigger halide phase segregation in the perovskite subcell, exacerbated under higher bias voltage through electron–phonon coupling. To address this, dimethylammonium ion (DMA+) incorporation delays perovskite crystallization by forming an intermediate phase, enhancing crystallinity, and reducing lattice structural defects. DMA+ with a larger ionic radius entering the A-site of lattice tilts the [PbX6]4- (X: I or Br) octahedral, enlarging the perovskite bandgap, shortening Pb–I bonds, and reinforcing the lattice. This mitigates halide escaping from the lattice and subsequent ion migration. Phase segregation in the perovskite subcell is significantly suppressed under high-power irradiation and bias voltage. Consequently, the perovskite subcell exhibits increased and stable quasi-Fermi-level splitting values, delivering a high open-circuit voltage of 1.34 V. Notably, 0.062-cm2 and 1.004-cm2 perovskite/organic tandem solar cells achieved remarkable efficiencies of 26.15% (certified of 25.34%) and 24.87%, respectively, exhibiting excellent operational stability of T90 ~ 1350 h.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"52 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143526467","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}
Qiao Xia, Xingxing Jiang, Chunbo Jiang, Haijun Zhang, Yilei Hu, Lu Qi, Chao Wu, Guangfeng Wei, Zheshuai Lin, Zhipeng Huang, Mark G. Humphrey, Chi Zhang
Tailored syntheses of non-centrosymmetric (NCS) second-order nonlinear optical (NLO) crystals, particularly those of metastable NCS polymorphs, remain extremely challenging due to the complex interactions of their constituent primitives. We report herein the first successful synthesis of a set of three nitrate supramolecular polymorphs (C2H5N4)(NO3) (α‑, β‑, and γ-phases) by a pH-modulation secondary-bond strategy, via the assembly of two types of π-conjugated planar primitives. Solutions of different pH result in differing orientation of secondary bonds between [C2H5N4] and [NO3] primitives. Secondary bonds dominate the packing of primitives in crystal lattices; varying these secondary bonds can afford NCS or centrosymmetric nitrate supramolecular polymorphs, with 2D α‑phase irreversibly transformed to 2D β‑phase in a solution of appropriate pH. These two polymorphs display distinctly different SHG responses and birefringences, ascribed to variation in stacking of 2D hydrogen-bonded layers resulting from the differing environmental pH. Supramolecular crystal structures comparison and theoretical studies confirm the crucial role played by secondary-bond interactions between adjacent primitives in the rare nitrate supramolecular polymorphs. This work paves the way in elucidating the supramolecular polymorph transition-mechanisms and correlating the polymorph structures and their NLO properties, and thereby discloses a new paradigm for development of high-performance NCS materials with tailored optical properties.
{"title":"pH-Dependent Switching Between Nonlinear-Optical-Active Nitrate-Based Supramolecular Polymorphs","authors":"Qiao Xia, Xingxing Jiang, Chunbo Jiang, Haijun Zhang, Yilei Hu, Lu Qi, Chao Wu, Guangfeng Wei, Zheshuai Lin, Zhipeng Huang, Mark G. Humphrey, Chi Zhang","doi":"10.1002/anie.202503136","DOIUrl":"https://doi.org/10.1002/anie.202503136","url":null,"abstract":"Tailored syntheses of non-centrosymmetric (NCS) second-order nonlinear optical (NLO) crystals, particularly those of metastable NCS polymorphs, remain extremely challenging due to the complex interactions of their constituent primitives. We report herein the first successful synthesis of a set of three nitrate supramolecular polymorphs (C2H5N4)(NO3) (α‑, β‑, and γ-phases) by a pH-modulation secondary-bond strategy, via the assembly of two types of π-conjugated planar primitives. Solutions of different pH result in differing orientation of secondary bonds between [C2H5N4] and [NO3] primitives. Secondary bonds dominate the packing of primitives in crystal lattices; varying these secondary bonds can afford NCS or centrosymmetric nitrate supramolecular polymorphs, with 2D α‑phase irreversibly transformed to 2D β‑phase in a solution of appropriate pH. These two polymorphs display distinctly different SHG responses and birefringences, ascribed to variation in stacking of 2D hydrogen-bonded layers resulting from the differing environmental pH. Supramolecular crystal structures comparison and theoretical studies confirm the crucial role played by secondary-bond interactions between adjacent primitives in the rare nitrate supramolecular polymorphs. This work paves the way in elucidating the supramolecular polymorph transition-mechanisms and correlating the polymorph structures and their NLO properties, and thereby discloses a new paradigm for development of high-performance NCS materials with tailored optical properties.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"34 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143526469","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}
Lithium-oxygen (Li-O2) batteries have attracted significant attention due to their ultra-high theoretical energy density, but are obstructed by the sluggish reaction kinetics at the cathode and high overpotential. Our previous researches have proved that energy fields such as light, force and heat are effective strategies to improve the reaction kinetics of Li-O2 batteries. Herein, we proposed a novel magnetic field-assisted Li-O2 batteries via a spin polarization strategy. By doping magnetic Mn2+ ions with spin polarization characteristics into CsPbBr3 (Mn-CsPbBr3) perovskite, a magnetic field-responsive cathode was designed and prepared. The incorporation of Mn2+ ions drives charge redistribution and spin polarization of CsPbBr3, which remarkably improve the carrier separation efficiency and the oxygen species adsorption energy. Increased spin-polarization of the magnetic elements by Zeeman effect in an external magnetic field results in the enhanced oxygen reduction and evolution reaction. In the magnetic field, a low overpotential of 0.40 V was obtained for Li-O2 batteries with Mn-CsPbBr3 cathodes which demonstrate an ultralow overpotential of 0.12 V and an ultra-high energy efficiency of 96.3% with the further illumination. The introduction of magnetic fields into the Li-O2 battery system and provides a new avenue for improving the reaction kinetics of rechargeable Li-O2 battery.
{"title":"A Magnetic Field-Assisted Lithium-Oxygen Batteries with Enhanced Reaction Kinetics by Spin-Polarization Strategy","authors":"Xin-Yuan Yuan, De-Hui Guan, Xiao-Xue Wang, Jian-You Li, Cheng-Lin Miao, Ji-Jing Xu","doi":"10.1002/anie.202421361","DOIUrl":"https://doi.org/10.1002/anie.202421361","url":null,"abstract":"Lithium-oxygen (Li-O2) batteries have attracted significant attention due to their ultra-high theoretical energy density, but are obstructed by the sluggish reaction kinetics at the cathode and high overpotential. Our previous researches have proved that energy fields such as light, force and heat are effective strategies to improve the reaction kinetics of Li-O2 batteries. Herein, we proposed a novel magnetic field-assisted Li-O2 batteries via a spin polarization strategy. By doping magnetic Mn2+ ions with spin polarization characteristics into CsPbBr3 (Mn-CsPbBr3) perovskite, a magnetic field-responsive cathode was designed and prepared. The incorporation of Mn2+ ions drives charge redistribution and spin polarization of CsPbBr3, which remarkably improve the carrier separation efficiency and the oxygen species adsorption energy. Increased spin-polarization of the magnetic elements by Zeeman effect in an external magnetic field results in the enhanced oxygen reduction and evolution reaction. In the magnetic field, a low overpotential of 0.40 V was obtained for Li-O2 batteries with Mn-CsPbBr3 cathodes which demonstrate an ultralow overpotential of 0.12 V and an ultra-high energy efficiency of 96.3% with the further illumination. The introduction of magnetic fields into the Li-O2 battery system and provides a new avenue for improving the reaction kinetics of rechargeable Li-O2 battery.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"32 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143526450","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}
Leihao Lu, Jianchang Xu, Xuehui Huang, Leyi Hu, Kangfan Ji, Chuhuan Jiang, Yanfang Wang, Yue Qin, Yang Zhang, Juan Zhang, Jiahao Hu, Shenxi Qian, Yingqi Huang, Hongzhen Bai, Xiangnan Zhang, Fuyao Liu, Zhen Gu, Jinqiang Wang
Injectable formulations with sustained and steady release capabilities are critically required to treat diseases requiring temporary or lifelong continuous therapy, especially for drugs with a short half-life. Additionally, achieving a sufficiently high drug loading in a single dose remains a persistent challenge. Herein, by mimicking the formation principles of mussel adhesive plaques, we have developed membrane-enclosed crystalline systems of insulin and progesterone as model macro- and small-molecular crystalline drugs. The system exhibits a substantial drug loading capacity (> 90%). It exhibits sustained and zero-order release kinetics, thereby facilitating the establishment of a subcutaneous reservoir containing a substantial drug load, enabling progressive and continuous release of the drug into the body. One single injection of membrane-enclosed insulin crystal can maintain normoglycemia in diabetic mice for up to 7 days. Meanwhile, membrane-coated progesterone crystals can sustain drug release in rats for over 7 days. The protein membrane can be cleared from the injection sites in 35 days. This system can serve as a versatile platform for the sustained release of various crystalline pharmaceuticals and treating distinct diseases.
{"title":"Mussel Foot Protein Membrane-Enclosed Crystalline Drug with Zero-Order Release Kinetics for Long-Acting Therapy","authors":"Leihao Lu, Jianchang Xu, Xuehui Huang, Leyi Hu, Kangfan Ji, Chuhuan Jiang, Yanfang Wang, Yue Qin, Yang Zhang, Juan Zhang, Jiahao Hu, Shenxi Qian, Yingqi Huang, Hongzhen Bai, Xiangnan Zhang, Fuyao Liu, Zhen Gu, Jinqiang Wang","doi":"10.1002/anie.202502205","DOIUrl":"https://doi.org/10.1002/anie.202502205","url":null,"abstract":"Injectable formulations with sustained and steady release capabilities are critically required to treat diseases requiring temporary or lifelong continuous therapy, especially for drugs with a short half-life. Additionally, achieving a sufficiently high drug loading in a single dose remains a persistent challenge. Herein, by mimicking the formation principles of mussel adhesive plaques, we have developed membrane-enclosed crystalline systems of insulin and progesterone as model macro- and small-molecular crystalline drugs. The system exhibits a substantial drug loading capacity (> 90%). It exhibits sustained and zero-order release kinetics, thereby facilitating the establishment of a subcutaneous reservoir containing a substantial drug load, enabling progressive and continuous release of the drug into the body. One single injection of membrane-enclosed insulin crystal can maintain normoglycemia in diabetic mice for up to 7 days. Meanwhile, membrane-coated progesterone crystals can sustain drug release in rats for over 7 days. The protein membrane can be cleared from the injection sites in 35 days. This system can serve as a versatile platform for the sustained release of various crystalline pharmaceuticals and treating distinct diseases.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"28 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143526452","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}
Giovanni Lissandrini, Davide Zeppilli, Francesca Lorandi, Krzysztof Matyjaszewski, Abdirisak A. Isse, Laura Orian, Marco Fantin
Photoinduced radical addition fragmentation chain transfer (PET-RAFT) polymerization typically requires high light intensity (>5 mW/cm2), limiting energy efficiency and scalability. We demonstrate that adding a base to PET-RAFT systems drastically enhances the reactivity of acidic chain transfer agents (CTAs) with Zn-based photocatalysts (Zn porphyrin and Zn phthalocyanine). This approach enables complete polymerization under microwatt light intensity (0.25 mW/cm2), a significant improvement over traditional PET-RAFT, which showed no conversion under the same conditions. Both acrylates and methacrylates polymerized efficiently with excellent chain-end fidelity. Reactivity was triggered chemically (via base addition) or electrochemically (via electrolytic reduction). Mechanistic studies reveal that base addition promotes a CTA-Zn photocatalyst complex, shifting the activation from bimolecular to more efficient unimolecular PET-RAFT.
{"title":"Photo-RAFT Polymerization under Microwatt Irradiation via Unimolecular Photoinduced Electron Transfer","authors":"Giovanni Lissandrini, Davide Zeppilli, Francesca Lorandi, Krzysztof Matyjaszewski, Abdirisak A. Isse, Laura Orian, Marco Fantin","doi":"10.1002/anie.202424225","DOIUrl":"https://doi.org/10.1002/anie.202424225","url":null,"abstract":"Photoinduced radical addition fragmentation chain transfer (PET-RAFT) polymerization typically requires high light intensity (>5 mW/cm2), limiting energy efficiency and scalability. We demonstrate that adding a base to PET-RAFT systems drastically enhances the reactivity of acidic chain transfer agents (CTAs) with Zn-based photocatalysts (Zn porphyrin and Zn phthalocyanine). This approach enables complete polymerization under microwatt light intensity (0.25 mW/cm2), a significant improvement over traditional PET-RAFT, which showed no conversion under the same conditions. Both acrylates and methacrylates polymerized efficiently with excellent chain-end fidelity. Reactivity was triggered chemically (via base addition) or electrochemically (via electrolytic reduction). Mechanistic studies reveal that base addition promotes a CTA-Zn photocatalyst complex, shifting the activation from bimolecular to more efficient unimolecular PET-RAFT.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"33 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143518454","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}
Darius Mazhari Dorooee, Séverine Ravez, Didier Vertommen, Nicolas Renault, Nicolas Papadopoulos, Romain Marteau, Emeline Charnelle, Karine Porte, Alexandre Gobert, Nathalie Hennuyer, Gaetan Herinckx, Maëla Pautric, Aurélie Jonneaux, Jean-Christophe Devedjian, David Devos, Bart Staels, Patricia Melnyk, Stefan Constantinescu, Raphaël Frédérick, Jamal El Bakali
Lipid metabolism is essential for cellular homeostasis, and its disruption is linked to various diseases. Acyl-coenzyme A synthetase long-chain family member 4 (ACSL4), a pivotal enzyme in lipid metabolism, has emerged as a therapeutic target for ferroptosis-related conditions and cancer. Antidiabetic drug rosiglitazone is the reference ACSL4 inhibitor. However, its potent activity on peroxisome proliferator-activated receptor gamma (PPARγ), a key regulator of lipid metabolism, represents a significant limitation. Here, we report the discovery and characterization of LIBX-A401 (compound 9), a potent ACSL4 inhibitor derived from rosiglitazone but devoid of PPARγ activity. We showed that its binding to ACSL4 is ATP-dependent. Using Hydrogen-Deuterium Exchange Mass Spectrometry, we demonstrate that ATP binding stabilizes the ACSL4 C-terminus, with LIBX-A401 further stabilizing this domain and altering the fatty acid gate-region. Photoaffinity labeling with a diazirine probe identified A329 within the fatty acid binding site, while molecular dynamics simulations and mutagenesis highlighted Q302 as critical for LIBX-A401 binding. LIBX-A401 exhibits significant anti-ferroptotic properties in cells, supported by demonstrated target engagement. These findings position LIBX-A401 as a valuable tool for studying ACSL4 in ferroptosis-related diseases and cancer, while its elucidated binding mode paves the way to the rational design of improved ACSL4 inhibitors with therapeutic potential.
{"title":"LIBX-A401: A Novel Selective Inhibitor of Acyl-CoA Synthetase Long Chain Family Member 4 (ACSL4) and Its Binding Mode","authors":"Darius Mazhari Dorooee, Séverine Ravez, Didier Vertommen, Nicolas Renault, Nicolas Papadopoulos, Romain Marteau, Emeline Charnelle, Karine Porte, Alexandre Gobert, Nathalie Hennuyer, Gaetan Herinckx, Maëla Pautric, Aurélie Jonneaux, Jean-Christophe Devedjian, David Devos, Bart Staels, Patricia Melnyk, Stefan Constantinescu, Raphaël Frédérick, Jamal El Bakali","doi":"10.1002/anie.202500518","DOIUrl":"https://doi.org/10.1002/anie.202500518","url":null,"abstract":"Lipid metabolism is essential for cellular homeostasis, and its disruption is linked to various diseases. Acyl-coenzyme A synthetase long-chain family member 4 (ACSL4), a pivotal enzyme in lipid metabolism, has emerged as a therapeutic target for ferroptosis-related conditions and cancer. Antidiabetic drug rosiglitazone is the reference ACSL4 inhibitor. However, its potent activity on peroxisome proliferator-activated receptor gamma (PPARγ), a key regulator of lipid metabolism, represents a significant limitation. Here, we report the discovery and characterization of LIBX-A401 (compound 9), a potent ACSL4 inhibitor derived from rosiglitazone but devoid of PPARγ activity. We showed that its binding to ACSL4 is ATP-dependent. Using Hydrogen-Deuterium Exchange Mass Spectrometry, we demonstrate that ATP binding stabilizes the ACSL4 C-terminus, with LIBX-A401 further stabilizing this domain and altering the fatty acid gate-region. Photoaffinity labeling with a diazirine probe identified A329 within the fatty acid binding site, while molecular dynamics simulations and mutagenesis highlighted Q302 as critical for LIBX-A401 binding. LIBX-A401 exhibits significant anti-ferroptotic properties in cells, supported by demonstrated target engagement. These findings position LIBX-A401 as a valuable tool for studying ACSL4 in ferroptosis-related diseases and cancer, while its elucidated binding mode paves the way to the rational design of improved ACSL4 inhibitors with therapeutic potential.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"52 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143518493","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}
Zhenhai Wen, Huibing Wang, Kai Chen, Zhiwen Lu, Shengjian Lin, Yalong Yuan, Xi Liu, Yu Zhang, Junxiang Chen
High-entropy materials are poised to revolutionize materials science and industrial applications due to their design flexibility, peculiar performance, and broad applicability. In this study, we present a proof-of-concept high-entropy engineered nanocarbon (HENC) co-doped with five nonmetal elements (B, F, P, S, and N), synthesized via in-situ polymerization modification of ZIF-8 followed by pyrolysis. The HENC exhibits outstanding performance as a non-metal electrocatalyst for the oxygen reduction reaction (ORR), with activity on par with benchmark Pt/C electrocatalysts and superior cyclic stability. Simulations and all-site calculations reveal that the synergistic effects of abundant heteroatoms and increased system entropy facilitate the formation of *O2 species, with N, P, and S acting as the key active elements, while co-doping with B and F further enhances stability. Notably, HENCs have been validated as cathode catalysts in zinc-air batteries, achieving an impressive peak power density of 604 mW cm−2 and demonstrating long-term stability over a 16-day period, outpacing the commercial Pt/C catalyst (542 mW cm−2). This work not only enriches the concept of high entropy and advances the understanding of high-entropy materials but also opens a new avenue for the development of high-performance low-cost catalysts.
{"title":"Nonmetallic High-Entropy Engineered Nanocarbons for Advanced ORR Electrocatalysis","authors":"Zhenhai Wen, Huibing Wang, Kai Chen, Zhiwen Lu, Shengjian Lin, Yalong Yuan, Xi Liu, Yu Zhang, Junxiang Chen","doi":"10.1002/anie.202501290","DOIUrl":"https://doi.org/10.1002/anie.202501290","url":null,"abstract":"High-entropy materials are poised to revolutionize materials science and industrial applications due to their design flexibility, peculiar performance, and broad applicability. In this study, we present a proof-of-concept high-entropy engineered nanocarbon (HENC) co-doped with five nonmetal elements (B, F, P, S, and N), synthesized via in-situ polymerization modification of ZIF-8 followed by pyrolysis. The HENC exhibits outstanding performance as a non-metal electrocatalyst for the oxygen reduction reaction (ORR), with activity on par with benchmark Pt/C electrocatalysts and superior cyclic stability. Simulations and all-site calculations reveal that the synergistic effects of abundant heteroatoms and increased system entropy facilitate the formation of *O2 species, with N, P, and S acting as the key active elements, while co-doping with B and F further enhances stability. Notably, HENCs have been validated as cathode catalysts in zinc-air batteries, achieving an impressive peak power density of 604 mW cm−2 and demonstrating long-term stability over a 16-day period, outpacing the commercial Pt/C catalyst (542 mW cm−2). This work not only enriches the concept of high entropy and advances the understanding of high-entropy materials but also opens a new avenue for the development of high-performance low-cost catalysts.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"27 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143526472","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}
Ning Liu, Jialong Jiang, Shiqi Zhang, Runhao Zhang, Mingming Xu, Zhonghang Chen, Peng Cheng, Wei Shi
Arrangement of donor-acceptor (D-A) components in order at a molecular level provides a means to achieve efficient electron-hole separation for promoting the activity of photocatalysts. Herein, we report the coordination assembly of D-A molecules with desired staggered energy levels in two isostructural metal-organic frameworks (MOFs) 1 and 2, which exhibit high photocatalytic hydrogen evolution activity without using any cocatalysts and photosensitizers. The modulation of active metal sites of the D-A MOFs leads to an increase of photocatalytic hydrogen evolution rates from 1260 to 3218 μmol h−1 g−1. A detailed mechanism study revealed that the energy bond defined by the D-A components assisted with metal centers is the key to efficiently generate photogenerated charge carriers, and 2 has an appropriate affinity to proton to reduce the energy barrier for hydrogen evolution. Besides, the enhanced proton transport kinetics based on the arrayed free carboxyl groups in the hydrogen bonded network endows 2 higher proton conductivity than 1, thus promoting the usage rate of active metal sites in 2 for enhanced hydrogen evolution reaction kinetics.
{"title":"Arrangement of Ordered D-A Components in a Metal-Organic Framework for Cocatalyst-Free Photocatalytic Hydrogen Evolution with Efficient Proton Conduction","authors":"Ning Liu, Jialong Jiang, Shiqi Zhang, Runhao Zhang, Mingming Xu, Zhonghang Chen, Peng Cheng, Wei Shi","doi":"10.1002/anie.202501141","DOIUrl":"https://doi.org/10.1002/anie.202501141","url":null,"abstract":"Arrangement of donor-acceptor (D-A) components in order at a molecular level provides a means to achieve efficient electron-hole separation for promoting the activity of photocatalysts. Herein, we report the coordination assembly of D-A molecules with desired staggered energy levels in two isostructural metal-organic frameworks (MOFs) 1 and 2, which exhibit high photocatalytic hydrogen evolution activity without using any cocatalysts and photosensitizers. The modulation of active metal sites of the D-A MOFs leads to an increase of photocatalytic hydrogen evolution rates from 1260 to 3218 μmol h−1 g−1. A detailed mechanism study revealed that the energy bond defined by the D-A components assisted with metal centers is the key to efficiently generate photogenerated charge carriers, and 2 has an appropriate affinity to proton to reduce the energy barrier for hydrogen evolution. Besides, the enhanced proton transport kinetics based on the arrayed free carboxyl groups in the hydrogen bonded network endows 2 higher proton conductivity than 1, thus promoting the usage rate of active metal sites in 2 for enhanced hydrogen evolution reaction kinetics.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"28 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143518491","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}
Xinhui Yu, Liwei Xue, Yiheng Liao, Li Xiao, Gongwei Wang, Lin Zhuang
CO2 electrolysis in alkaline media presents advantages by suppressing the competitive hydrogen evolution reaction and enhancing the CO2 reduction selectivity. However, it suffers from the carbonation issue, leading to substantial carbon loss due to CO2 transmembrane transport. To tackle this issue, we here put forward a redox mediator (RM)-coupled electrolysis strategy. By integrating a highly reversible redox couple, this approach spatially separates the cathodic CO2 reduction and the anodic oxygen evolution reactions into two electrolyzers, thereby enabling the recovery and reuse of transmembrane CO2. Anthraquinone-2,7-disulfonic acid (AQDS) was chosen as the redox mediator owing to its suitable redox potential, excellent electrochemical reversibility, high solubility, and non-transmembrane shuttling characteristics. It allowed the RM-coupled electrolysis system to operate continuously at 100 mA/cm2, maintaining a high faradaic efficiency for CO2-to-CO conversion consistently around 90%, while effectively capturing the transmembrane CO2. This proof-of-concept demonstration validates the feasibility of RM-coupled electrolysis and highlights its significant potential to advance the practical application of CO2 electrolysis.
{"title":"Redox-Mediated CO2 Electrolysis for Recovering Transmembrane Carbon Loss","authors":"Xinhui Yu, Liwei Xue, Yiheng Liao, Li Xiao, Gongwei Wang, Lin Zhuang","doi":"10.1002/anie.202502420","DOIUrl":"https://doi.org/10.1002/anie.202502420","url":null,"abstract":"CO2 electrolysis in alkaline media presents advantages by suppressing the competitive hydrogen evolution reaction and enhancing the CO2 reduction selectivity. However, it suffers from the carbonation issue, leading to substantial carbon loss due to CO2 transmembrane transport. To tackle this issue, we here put forward a redox mediator (RM)-coupled electrolysis strategy. By integrating a highly reversible redox couple, this approach spatially separates the cathodic CO2 reduction and the anodic oxygen evolution reactions into two electrolyzers, thereby enabling the recovery and reuse of transmembrane CO2. Anthraquinone-2,7-disulfonic acid (AQDS) was chosen as the redox mediator owing to its suitable redox potential, excellent electrochemical reversibility, high solubility, and non-transmembrane shuttling characteristics. It allowed the RM-coupled electrolysis system to operate continuously at 100 mA/cm2, maintaining a high faradaic efficiency for CO2-to-CO conversion consistently around 90%, while effectively capturing the transmembrane CO2. This proof-of-concept demonstration validates the feasibility of RM-coupled electrolysis and highlights its significant potential to advance the practical application of CO2 electrolysis.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"7 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143518455","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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