Saisai Yu, Siyuan Yang, Miao Yang, Ju Yang, Ziye Song, Dingyue Hu, Heng Ji, Zhe Jia, Ming Liu
Integrating two or more materials to construct membranes with heterogeneous pore structures is an effective strategy for enhancing separation performance. Regularly arranging these heterogeneous pores can significantly optimize the combined effect of the introduced components. Porous Organic Cages (POCs), an emerging subclass of porous materials composed of discrete molecules, assemble to form interconnected pores and exhibit permanent porosity in the solid state. A unique feature of POCs is their modularity, enabling a "mix and match" approach to create co-crystal structures driven by the intermolecular interactions. Herein, we adopted the cocrystallization strategy for fabricating gas separation membranes. We prepared membranes from a series of [4+6] imine cage pairs, which vary in cavity sizes and include cages with fluorescence properties. By optimizing the cocrystalization conditions, we successfully fabricated continuous, defect-free gas membranes, benefiting from chiral recognition interactions. By introducing regularly alternating small and large pores, we addressed challenges such as the trade-off between permeability and selectivity in gas separation membrane. Moreover, the cocrystallization strategy has been proven effective for other molecular systems besides POCs, such as macrocycles, for the preparation of co-crystal membranes. This method broadens the scope for fabricating high-performance gas separation membranes with ordered heterogeneous pores.
{"title":"Regularly Arranged Heterogeneous Pores in Gas Separation Membranes Constructed by Cocrystallization of Porous Organic Molecules","authors":"Saisai Yu, Siyuan Yang, Miao Yang, Ju Yang, Ziye Song, Dingyue Hu, Heng Ji, Zhe Jia, Ming Liu","doi":"10.1002/anie.202420086","DOIUrl":"https://doi.org/10.1002/anie.202420086","url":null,"abstract":"Integrating two or more materials to construct membranes with heterogeneous pore structures is an effective strategy for enhancing separation performance. Regularly arranging these heterogeneous pores can significantly optimize the combined effect of the introduced components. Porous Organic Cages (POCs), an emerging subclass of porous materials composed of discrete molecules, assemble to form interconnected pores and exhibit permanent porosity in the solid state. A unique feature of POCs is their modularity, enabling a \"mix and match\" approach to create co-crystal structures driven by the intermolecular interactions. Herein, we adopted the cocrystallization strategy for fabricating gas separation membranes. We prepared membranes from a series of [4+6] imine cage pairs, which vary in cavity sizes and include cages with fluorescence properties. By optimizing the cocrystalization conditions, we successfully fabricated continuous, defect-free gas membranes, benefiting from chiral recognition interactions. By introducing regularly alternating small and large pores, we addressed challenges such as the trade-off between permeability and selectivity in gas separation membrane. Moreover, the cocrystallization strategy has been proven effective for other molecular systems besides POCs, such as macrocycles, for the preparation of co-crystal membranes. This method broadens the scope for fabricating high-performance gas separation membranes with ordered heterogeneous pores.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"29 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968517","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}
Hyunlim Kim, Younggyu Seo, Jaewoo Park, Eunsung Lee, Hyunchul Oh
Efficient separation of hydrogen isotopes, especially deuterium (D2), is pivotal for advancing industries such as nuclear fusion, semiconductor processing, and metabolic imaging. Current technologies, including cryogenic distillation and Girdler sulfide processes, suffer from significant limitations in selectivity and cost-effectiveness. Herein, we introduce a novel approach utilizing an imidazolium-based Metal-Organic Framework (MOF), JCM-1, designed to enhance D2/H2 separation through temperature-dependent gate-opening controlled by ion exchange. By substituting NO3⁻ ions in JCM-1(NO3⁻) with Cl⁻ ions to form JCM-1(Cl⁻), we precisely modulate the gate-opening threshold, achieving a significant enhancement in isotope selectivity. JCM-1(NO3⁻) exhibited a D2/H2 selectivity (SD2/H2) of 14.4 at 30 K and 1 bar, while JCM-1(Cl⁻) achieved an exceptional selectivity of 27.7 at 50 K and 1 mbar. This heightened performance is attributed to the reduced pore aperture and higher gate-opening temperature resulting from the Cl⁻ exchange, which optimizes the selective adsorption of D2. Our findings reveal that JCM-1 frameworks, with their tunable gate-opening properties, offer a highly efficient and adaptable platform for hydrogen isotope separation. This work not only advances the understanding of ion-exchanged MOFs but also opens new pathways for targeted applications in isotope separation and other gas separation processes.
{"title":"A Gate-Opening Control Strategy via Nitrate–Chloride Anion Exchange for Enhanced Hydrogen Isotope Separation in Metal-Organic Frameworks","authors":"Hyunlim Kim, Younggyu Seo, Jaewoo Park, Eunsung Lee, Hyunchul Oh","doi":"10.1002/anie.202421756","DOIUrl":"https://doi.org/10.1002/anie.202421756","url":null,"abstract":"Efficient separation of hydrogen isotopes, especially deuterium (D2), is pivotal for advancing industries such as nuclear fusion, semiconductor processing, and metabolic imaging. Current technologies, including cryogenic distillation and Girdler sulfide processes, suffer from significant limitations in selectivity and cost-effectiveness. Herein, we introduce a novel approach utilizing an imidazolium-based Metal-Organic Framework (MOF), JCM-1, designed to enhance D2/H2 separation through temperature-dependent gate-opening controlled by ion exchange. By substituting NO3⁻ ions in JCM-1(NO3⁻) with Cl⁻ ions to form JCM-1(Cl⁻), we precisely modulate the gate-opening threshold, achieving a significant enhancement in isotope selectivity. JCM-1(NO3⁻) exhibited a D2/H2 selectivity (SD2/H2) of 14.4 at 30 K and 1 bar, while JCM-1(Cl⁻) achieved an exceptional selectivity of 27.7 at 50 K and 1 mbar. This heightened performance is attributed to the reduced pore aperture and higher gate-opening temperature resulting from the Cl⁻ exchange, which optimizes the selective adsorption of D2. Our findings reveal that JCM-1 frameworks, with their tunable gate-opening properties, offer a highly efficient and adaptable platform for hydrogen isotope separation. This work not only advances the understanding of ion-exchanged MOFs but also opens new pathways for targeted applications in isotope separation and other gas separation processes.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"6 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968522","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}
Bo Zhang, Chang-Tai Li, Han-Yu Wang, Han Fang, Rui Feng, Mei-Hui Yu, Wei Li, Ze Chang, Xian-He Bu
The application of temperature‐compensated photonic device is hampered by poor accuracy and overly simplistic functions of propagation in photonic integrated circuits (PICs) field. Herein, we report a new library of donor‐acceptor metal‐organic framework (D‐A MOF) with thermally activated delayed fluorescence (TADF) and the fabricating of temperature‐compensated photonic device by virtue of the unique temperature response character of TADF emitters. Highly tunable through‐space charge transfer (TSCT) of TADF was realized within the D‐A MOFs through a novel strategy that synergistically combines the internal heavy atom effect (HAE) with an external HAE, induced by the incorporation of heavy atoms into different components, achieving the regulable photophysical indicators including adjustable PL wavelength (534 to 592 nm) and surging quantum yield (5.02%‐47.39%). Further investigation of the impact of external HAE on TADF was conducted through crystal structures and Hirshfeld surface plots of four D‐A regimes featuring substituent‐based linkers. Notably, temperature‐compensated photonic device based on heterocrystal was fabricated through integrating D‐A MOFs with contrary temperature response. The emission signal output of the heterojunction remained nearly stable in 215 K to 295 K range, highlighting the promising potential application of TADF D‐A MOF featuring sensitive temperature response in PICs field.
{"title":"Regulation of TADF by Internal and External Heavy Atom Effect in D‐A MOF for Heterocrystal based Temperature‐Compensated Photonic Device","authors":"Bo Zhang, Chang-Tai Li, Han-Yu Wang, Han Fang, Rui Feng, Mei-Hui Yu, Wei Li, Ze Chang, Xian-He Bu","doi":"10.1002/anie.202424593","DOIUrl":"https://doi.org/10.1002/anie.202424593","url":null,"abstract":"The application of temperature‐compensated photonic device is hampered by poor accuracy and overly simplistic functions of propagation in photonic integrated circuits (PICs) field. Herein, we report a new library of donor‐acceptor metal‐organic framework (D‐A MOF) with thermally activated delayed fluorescence (TADF) and the fabricating of temperature‐compensated photonic device by virtue of the unique temperature response character of TADF emitters. Highly tunable through‐space charge transfer (TSCT) of TADF was realized within the D‐A MOFs through a novel strategy that synergistically combines the internal heavy atom effect (HAE) with an external HAE, induced by the incorporation of heavy atoms into different components, achieving the regulable photophysical indicators including adjustable PL wavelength (534 to 592 nm) and surging quantum yield (5.02%‐47.39%). Further investigation of the impact of external HAE on TADF was conducted through crystal structures and Hirshfeld surface plots of four D‐A regimes featuring substituent‐based linkers. Notably, temperature‐compensated photonic device based on heterocrystal was fabricated through integrating D‐A MOFs with contrary temperature response. The emission signal output of the heterojunction remained nearly stable in 215 K to 295 K range, highlighting the promising potential application of TADF D‐A MOF featuring sensitive temperature response in PICs field.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"2 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142961574","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}
Wenxiang Zhu, Mengjie Ma, Dongdong Gao, Jinxin Chen, Hui Huang, Kun Feng, Qun Wang, Jie Wu, Penghao Li, Jinzeng Guo, Zhenglong Fan, Jun Zhong, Qi Shao, Fan Liao, Yang Liu, Mingwang Shao, Zhenhui Kang
Developing durable IrO2‐based electrocatalysts with high oxygen evolution reaction (OER) activity under acidic condition is crucial for proton exchange membrane electrolyzers. While oxygen defects are considered potentially important in OER, their direct relationship with catalytic activity has yet to be established. In this study, we introduced abundant oxygen vacancies through Re doping in 2D IrO2 (Re0.03Ir0.97O2), demonstrating their decisive role in enhancing OER performance. The Re0.03Ir0.97O2 catalyst exhibited excellent OER performance with an overpotential of 193 mV at 10 mA cm‐2 and sustained activity for over 650 hours, significantly surpassing the undoped catalyst. Moreover, it maintained operation at a cell voltage of 1.70 V (~1200 mA cm‐2) for over 140 hours without significant performance degradation. Theoretical calculations coupled with cyclic voltammetry, transient potential scanning and in‐situ characterizations confirmed the adsorbate evolving mechanism on Re0.03Ir0.97O2, as well as the critical role of Re‐induced oxygen vacancies in enhancing OER performance. These findings highlight that oxygen defects directly influence OER activity, providing guidance for the application of oxygen vacancy engineering in electrocatalyst design.
{"title":"Establishing the Link Between Oxygen Vacancy and Activity Enhancement in Acidic Water Oxidation of Trigonal Iridium Oxide","authors":"Wenxiang Zhu, Mengjie Ma, Dongdong Gao, Jinxin Chen, Hui Huang, Kun Feng, Qun Wang, Jie Wu, Penghao Li, Jinzeng Guo, Zhenglong Fan, Jun Zhong, Qi Shao, Fan Liao, Yang Liu, Mingwang Shao, Zhenhui Kang","doi":"10.1002/anie.202423353","DOIUrl":"https://doi.org/10.1002/anie.202423353","url":null,"abstract":"Developing durable IrO2‐based electrocatalysts with high oxygen evolution reaction (OER) activity under acidic condition is crucial for proton exchange membrane electrolyzers. While oxygen defects are considered potentially important in OER, their direct relationship with catalytic activity has yet to be established. In this study, we introduced abundant oxygen vacancies through Re doping in 2D IrO2 (Re0.03Ir0.97O2), demonstrating their decisive role in enhancing OER performance. The Re0.03Ir0.97O2 catalyst exhibited excellent OER performance with an overpotential of 193 mV at 10 mA cm‐2 and sustained activity for over 650 hours, significantly surpassing the undoped catalyst. Moreover, it maintained operation at a cell voltage of 1.70 V (~1200 mA cm‐2) for over 140 hours without significant performance degradation. Theoretical calculations coupled with cyclic voltammetry, transient potential scanning and in‐situ characterizations confirmed the adsorbate evolving mechanism on Re0.03Ir0.97O2, as well as the critical role of Re‐induced oxygen vacancies in enhancing OER performance. These findings highlight that oxygen defects directly influence OER activity, providing guidance for the application of oxygen vacancy engineering in electrocatalyst design.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"36 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142961602","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}
Ruthenium dioxide (RuO2) is a benchmark electrocatalyst for proton exchange membrane water electrolyzers (PEMWE), but its stability during the oxygen evolution reaction (OER) is often compromised by lattice oxygen involvement and metal dissolution. Despite that the typical synthesis of RuO2 produces chloride residues, the underlying function of chloride have not well investigated. In this study, we synthesized chlorine‐containing RuO2 (RuO2‐Cl) and pure RuO2 catalysts with similar morphology and crystallinity. RuO2‐Cl demonstrated superior stability, three times greater than that of pure RuO2, and a lower overpotential of 176 mV at 10 mA cm‐2. Furthermore, the RuO2‐Cl catalysts that were in situ synthesized on a platinum‐coated titanium felt could maintain high performance for up to 1200 hours at 100 mA cm‐2. Computational and experimental analyses show that chloride stabilizes RuO2 by substituting the bridging oxygen atoms, which subsequently inhibits lattice oxygen evolution and Ru demetallation. Notably, this substitution also lowers the energy barrier of the rate‐determining step by strengthening the binding of *OOH intermediates. These findings offer new insights into the previously unknown role of chloride residues and how to improve RuO2 stability.
{"title":"Chloride Residues in RuO2 Catalysts Enhance Its Stability and Efficiency for Acidic Oxygen Evolution Reaction","authors":"Huile Jin, Jiadong Chen, Menghui Qi, Yun Yang, Xiaofen Xiao, Ying Li, Yong Wang","doi":"10.1002/anie.202420860","DOIUrl":"https://doi.org/10.1002/anie.202420860","url":null,"abstract":"Ruthenium dioxide (RuO2) is a benchmark electrocatalyst for proton exchange membrane water electrolyzers (PEMWE), but its stability during the oxygen evolution reaction (OER) is often compromised by lattice oxygen involvement and metal dissolution. Despite that the typical synthesis of RuO2 produces chloride residues, the underlying function of chloride have not well investigated. In this study, we synthesized chlorine‐containing RuO2 (RuO2‐Cl) and pure RuO2 catalysts with similar morphology and crystallinity. RuO2‐Cl demonstrated superior stability, three times greater than that of pure RuO2, and a lower overpotential of 176 mV at 10 mA cm‐2. Furthermore, the RuO2‐Cl catalysts that were in situ synthesized on a platinum‐coated titanium felt could maintain high performance for up to 1200 hours at 100 mA cm‐2. Computational and experimental analyses show that chloride stabilizes RuO2 by substituting the bridging oxygen atoms, which subsequently inhibits lattice oxygen evolution and Ru demetallation. Notably, this substitution also lowers the energy barrier of the rate‐determining step by strengthening the binding of *OOH intermediates. These findings offer new insights into the previously unknown role of chloride residues and how to improve RuO2 stability.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"62 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142961570","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}
Tingting Xu, Huaqun Zhou, Xiaofei Zhang, Tun Seng Herng, Jun Ding, Chunyan Chi, Jun Zhu
Radical covalent organic frameworks (RCOFs) have demonstrated significant potential in redox catalysis and energy conversion applications. However, the synthesis of stable RCOFs with well-defined neutral carbon radical centers is challenging due to the inherent radical instability, limited synthetic methods and characterization difficulties. Building upon the understanding of stable carbon radicals and structural modulations for preparing crystalline COFs, herein we report the synthesis of a crystalline carbon-centered RCOF through a facile post-oxidation process. Moreover, the RCOF demonstrated outstanding catalytic activity in the 4e- oxygen reduction reaction (ORR) with a half-wave potential of 0.82 V (vs. RHE) and electron transfer number of 3.98, among the highest in reported COF-based electrocatalysts. The promoted 4e- and suppressed 2e- ORR pathway (99.5% vs. 0.5%) can be attributed to facilitated reaction initiation and smoother transition steps at the carbon radical sites, which is practically beneficial for minimizing peroxide formation, thus contributing to safer and more sustainable fuel cell and metal-air battery applications. Overall, our study not only provided a facile strategy for preparing stable RCOFs with well-defined neutral carbon radical centers but also demonstrated their capability to fine-tune the redox catalytic activity of COF materials, which could be potentially useful in electrocatalysis and energy conversion applications.
{"title":"Covalent Organic Frameworks with Carbon-centered Radical Sites for Promoting the 4e- Oxygen Reduction Reaction","authors":"Tingting Xu, Huaqun Zhou, Xiaofei Zhang, Tun Seng Herng, Jun Ding, Chunyan Chi, Jun Zhu","doi":"10.1002/anie.202424449","DOIUrl":"https://doi.org/10.1002/anie.202424449","url":null,"abstract":"Radical covalent organic frameworks (RCOFs) have demonstrated significant potential in redox catalysis and energy conversion applications. However, the synthesis of stable RCOFs with well-defined neutral carbon radical centers is challenging due to the inherent radical instability, limited synthetic methods and characterization difficulties. Building upon the understanding of stable carbon radicals and structural modulations for preparing crystalline COFs, herein we report the synthesis of a crystalline carbon-centered RCOF through a facile post-oxidation process. Moreover, the RCOF demonstrated outstanding catalytic activity in the 4e- oxygen reduction reaction (ORR) with a half-wave potential of 0.82 V (vs. RHE) and electron transfer number of 3.98, among the highest in reported COF-based electrocatalysts. The promoted 4e- and suppressed 2e- ORR pathway (99.5% vs. 0.5%) can be attributed to facilitated reaction initiation and smoother transition steps at the carbon radical sites, which is practically beneficial for minimizing peroxide formation, thus contributing to safer and more sustainable fuel cell and metal-air battery applications. Overall, our study not only provided a facile strategy for preparing stable RCOFs with well-defined neutral carbon radical centers but also demonstrated their capability to fine-tune the redox catalytic activity of COF materials, which could be potentially useful in electrocatalysis and energy conversion applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"86 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142961885","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}
Yuhan Gui, Rui Hou, Yuchen Huang, Yu Zhou, Shihao Liu, Ling Meng, Ying Li, Fong Sang Lam, Ruoyun Ding, Yan Cao, Gang Li, Xiaojie Lu, Xiaoyu Li
Small molecules that can bind to specific cells have broad applications in cancer diagnosis and treatment. Screening large chemical libraries against live cells is an effective strategy for discovering cell‐targeting ligands. The DNA‐encoded chemical library (DEL or DECL) technology has emerged as a robust tool in drug discovery and has been successfully utilized in identifying ligands for biological targets. However, nearly all DEL selections have predefined targets, while target‐agnostic DEL selections interrogating the entire cell surface remain underexplored. Herein, we systematically optimized a cell‐based DEL selection method against cancer cells without predefined targets. A 104.96‐million‐member DEL was selected against MDA‐MB‐231 and MCF‐7 breast cancer cells, representing high and low metastatic properties, respectively, which led to the identification of cell‐specific small molecules. We further demonstrated cell‐targeting applications of these ligands in cancer photodynamic therapy and targeted drug delivery. Finally, leveraging the DNA tag of DEL compounds, we identified α‐enolase (ENO1) as the cell surface receptor of one of the ligands targeting the more aggressive MDA‐MB‐231 cells. Overall, this work offers an efficient approach for discovering cell‐targeting small molecule ligands by using DELs and demonstrates that DELs can be a useful tool to identify specific surface receptors on cancer cells.
{"title":"Discovering Cell‐Targeting Ligands and Cell‐Surface Receptors by Selection of DNA‐Encoded Chemical Libraries against Cancer Cells without Predefined Targets","authors":"Yuhan Gui, Rui Hou, Yuchen Huang, Yu Zhou, Shihao Liu, Ling Meng, Ying Li, Fong Sang Lam, Ruoyun Ding, Yan Cao, Gang Li, Xiaojie Lu, Xiaoyu Li","doi":"10.1002/anie.202421172","DOIUrl":"https://doi.org/10.1002/anie.202421172","url":null,"abstract":"Small molecules that can bind to specific cells have broad applications in cancer diagnosis and treatment. Screening large chemical libraries against live cells is an effective strategy for discovering cell‐targeting ligands. The DNA‐encoded chemical library (DEL or DECL) technology has emerged as a robust tool in drug discovery and has been successfully utilized in identifying ligands for biological targets. However, nearly all DEL selections have predefined targets, while target‐agnostic DEL selections interrogating the entire cell surface remain underexplored. Herein, we systematically optimized a cell‐based DEL selection method against cancer cells without predefined targets. A 104.96‐million‐member DEL was selected against MDA‐MB‐231 and MCF‐7 breast cancer cells, representing high and low metastatic properties, respectively, which led to the identification of cell‐specific small molecules. We further demonstrated cell‐targeting applications of these ligands in cancer photodynamic therapy and targeted drug delivery. Finally, leveraging the DNA tag of DEL compounds, we identified α‐enolase (ENO1) as the cell surface receptor of one of the ligands targeting the more aggressive MDA‐MB‐231 cells. Overall, this work offers an efficient approach for discovering cell‐targeting small molecule ligands by using DELs and demonstrates that DELs can be a useful tool to identify specific surface receptors on cancer cells.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"45 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142961568","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}
Ghewa AlSabeh, Vladislav Slama, Ming Ren, Masaud Almalki, Lukas Pfeifer, Dominik J. Kubicki, Paul Zimmermann, Alexander Hinderhofer, Fabiola Faini, Davide Moia, Mostafa Othman, Felix T. Eickemeyer, Virginia Carnevali, Nikolaos Lempesis, Andrea Vezzosi, Fatemeh Ansari, Frank Schreiber, Joachim Maier, Christian M. Wolff, Aïcha Hessler-Wyser, Christophe Ballif, Giulia Grancini, Ursula Rothlisberger, Michael Grätzel, Jovana V. Milic
Metal halide perovskites have shown exceptional potential in converting solar energy to electric power in photovoltaics, yet their application is hampered by limited operational stability. This stimulated the development of hybrid layered (two‐dimensional, 2D) halide perovskites based on hydrophobic organic spacers, templating perovskite slabs, as a more stable alternative. However, conventional organic spacer cations are electronically insulating, resulting in charge confinement within the inorganic slabs, thus limiting their functionality. This can be ameliorated by extending the π‐conjugation of the spacer cations. We demonstrate the capacity to access Ruddlesden‐Popper and Dion‐Jacobson 2D perovskites incorporating for the first time aryl‐acetylene‐based (4‐ethynylphenyl)methylammonium (BMAA) and buta‐1,3‐diyne‐1,4‐diylbis(4,1‐phenylene)dimethylammonium (BDAA) spacers, respectively. We assess their unique opto(electro)ionic characteristics by a combination of techniques and apply them in mixed‐dimensional perovskite solar cells that show superior device performances with a power conversion efficiency of up to 23% and higher operational stability, opening the way for multifunctionality in layered hybrid materials and their application.
{"title":"Aryl‐Acetylene Layered Hybrid Perovskites in Photovoltaics","authors":"Ghewa AlSabeh, Vladislav Slama, Ming Ren, Masaud Almalki, Lukas Pfeifer, Dominik J. Kubicki, Paul Zimmermann, Alexander Hinderhofer, Fabiola Faini, Davide Moia, Mostafa Othman, Felix T. Eickemeyer, Virginia Carnevali, Nikolaos Lempesis, Andrea Vezzosi, Fatemeh Ansari, Frank Schreiber, Joachim Maier, Christian M. Wolff, Aïcha Hessler-Wyser, Christophe Ballif, Giulia Grancini, Ursula Rothlisberger, Michael Grätzel, Jovana V. Milic","doi":"10.1002/anie.202417432","DOIUrl":"https://doi.org/10.1002/anie.202417432","url":null,"abstract":"Metal halide perovskites have shown exceptional potential in converting solar energy to electric power in photovoltaics, yet their application is hampered by limited operational stability. This stimulated the development of hybrid layered (two‐dimensional, 2D) halide perovskites based on hydrophobic organic spacers, templating perovskite slabs, as a more stable alternative. However, conventional organic spacer cations are electronically insulating, resulting in charge confinement within the inorganic slabs, thus limiting their functionality. This can be ameliorated by extending the π‐conjugation of the spacer cations. We demonstrate the capacity to access Ruddlesden‐Popper and Dion‐Jacobson 2D perovskites incorporating for the first time aryl‐acetylene‐based (4‐ethynylphenyl)methylammonium (BMAA) and buta‐1,3‐diyne‐1,4‐diylbis(4,1‐phenylene)dimethylammonium (BDAA) spacers, respectively. We assess their unique opto(electro)ionic characteristics by a combination of techniques and apply them in mixed‐dimensional perovskite solar cells that show superior device performances with a power conversion efficiency of up to 23% and higher operational stability, opening the way for multifunctionality in layered hybrid materials and their application.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"36 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142961634","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}
Qiang Yan, Cuiqin Yang, Yulian Zhang, Miaomiao Xu, Jianfeng Li
Hydrogen sulfide (H2S), as a gasotransmitter, not only plays a vital role in mediating many cellular activities but also manifests exciting applications in clinical therapy. However, one main obstacle in using H2S as a gaseous therapeutic agent is to realize on‐demand storage and delivery of gas, and thus, it is of great importance to develop H2S‐donating vehicle platforms. Although a variety of polymer‐based gas‐releasing carriers have been designed, almost all the systems are limited to spherical structures. Here we explore the role of polymer self‐assembled morphologies, especially toward those non‐spherical nanostructures, on the H2S release capacity. A kind of tubular polymersomes (i.e. tubesomes), formed by the membrane stretching of polythionoester‐containing block copolymer vesicles, exhibit enhanced cysteine‐responsive H2S‐releasing behavior in contrast to their spherical counterparts. Moreover, we found that the amount and rate of H2S release from diverse polymersomes is relied on the extent of membrane elongation, which allows us to regulate the gas releasing kinetics through tailoring the membrane geometries. More importantly, it is demonstrated that the tubesomes as polymer‐type H2S donors have better anticancer performance than those spherical polymersomes. This would inspire new possibilities to boost gas therapeutic efficacy through shaping the morphology of gas nanovehicles.
{"title":"Gas‐Releasing Polymer Tubesomes: Boosting Gas Delivery of Nanovehicles via Membrane Stretching","authors":"Qiang Yan, Cuiqin Yang, Yulian Zhang, Miaomiao Xu, Jianfeng Li","doi":"10.1002/anie.202421405","DOIUrl":"https://doi.org/10.1002/anie.202421405","url":null,"abstract":"Hydrogen sulfide (H2S), as a gasotransmitter, not only plays a vital role in mediating many cellular activities but also manifests exciting applications in clinical therapy. However, one main obstacle in using H2S as a gaseous therapeutic agent is to realize on‐demand storage and delivery of gas, and thus, it is of great importance to develop H2S‐donating vehicle platforms. Although a variety of polymer‐based gas‐releasing carriers have been designed, almost all the systems are limited to spherical structures. Here we explore the role of polymer self‐assembled morphologies, especially toward those non‐spherical nanostructures, on the H2S release capacity. A kind of tubular polymersomes (i.e. tubesomes), formed by the membrane stretching of polythionoester‐containing block copolymer vesicles, exhibit enhanced cysteine‐responsive H2S‐releasing behavior in contrast to their spherical counterparts. Moreover, we found that the amount and rate of H2S release from diverse polymersomes is relied on the extent of membrane elongation, which allows us to regulate the gas releasing kinetics through tailoring the membrane geometries. More importantly, it is demonstrated that the tubesomes as polymer‐type H2S donors have better anticancer performance than those spherical polymersomes. This would inspire new possibilities to boost gas therapeutic efficacy through shaping the morphology of gas nanovehicles.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"16 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142961573","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}
A synergistic photoredox/cobalt/chromium triple catalysis system for regioselective, enantioselective, and diastereoselective 1,4‐hydrocarbonation of readily available 1,3‐enyne precursors was explored, providing a modular synthetic platform for various trisubstituted axially chiral allenes bearing an extra central chirality. The protocol features a broad substrate scope, good functional group tolerance, excellent selectivity, and mild reaction conditions. Furthermore, a possible reaction mechanism is proposed based on numerous control experiments and density functional theory calculations.
{"title":"Catalytic Asymmetric 1,4‐Hydrocarbonation of 1,3‐Enynes via Photoredox/Cobalt/Chromium Triple Catalysis","authors":"Ju-Song Yang, Xing-Yu Wang, Yong-Yao Li, Fu-Min Zhang, Xiao-Ming Zhang, Yongqiang Tu","doi":"10.1002/anie.202420563","DOIUrl":"https://doi.org/10.1002/anie.202420563","url":null,"abstract":"A synergistic photoredox/cobalt/chromium triple catalysis system for regioselective, enantioselective, and diastereoselective 1,4‐hydrocarbonation of readily available 1,3‐enyne precursors was explored, providing a modular synthetic platform for various trisubstituted axially chiral allenes bearing an extra central chirality. The protocol features a broad substrate scope, good functional group tolerance, excellent selectivity, and mild reaction conditions. Furthermore, a possible reaction mechanism is proposed based on numerous control experiments and density functional theory calculations.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"40 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142961569","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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