The catalytic hydrosilylation of alkynes with hydrosilanes is the most straightforward and atom-efficient method for the synthesis of silylalkenes. However, the hydrosilylation of unsymmetrical internal alkynes often encounters regio- and stereoselectivity challenges. Herein, we report the regio- and syn-stereoselective hydrosilylation of unsymmetrical internal alkynes bearing heteroatom functional groups with hydrosilanes by half-sandwich scandium catalyst. This protocol offers an atom-efficient route for the synthesis of a new family of heteroatom (O, S or N)-functionalized multisubstituted silylalkenes from a variety of internal homopropargyl thioethers, ethers and tertiary amines and hydrosilanes, featuring 100% atom-efficiency, broad substrate scope, and excellent regio- and syn-stereoselectivity (>19:1 r.r. and >19:1 syn/anti). The mechanistic details have been elucidated by control experiments and isolation and examination of some key reaction intermediates. It was revealed that an interaction between the heteroatom (O, S or N) in the internal alkynes and the Sc center was critical for achieving the unprecedented high selectivity.
{"title":"Heteroatom-Assisted Regio- and Stereoselective Hydrosilylation of Unsymmetric Internal Alkynes by Scandium Catalyst","authors":"Yuanhong Ma, Aniket Mishra, Tenggang Jiao, Wendi Chang, Shao-Jie Lou, Masayoshi Nishiura, Xuefeng Cong, Zhaomin Hou","doi":"10.1002/anie.202502665","DOIUrl":"https://doi.org/10.1002/anie.202502665","url":null,"abstract":"The catalytic hydrosilylation of alkynes with hydrosilanes is the most straightforward and atom-efficient method for the synthesis of silylalkenes. However, the hydrosilylation of unsymmetrical internal alkynes often encounters regio- and stereoselectivity challenges. Herein, we report the regio- and syn-stereoselective hydrosilylation of unsymmetrical internal alkynes bearing heteroatom functional groups with hydrosilanes by half-sandwich scandium catalyst. This protocol offers an atom-efficient route for the synthesis of a new family of heteroatom (O, S or N)-functionalized multisubstituted silylalkenes from a variety of internal homopropargyl thioethers, ethers and tertiary amines and hydrosilanes, featuring 100% atom-efficiency, broad substrate scope, and excellent regio- and syn-stereoselectivity (>19:1 r.r. and >19:1 syn/anti). The mechanistic details have been elucidated by control experiments and isolation and examination of some key reaction intermediates. It was revealed that an interaction between the heteroatom (O, S or N) in the internal alkynes and the Sc center was critical for achieving the unprecedented high selectivity.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"13 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435689","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}
Sten V. Lambeets, Naseeha Cardwell, Isaac Onyango, Mark G. Wirth, Eric Vo, Yong Wang, Pierre Gaspard, Cornelius F. Ivory, Daniel E Perea, Thierry Visart de Bocarmé, Jean-Sabin McEwen
We quantify the effects of intensely applied electric fields on the Fe oxidation mechanism. The specimen are pristine Fe single crystals exposing a variety of surface structures identified by field ion microscopy. These crystals are simultaneously exposed to low pressures of pure oxygen gas, on the order of 10‐7 mbar, while applying intense electric fields on their surface of several tens of volts per nanometer. The local composition of the different surface structures is probed directly and in real time using an Environmental Atom Probe and successfully compared with first principles‐based models. We found that rough Fe{244} and Fe{112} facets are more reactive toward oxygen than compact Fe{024} and Fe{011} facets. Results demonstrate that the influence of an electric field on the oxidation kinetics depends on the timescales that are involved as the system evolves toward equilibrium. The initial oxidation kinetics show that strong increases in electric fields facilitate the formation of an oxide. However, as one approaches equilibrium, high field values mitigate this formation. Ultimately, this study elucidates how high externally applied electric fields can be utilized to dynamically exploit reaction dynamics at the nanoscale towards desired products in a catalytic reaction at mild reaction conditions.
{"title":"Elucidating the Role of Electric Fields in Fe Oxidation via an Environmental Atom Probe","authors":"Sten V. Lambeets, Naseeha Cardwell, Isaac Onyango, Mark G. Wirth, Eric Vo, Yong Wang, Pierre Gaspard, Cornelius F. Ivory, Daniel E Perea, Thierry Visart de Bocarmé, Jean-Sabin McEwen","doi":"10.1002/anie.202423434","DOIUrl":"https://doi.org/10.1002/anie.202423434","url":null,"abstract":"We quantify the effects of intensely applied electric fields on the Fe oxidation mechanism. The specimen are pristine Fe single crystals exposing a variety of surface structures identified by field ion microscopy. These crystals are simultaneously exposed to low pressures of pure oxygen gas, on the order of 10‐7 mbar, while applying intense electric fields on their surface of several tens of volts per nanometer. The local composition of the different surface structures is probed directly and in real time using an Environmental Atom Probe and successfully compared with first principles‐based models. We found that rough Fe{244} and Fe{112} facets are more reactive toward oxygen than compact Fe{024} and Fe{011} facets. Results demonstrate that the influence of an electric field on the oxidation kinetics depends on the timescales that are involved as the system evolves toward equilibrium. The initial oxidation kinetics show that strong increases in electric fields facilitate the formation of an oxide. However, as one approaches equilibrium, high field values mitigate this formation. Ultimately, this study elucidates how high externally applied electric fields can be utilized to dynamically exploit reaction dynamics at the nanoscale towards desired products in a catalytic reaction at mild reaction conditions.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"80 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427096","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}
Specific recognition with optical responses towards the analytes which are structurally diverse and weak chemical‐active remains a big challenge but is of great significance. Here, a zinc(II) enhanced fluorescent emission probe was developed by conjugated modulating and metal bridging to specifically recognition synthetic cannabinoids (SCs). The transformed luminescence mechanism from excimer emission to fluorescence resonance energy transfer was demonstrated upon the integration of coordination and non‐covalent interactions towards target SCs. As a result, the specific and instant detection of the certain type SCs (MDMB‐CA series) was achieved in complicated sample medium. Hence, we envisage that this work would not only offer a novel recognition strategy for SCs, but also advance the development of the optical sensing probe especially for analyzing the substances with diverse structures and weak chemical‐activity, as well as for fighting against the illicit drugs.
{"title":"Zinc(II)‐Enhanced Excimer Probe for Recognition of MDMB‐CA Synthetic Cannabinoids","authors":"Yihang Wang, Jiahao Dong, Yuan Liu, Longlong Liang, Yuwan Du, Xincun Dou","doi":"10.1002/anie.202423576","DOIUrl":"https://doi.org/10.1002/anie.202423576","url":null,"abstract":"Specific recognition with optical responses towards the analytes which are structurally diverse and weak chemical‐active remains a big challenge but is of great significance. Here, a zinc(II) enhanced fluorescent emission probe was developed by conjugated modulating and metal bridging to specifically recognition synthetic cannabinoids (SCs). The transformed luminescence mechanism from excimer emission to fluorescence resonance energy transfer was demonstrated upon the integration of coordination and non‐covalent interactions towards target SCs. As a result, the specific and instant detection of the certain type SCs (MDMB‐CA series) was achieved in complicated sample medium. Hence, we envisage that this work would not only offer a novel recognition strategy for SCs, but also advance the development of the optical sensing probe especially for analyzing the substances with diverse structures and weak chemical‐activity, as well as for fighting against the illicit drugs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"11 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427081","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}
Katherine M. Marczenko, Hélène P. A. Mercier, James T. Goettel, Gary J. Schrobilgen
Following our report of the first coordination complex between a noble-gas compound and a crown ether, (CH2CH2O)5XeO3, the reactions and structures of XeO3 complexes with 12-crown-4 and 18-crown-6 were investigated. The reactions of 12-crown-4 and 18-crown-6 with XeO3 in dilute aqueous HF solutions yielded (CH2CH2O)4XeO3 and [(CH2CH2O)6(H2O)XeO3]2∙2H2O∙HF, whereas reactions of 12-crown-4 and 18-crown-6 in acetone solutions with moist solid XeO3 yielded (CH2CH2O)4XeO3 and [(CH2CH2O)6(H2O)XeO3]∙H2O. The (CH2CH2O)4XeO3 and [(CH2CH2O)6(H2O)XeO3]∙H2O complexes are air-stable and shock-insensitive, whereas [(CH2CH2O)6(H2O)XeO3]2∙2H2O∙HF is a treacherous, shock-sensitive detonator. Low-temperature X-ray crystal structures show that XeO3 is coordinated to the crown ether and H2O through short Xe---O contacts. Mappings of the XeO3 Hirshfeld surfaces onto 12-crown-4 and 18-crown-6 in (CH2CH2O)4XeO3 and [(CH2CH2O)6(H2O)XeO3]∙H2O reveal regions of negative electrostatic potential (EP) on the oxygen atoms of the crown ethers and regions of high positive EP on the Xe(VI) atom of XeO3 that are consistent with σ-hole bonds. The calculated gas-phase geometries, Wiberg bond valences and indices, and empirical bond valences corroborate the descriptions of the shortest Xe---Ocrown/H2O contacts as σ-hole bonds. The 12-crown-4, 15-crown-5, and 18-crown-6 complexes of XeO3 are also compared with the X-ray crystal structures and calculated gas-phase structures of their SbF3 and SbCl3 analogues.
{"title":"Xenon Trioxide Coordination Complexes of Crown Ethers: (CH2CH2O)4XeO3, and Xe(VI) Hydrates [(CH2CH2O)6(H2O)XeO3]∙H2O and [(CH2CH2O)6(H2O)XeO3]2∙2H2O∙HF","authors":"Katherine M. Marczenko, Hélène P. A. Mercier, James T. Goettel, Gary J. Schrobilgen","doi":"10.1002/anie.202425216","DOIUrl":"https://doi.org/10.1002/anie.202425216","url":null,"abstract":"Following our report of the first coordination complex between a noble-gas compound and a crown ether, (CH2CH2O)5XeO3, the reactions and structures of XeO3 complexes with 12-crown-4 and 18-crown-6 were investigated. The reactions of 12-crown-4 and 18-crown-6 with XeO3 in dilute aqueous HF solutions yielded (CH2CH2O)4XeO3 and [(CH2CH2O)6(H2O)XeO3]2∙2H2O∙HF, whereas reactions of 12-crown-4 and 18-crown-6 in acetone solutions with moist solid XeO3 yielded (CH2CH2O)4XeO3 and [(CH2CH2O)6(H2O)XeO3]∙H2O. The (CH2CH2O)4XeO3 and [(CH2CH2O)6(H2O)XeO3]∙H2O complexes are air-stable and shock-insensitive, whereas [(CH2CH2O)6(H2O)XeO3]2∙2H2O∙HF is a treacherous, shock-sensitive detonator. Low-temperature X-ray crystal structures show that XeO3 is coordinated to the crown ether and H2O through short Xe---O contacts. Mappings of the XeO3 Hirshfeld surfaces onto 12-crown-4 and 18-crown-6 in (CH2CH2O)4XeO3 and [(CH2CH2O)6(H2O)XeO3]∙H2O reveal regions of negative electrostatic potential (EP) on the oxygen atoms of the crown ethers and regions of high positive EP on the Xe(VI) atom of XeO3 that are consistent with σ-hole bonds. The calculated gas-phase geometries, Wiberg bond valences and indices, and empirical bond valences corroborate the descriptions of the shortest Xe---Ocrown/H2O contacts as σ-hole bonds. The 12-crown-4, 15-crown-5, and 18-crown-6 complexes of XeO3 are also compared with the X-ray crystal structures and calculated gas-phase structures of their SbF3 and SbCl3 analogues.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"137 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427319","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}
Synthesis of urea through electrocatalytic coupling reaction of CO2 with nitrite (NO2‐) represents a sustainable means to substitute the conventional energy‐intensive urea synthetic protocol. The direct conversion of dilute NO2‐ in real wastewaters to urea with high efficiency is still a significant challenge, as C‐intermediates tend to go through an extensive reduction achieving mostly C‐containing productions due to the lack of N‐intermediates, originating from slow diffusion rate of NO2‐. Herein, we report the charge‐polarized Feδ‐‐Cuδ+ dual sites in metal/carbon heterojunction material (Cu@Fe‐N‐C) for co‐reduction of CO2 and dilute NO2‐ solution (100 ppm NO2‐‐N). The electron‐rich single Fe atoms dispersed N‐doped carbon (Fe‐N‐C) restrain *CO desorption, and the electron‐deficient Cu nanoparticles (Cu) promote the deep reduction of NO2– to *NH2. As a result, the obtained Cu@Fe‐N‐C exhibits a high Faradic efficiency for urea of 50.05% with a yield of 850.57 mg h‐1 g‐1 at ‐0.35 V (vs. RHE) in a flow cell. Moreover, Curea‐selectivity reaches to 100% and a near‐unity selectivity for the value‐added urea and NH3 is realized. The present results provide a valuable reference for the design of new catalysts for efficient synthesis of C‐N compounds in dilute NO2‐ solution.
{"title":"Charge Polarization Boosting Electrochemical Urea Synthesis by Co‐Reduction of CO2 and Nitrite in Dilute Concentrations with a Unity Carbon Selectivity","authors":"Zhihao Feng, Lu-Hua Zhang, Yabo Guo, Jiangyi Guo, Fei Li, Fengshou Yu","doi":"10.1002/anie.202500262","DOIUrl":"https://doi.org/10.1002/anie.202500262","url":null,"abstract":"Synthesis of urea through electrocatalytic coupling reaction of CO2 with nitrite (NO2‐) represents a sustainable means to substitute the conventional energy‐intensive urea synthetic protocol. The direct conversion of dilute NO2‐ in real wastewaters to urea with high efficiency is still a significant challenge, as C‐intermediates tend to go through an extensive reduction achieving mostly C‐containing productions due to the lack of N‐intermediates, originating from slow diffusion rate of NO2‐. Herein, we report the charge‐polarized Feδ‐‐Cuδ+ dual sites in metal/carbon heterojunction material (Cu@Fe‐N‐C) for co‐reduction of CO2 and dilute NO2‐ solution (100 ppm NO2‐‐N). The electron‐rich single Fe atoms dispersed N‐doped carbon (Fe‐N‐C) restrain *CO desorption, and the electron‐deficient Cu nanoparticles (Cu) promote the deep reduction of NO2– to *NH2. As a result, the obtained Cu@Fe‐N‐C exhibits a high Faradic efficiency for urea of 50.05% with a yield of 850.57 mg h‐1 g‐1 at ‐0.35 V (vs. RHE) in a flow cell. Moreover, Curea‐selectivity reaches to 100% and a near‐unity selectivity for the value‐added urea and NH3 is realized. The present results provide a valuable reference for the design of new catalysts for efficient synthesis of C‐N compounds in dilute NO2‐ solution.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"18 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427087","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}
Bowen Jiang, Heng Zhang, Rui Pan, Min Ji, Lin Zhu, Guoju Zhang, Jing Liu, Huihui Shi, Huang Huang, Shu Wan, Kuibo Yin, Litao Sun
The overly simplistic geometric and electronic structures of single-atom catalysts have become a significant bottleneck in the field of single-atom sensing, impeding both the design of highly efficient electrochemical sensors and the establishment of structure-activity relationships. To address these challenges, we present a novel strategy to boost the sensing performance of single-atom catalysts by precisely tuning the single-atomic interdistance (SAD) in correlated single-atom catalysts (c-SACs). A series of Ru-based c-SACs (Rud=6.2 Å, Rud=7.0 Å, and Rud=9.3 Å) are synthesized with predetermined SAD values, which are comprehensively characterized by various techniques. Electrochemical studies on uric acid (UA) oxidation reveal that Rud=6.2 Å demonstrates an extraordinary sensitivity of 9.83 μA μM-1cm-2, which is superior to most of electrochemistry biosensors reported previously. Kinetic analysis and product examination unveil that the 6.2 Å Ru SAD instigates a distinctive three-electron oxidation of UA, with an extra electron transfer compared to the conventional two-electron pathway, which fundamentally enhances its sensitivity. Density functional theory calculations confirm the optimal SAD facilitates dual-site UA adsorption and accelerated charge transfer dynamics. This investigation provides novel insights into the strategic engineering of high-performance SAC-based electrochemical sensors by precisely controlling the atomic-scale structure of active sites.
{"title":"Three-Electron Uric Acid Oxidation via Interdistance-Dependent Switching Pathways in Correlated Single-Atom Catalysts for Boosting Sensing Signals","authors":"Bowen Jiang, Heng Zhang, Rui Pan, Min Ji, Lin Zhu, Guoju Zhang, Jing Liu, Huihui Shi, Huang Huang, Shu Wan, Kuibo Yin, Litao Sun","doi":"10.1002/anie.202500474","DOIUrl":"https://doi.org/10.1002/anie.202500474","url":null,"abstract":"The overly simplistic geometric and electronic structures of single-atom catalysts have become a significant bottleneck in the field of single-atom sensing, impeding both the design of highly efficient electrochemical sensors and the establishment of structure-activity relationships. To address these challenges, we present a novel strategy to boost the sensing performance of single-atom catalysts by precisely tuning the single-atomic interdistance (SAD) in correlated single-atom catalysts (c-SACs). A series of Ru-based c-SACs (Rud=6.2 Å, Rud=7.0 Å, and Rud=9.3 Å) are synthesized with predetermined SAD values, which are comprehensively characterized by various techniques. Electrochemical studies on uric acid (UA) oxidation reveal that Rud=6.2 Å demonstrates an extraordinary sensitivity of 9.83 μA μM-1cm-2, which is superior to most of electrochemistry biosensors reported previously. Kinetic analysis and product examination unveil that the 6.2 Å Ru SAD instigates a distinctive three-electron oxidation of UA, with an extra electron transfer compared to the conventional two-electron pathway, which fundamentally enhances its sensitivity. Density functional theory calculations confirm the optimal SAD facilitates dual-site UA adsorption and accelerated charge transfer dynamics. This investigation provides novel insights into the strategic engineering of high-performance SAC-based electrochemical sensors by precisely controlling the atomic-scale structure of active sites.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435688","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}
Polyethylene terephthalate (PET), polystyrene (PS), and polyvinyl chloride (PVC) are the most commonly used polymers in plastic products. Therefore, endowing these polymers with unique optical properties would significantly enhance their overall technological value. Herein, we synthesized a phosphorescent molecule, 2,2'‐diphenyl‐3,3'‐bibenzofuran (DBF), with notable reversible photochromic properties (switching between colorless and deep red) as the guest and constructed a doped system with the above polymers as the hosts. All doped materials exhibited both room‐temperature phosphorescence and reversible photochromic properties. The guest molecule exhibited strong reversible cyclization activity and small conformational changes during the reaction process, as well as moderate rigidity of the host matrix, which enabled the uncommon coexistence of these two properties in the doped system. Finally, DBF/PET was successfully formed into a transparent and uniform film with a length of 200 m, a width of 20 cm, a thickness of only 60‐70 μm. This film exhibited excellent thermal‐stability, sensitivity, and resistance to photo‐fatigue, indicating its applicability in industrial production.
{"title":"Large‐area, Ultra‐thin Organic Films with Both Photochromic and Phosphorescence Properties","authors":"Chuanli Chen, Weijing Zhang, Zeng Wang, Xin Wang, Jianhui Yang, Yue Ren, Ziqi Huang, Wenbo Dai, Xiaobo Huang, Yunxiang Lei","doi":"10.1002/anie.202501448","DOIUrl":"https://doi.org/10.1002/anie.202501448","url":null,"abstract":"Polyethylene terephthalate (PET), polystyrene (PS), and polyvinyl chloride (PVC) are the most commonly used polymers in plastic products. Therefore, endowing these polymers with unique optical properties would significantly enhance their overall technological value. Herein, we synthesized a phosphorescent molecule, 2,2'‐diphenyl‐3,3'‐bibenzofuran (DBF), with notable reversible photochromic properties (switching between colorless and deep red) as the guest and constructed a doped system with the above polymers as the hosts. All doped materials exhibited both room‐temperature phosphorescence and reversible photochromic properties. The guest molecule exhibited strong reversible cyclization activity and small conformational changes during the reaction process, as well as moderate rigidity of the host matrix, which enabled the uncommon coexistence of these two properties in the doped system. Finally, DBF/PET was successfully formed into a transparent and uniform film with a length of 200 m, a width of 20 cm, a thickness of only 60‐70 μm. This film exhibited excellent thermal‐stability, sensitivity, and resistance to photo‐fatigue, indicating its applicability in industrial production.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"180 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427083","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}
Yuhang Wang, Di Zhang, Bin Sun, Xue Jia, Linda Zhang, Hefeng Cheng, Jun Fan, Hao Li
In their Communication (e202418228), Hao Li and co-workers reveal an exciting contrast: the electric field response of the binding strength of *OCHO on Sn-N4-C and polyatomic Sn displays opposite behaviors. This response results in a fascinating, opposite pH-dependent volcano evolution for Sn-N4-C and polyatomic Sn. Most importantly, we propose that distinct strategies are necessary for designing catalysts using single-atom versus polyatomic metal catalysts.
{"title":"Frontispiece: Divergent Activity Shifts of Tin-Based Catalysts for Electrochemical CO2 Reduction: pH-Dependent Behavior of Single-Atom Versus Polyatomic Structures","authors":"Yuhang Wang, Di Zhang, Bin Sun, Xue Jia, Linda Zhang, Hefeng Cheng, Jun Fan, Hao Li","doi":"10.1002/anie.202580861","DOIUrl":"https://doi.org/10.1002/anie.202580861","url":null,"abstract":"<p>In their Communication (e202418228), Hao Li and co-workers reveal an exciting contrast: the electric field response of the binding strength of *OCHO on Sn-N4-C and polyatomic Sn displays opposite behaviors. This response results in a fascinating, opposite pH-dependent volcano evolution for Sn-N4-C and polyatomic Sn. Most importantly, we propose that distinct strategies are necessary for designing catalysts using single-atom versus polyatomic metal catalysts.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"64 8","pages":""},"PeriodicalIF":16.1,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/anie.202580861","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143431286","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Precise and effective patterning strategies are essential for integrating metal‐organic frameworks (MOFs) into microelectronics, photonics, sensors, and other solid‐state devices. Direct lithography of MOFs with light and other irradiation sources has emerged as a promising patterning strategy. However, existing direct lithography methods often rely on the irradiation‐induced amorphization of the MOFs structures and the breaking of strong covalent bonds in their organic linkers. High‐energy sources (such as X‐rays or electron beams) and large irradiation doses—conditions unfavorable for scalable patterning—are thus required. Here, we report a photoinduced fluorination chemistry for patterning various zeolitic imidazolate frameworks (ZIFs) under mild UV irradiation. Using UV doses as low as 10 mJ cm–2, light‐sensitive fluorine‐containing molecules covalently bond to ZIFs and enhance their stability in water. This creates a water‐stability contrast between ZIFs in exposed and unexposed regions, enabling scalable direct photolithography of ZIFs with high resolution (2 μm) on 4‐inch wafers and flexible substrates. The patterned ZIFs preserve their original crystallinity and porous properties while gaining increased hydrophobicity. This allows for the demonstration of a water‐responsive fluorescent MOFs array with implications in sensing and multicolor information encryption.
{"title":"Direct Photopatterning of Zeolitic Imidazolate Frameworks via Photoinduced Fluorination","authors":"Xiaoli Tian, Wenjun Li, Fu Li, Mingfeng Cai, Yilong Si, Hao Tang, Haifang Li, Hao Zhang","doi":"10.1002/anie.202500476","DOIUrl":"https://doi.org/10.1002/anie.202500476","url":null,"abstract":"Precise and effective patterning strategies are essential for integrating metal‐organic frameworks (MOFs) into microelectronics, photonics, sensors, and other solid‐state devices. Direct lithography of MOFs with light and other irradiation sources has emerged as a promising patterning strategy. However, existing direct lithography methods often rely on the irradiation‐induced amorphization of the MOFs structures and the breaking of strong covalent bonds in their organic linkers. High‐energy sources (such as X‐rays or electron beams) and large irradiation doses—conditions unfavorable for scalable patterning—are thus required. Here, we report a photoinduced fluorination chemistry for patterning various zeolitic imidazolate frameworks (ZIFs) under mild UV irradiation. Using UV doses as low as 10 mJ cm–2, light‐sensitive fluorine‐containing molecules covalently bond to ZIFs and enhance their stability in water. This creates a water‐stability contrast between ZIFs in exposed and unexposed regions, enabling scalable direct photolithography of ZIFs with high resolution (2 μm) on 4‐inch wafers and flexible substrates. The patterned ZIFs preserve their original crystallinity and porous properties while gaining increased hydrophobicity. This allows for the demonstration of a water‐responsive fluorescent MOFs array with implications in sensing and multicolor information encryption.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427085","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}
Long Yi, Tao Jiang, Ren Ren, Ji Cao, Joshua B. Edel, Aleksandar P. Ivanov, Longhua Tang
Quantum mechanical tunnelling sensors (QMTs) have emerged as a promising technology for next‐generation single‐molecule detection. When QMT sensors are combined with redox species, repeated oxidation and reduction (redox cycling) can also be observed. We developed robust QMT probes with electrode gap distances below 2 nm. Using the generator‐collector (GC) mode, we verified that redox cycling of the ferrocyanide/ferricyanide (Fe(CN)63‐/4‐) couple occurs both in the tunnelling regime and on the electrode surface. Our findings indicated that the current enhancement is affected by both the gap distance and surface modifications of the probes. These QMT probes exhibited remarkable sensitivity, capable of detecting Fe(CN)63‐/4‐ concentrations as low as sub‐picomolar levels. Utilising this ability to modulate redox reactions, we adapted the QMT probes to serve as electrochemical sensors for detecting viral proteins. By modifying the electrode surfaces, our functionalised QMT probes achieved sub‐pM detection limits with high selectivity in biofluids such as nasopharyngeal secretions. These findings highlight the potential of QMT probes to develop into a new class of electrochemical tunnelling sensors, offering significant advancements in biomedical diagnostics.
{"title":"Quantum Mechanical Tunnelling Probes with Redox Cycling for Ultra‐Sensitive Detection of Biomolecules","authors":"Long Yi, Tao Jiang, Ren Ren, Ji Cao, Joshua B. Edel, Aleksandar P. Ivanov, Longhua Tang","doi":"10.1002/anie.202501941","DOIUrl":"https://doi.org/10.1002/anie.202501941","url":null,"abstract":"Quantum mechanical tunnelling sensors (QMTs) have emerged as a promising technology for next‐generation single‐molecule detection. When QMT sensors are combined with redox species, repeated oxidation and reduction (redox cycling) can also be observed. We developed robust QMT probes with electrode gap distances below 2 nm. Using the generator‐collector (GC) mode, we verified that redox cycling of the ferrocyanide/ferricyanide (Fe(CN)63‐/4‐) couple occurs both in the tunnelling regime and on the electrode surface. Our findings indicated that the current enhancement is affected by both the gap distance and surface modifications of the probes. These QMT probes exhibited remarkable sensitivity, capable of detecting Fe(CN)63‐/4‐ concentrations as low as sub‐picomolar levels. Utilising this ability to modulate redox reactions, we adapted the QMT probes to serve as electrochemical sensors for detecting viral proteins. By modifying the electrode surfaces, our functionalised QMT probes achieved sub‐pM detection limits with high selectivity in biofluids such as nasopharyngeal secretions. These findings highlight the potential of QMT probes to develop into a new class of electrochemical tunnelling sensors, offering significant advancements in biomedical diagnostics.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427095","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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