Pub Date : 2026-03-25DOI: 10.1002/anie.2026-m1803062800
Éva Bartus, Edit Wéber, Attila Tököli, Ferenc Bogár, Momen R. F. Mohamed, Gábor Kecskeméti, Zoltán Szabó, Zoltán Kele, András Perczel, Márton Gadanecz, Zoltán Orgován, György M. Keserű, Tamás A. Martinek
In Research Article (e18911), Tamás A. Martinek and co-workers illustrate chemical evolution as an intermediate step that connects chemical reaction networks to the emergence of biologically relevant evolutionary behavior. The system includes a protein catalyst that accelerates light-driven replication and competitive selection among primitive peptidic replicators. The mechanism provides a possible explanation of how simple chemical autocatalytic processes can lead to external energy-driven selection and complexity.
在研究文章（e18911）中，Tamás A. Martinek和他的同事说明了化学进化是连接化学反应网络和生物相关进化行为出现的中间步骤。该系统包括一种蛋白质催化剂，可以加速光驱动复制和原始肽复制子之间的竞争选择。该机制为简单的化学自催化过程如何导致外部能量驱动的选择和复杂性提供了可能的解释。
{"title":"Inside Front Cover: Light-Driven Competitive Selection in a Protein-Catalyzed Dissipative Peptide Replication","authors":"Éva Bartus, Edit Wéber, Attila Tököli, Ferenc Bogár, Momen R. F. Mohamed, Gábor Kecskeméti, Zoltán Szabó, Zoltán Kele, András Perczel, Márton Gadanecz, Zoltán Orgován, György M. Keserű, Tamás A. Martinek","doi":"10.1002/anie.2026-m1803062800","DOIUrl":"https://doi.org/10.1002/anie.2026-m1803062800","url":null,"abstract":"In Research Article (e18911), Tamás A. Martinek and co-workers illustrate chemical evolution as an intermediate step that connects chemical reaction networks to the emergence of biologically relevant evolutionary behavior. The system includes a protein catalyst that accelerates light-driven replication and competitive selection among primitive peptidic replicators. The mechanism provides a possible explanation of how simple chemical autocatalytic processes can lead to external energy-driven selection and complexity.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"52 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507657","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}
Ni-based catalysts are extensively studied for the dry reforming of methane (DRM), which converts CO2 and CH4—the two most abundant greenhouse gases—into syngas for downstream chemical synthesis. The harsh reaction conditions required for DRM lead to coking, metal aggregation. Although multiple mechanisms have been proposed, the molecular-level understanding of the reaction remains debated. Here, we report the synthesis of θ-Al2O3-supported Ni DRM catalysts via surface organometallic chemistry (SOMC) and report its outstanding activity and stability. The resulting Ni nanoparticles remain highly dispersed, with an average size of 5.3 ± 1.3 nm even after reduction at 900°C. This model catalyst exhibits distinct temperature-dependent behavior during DRM, with marked structural and mechanistic differences observed within a narrow 50°C range. In situ x-ray absorption spectroscopy (XAS) and ex situ synchrotron x-ray diffraction (XRD) reveal a dynamic induction process involving rapid Ni oxidation, followed by reduction and carbon insertion into the Ni lattice at 850°C, forming a carbide-like NiCx phase. At 800°C, incorporation of carbon is limited, thus leading to surface coking and catalyst deactivation. Furthermore, gas-switching experiments confirm the importance of a carbide cycle at 850°C, enabling continuous carbon removal and sustained catalytic stability.
{"title":"Initiation: A Critical Step for High Activity and Stability in Ni-Based Methane Dry Reforming Catalysts Supported on θ-Al2O3","authors":"Wei Wang, Milivoj Plodinec, Wei Zhou, Christophe Copéret","doi":"10.1002/anie.1716058","DOIUrl":"https://doi.org/10.1002/anie.1716058","url":null,"abstract":"Ni-based catalysts are extensively studied for the dry reforming of methane (DRM), which converts CO<sub>2</sub> and CH<sub>4</sub>—the two most abundant greenhouse gases—into syngas for downstream chemical synthesis. The harsh reaction conditions required for DRM lead to coking, metal aggregation. Although multiple mechanisms have been proposed, the molecular-level understanding of the reaction remains debated. Here, we report the synthesis of <i>θ</i>-Al<sub>2</sub>O<sub>3</sub>-supported Ni DRM catalysts via surface organometallic chemistry (SOMC) and report its outstanding activity and stability. The resulting Ni nanoparticles remain highly dispersed, with an average size of 5.3 ± 1.3 nm even after reduction at 900°C. This model catalyst exhibits distinct temperature-dependent behavior during DRM, with marked structural and mechanistic differences observed within a narrow 50°C range. In situ x-ray absorption spectroscopy (XAS) and ex situ synchrotron x-ray diffraction (XRD) reveal a dynamic induction process involving rapid Ni oxidation, followed by reduction and carbon insertion into the Ni lattice at 850°C, forming a carbide-like NiC<sub>x</sub> phase. At 800°C, incorporation of carbon is limited, thus leading to surface coking and catalyst deactivation. Furthermore, gas-switching experiments confirm the importance of a carbide cycle at 850°C, enabling continuous carbon removal and sustained catalytic stability.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"17 10 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507692","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}
Weirong Li, Mengyu Liu, Zixuan Liao, Zhongxiang Peng, Xingxin Shao, Jun Liu, Lixiang Wang
Small-molecule electron acceptors with donor–acceptor (D–A) structures have emerged as attractive materials for organic optoelectronics, yet achieving strong absorption in the short-wavelength infrared (SWIR, 1000–3000 nm) region remains a fundamental challenge. Here, a resonant N—B←N unit, bis(borondifluoride)-8-imidazodipyrromethene (BIP), is introduced as a new electron-deficient core for constructing D–A type SWIR acceptors. Incorporation of the BIP unit induces a pronounced bathochromic shift of 255 nm and affords an ultranarrow optical bandgap of 0.86 eV, with thin-film absorption extending to 1450 nm. The resulting acceptor, BIP-M1, exhibits a high molar extinction coefficient of 3.8 × 105 M−1 cm−1 and an exceptionally small Stokes shift of 0.054 eV, indicative of its strong SWIR absorption capability and suppressed nonradiative losses. Photodiode-type organic photodetectors based on BIP-M1 enable sensitive photoresponse over a broad spectral range from 300 to 1400 nm, delivering a responsivity of 0.18 A W−1 and a specific detectivity of 3.93 × 1011 Jones at 1200 nm, together with an ultralow Urbach energy of 19.19 meV. This study identifies resonant N—B←N units as powerful structural motifs for small bandgap molecular design and establishes BIP-based small molecular acceptors as a promising platform for next-generation SWIR optoelectronics.
{"title":"An Electron Acceptor With bis(Borondifluoride)-8-imidazodipyrromethene as the Core for Short-Wavelength Infrared Photoresponse","authors":"Weirong Li, Mengyu Liu, Zixuan Liao, Zhongxiang Peng, Xingxin Shao, Jun Liu, Lixiang Wang","doi":"10.1002/anie.3239137","DOIUrl":"https://doi.org/10.1002/anie.3239137","url":null,"abstract":"Small-molecule electron acceptors with donor–acceptor (D–A) structures have emerged as attractive materials for organic optoelectronics, yet achieving strong absorption in the short-wavelength infrared (SWIR, 1000–3000 nm) region remains a fundamental challenge. Here, a resonant N—B←N unit, bis(borondifluoride)-8-imidazodipyrromethene (BIP), is introduced as a new electron-deficient core for constructing D–A type SWIR acceptors. Incorporation of the BIP unit induces a pronounced bathochromic shift of 255 nm and affords an ultranarrow optical bandgap of 0.86 eV, with thin-film absorption extending to 1450 nm. The resulting acceptor, BIP-M1, exhibits a high molar extinction coefficient of 3.8 × 10<sup>5</sup> M<sup>−</sup><sup>1</sup> cm<sup>−</sup><sup>1</sup> and an exceptionally small Stokes shift of 0.054 eV, indicative of its strong SWIR absorption capability and suppressed nonradiative losses. Photodiode-type organic photodetectors based on BIP-M1 enable sensitive photoresponse over a broad spectral range from 300 to 1400 nm, delivering a responsivity of 0.18 A W<sup>−</sup><sup>1</sup> and a specific detectivity of 3.93 × 10<sup>11</sup> Jones at 1200 nm, together with an ultralow Urbach energy of 19.19 meV. This study identifies resonant N—B←N units as powerful structural motifs for small bandgap molecular design and establishes BIP-based small molecular acceptors as a promising platform for next-generation SWIR optoelectronics.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507658","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}
Oksana Karychort, Jan Priessnitz, Volodymyr Buturlim, Mitja Krnel, Iñigo Robredo, Nazar Zaremba, Ulrich Burkhardt, Helge Rosner, Andrew Fitch, Markus König, Fabrice Wilhelm, Olha Zhak, Dileep Krishnan, Ivan Soldatov, Rudolf Schäfer, Maia Vergniory, Libor Šmejkal, Theo Siegrist, Berit H. Goodge, Krzysztof Gofryk, Yurii Prots, Eteri Svanidze
Magnetostrictive materials are of interest not only from a fundamental perspective but also for their potential applications, spanning spintronics to energy harvesting. A new magnetostrictive material—SmFe5As3—reveals a complex interplay between magnetostriction, magnetic properties, and the crystal structure behavior. The ground state of SmFe5As3 is ferrimagnetic, as evidenced by magnetic susceptibility data, band-structure calculations, and XANES measurements. At K, part of the Fe sublattice reorients, transitioning into a ferromagnetic state. This is followed by an entrance into the paramagnetic state at K. The effects observed in the magnetic measurements are accompanied by structural phase transitions. All three phases—below , between and , and above —are described by the same structural motif of the UCr5P3 type (monoclinic space group ), differing only in the degree of deformation of the Fe–As framework. The new material exhibits giant magnetostriction of . Dilatometry measurements on a SmFe5As3 single crystal indicate strongly diverse behavior, exhibiting not only negative, but also zero, as well as positive thermo-elastic effects.
{"title":"Giant Magnetostriction in Ferrimagnetic SmFe5As3","authors":"Oksana Karychort, Jan Priessnitz, Volodymyr Buturlim, Mitja Krnel, Iñigo Robredo, Nazar Zaremba, Ulrich Burkhardt, Helge Rosner, Andrew Fitch, Markus König, Fabrice Wilhelm, Olha Zhak, Dileep Krishnan, Ivan Soldatov, Rudolf Schäfer, Maia Vergniory, Libor Šmejkal, Theo Siegrist, Berit H. Goodge, Krzysztof Gofryk, Yurii Prots, Eteri Svanidze","doi":"10.1002/anie.202522578","DOIUrl":"https://doi.org/10.1002/anie.202522578","url":null,"abstract":"Magnetostrictive materials are of interest not only from a fundamental perspective but also for their potential applications, spanning spintronics to energy harvesting. A new magnetostrictive material—SmFe<sub>5</sub>As<sub>3</sub>—reveals a complex interplay between magnetostriction, magnetic properties, and the crystal structure behavior. The ground state of SmFe<sub>5</sub>As<sub>3</sub> is ferrimagnetic, as evidenced by magnetic susceptibility data, band-structure calculations, and XANES measurements. At <span data-altimg=\"/cms/asset/71b9c406-3938-4f3b-8adf-f6b00ce1d493/anie71879-math-0001.png\"></span><math></math> K, part of the Fe sublattice reorients, transitioning into a ferromagnetic state. This is followed by an entrance into the paramagnetic state at <span data-altimg=\"/cms/asset/99748d25-47cf-43bc-88ef-464e839dc7f7/anie71879-math-0002.png\"></span><math></math> K. The effects observed in the magnetic measurements are accompanied by structural phase transitions. All three phases—below <span data-altimg=\"/cms/asset/39ae4903-4b2e-4e4f-ac94-7466a9d6380b/anie71879-math-0003.png\"></span><math></math>, between <span data-altimg=\"/cms/asset/94b370be-d542-4357-b54b-ce30eea1c0b3/anie71879-math-0004.png\"></span><math></math> and <span data-altimg=\"/cms/asset/760cd99d-ba00-4f08-b8bd-09032ddbcedb/anie71879-math-0005.png\"></span><math></math>, and above <span data-altimg=\"/cms/asset/e2f99140-116d-405b-b2fb-3593926eabc6/anie71879-math-0006.png\"></span><math></math>—are described by the same structural motif of the UCr<sub>5</sub>P<sub>3</sub> type (monoclinic space group <span data-altimg=\"/cms/asset/bc870d8f-3519-4e49-86f8-04d35a8c4c1b/anie71879-math-0007.png\"></span><math></math>), differing only in the degree of deformation of the Fe–As framework. The new material exhibits giant magnetostriction of <span data-altimg=\"/cms/asset/77e96ed1-0c34-47dd-a2f9-f224e6c2f5e1/anie71879-math-0008.png\"></span><math></math>. Dilatometry measurements on a SmFe<sub>5</sub>As<sub>3</sub> single crystal indicate strongly diverse behavior, exhibiting not only negative, but also zero, as well as positive thermo-elastic effects.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"49 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506946","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}
Yuejiang Han, Chunqing Ji, Mingyao He, Yuning Lou, Pengbo Duanmu, Lin Liu, Daqiang Yuan, Zhengbo Han
Ultra-microporous molecular sieving materials offer exceptional size- and shape-selective gas separation, yet their practical use is often limited by slow diffusion kinetics and low adsorption capacities. Here, we report a low-cost manganese-based metal-organic framework (MOF), Mn-dcbp, featuring an adaptive “corner-pocket” channel structure. While retaining C2H2/C2H4 sieving selectivity, the material successfully integrates a high acetylene (C2H2) uptake (126.3 cm3/cm3) with ultrafast diffusion kinetics (k = 0.01863 s−1). In situ single-crystal x-ray diffraction reveals a sub-angstrom-level structural adaptation mechanism induced by C2H2, leading to ordered, high-density packing of C2H2 within the channels and achieving a record storage density of 1.02 g/mL. Strong host–guest interactions enable the material to maintain excellent C2H2 adsorption capacity (110.6 cm3/cm3) even at elevated temperatures (75 °C), while also demonstrating superior separation performance for C2H2/C2H4 and C2H2/CO2 gas mixtures. Furthermore, Mn-dcbp can be produced on a large scale via an environmentally friendly route and exhibits excellent, water, thermal, and cycling stability, which is crucial for potential industrial implementation.
{"title":"Adaptive Corner-Pocket Channels in a Metal-Organic Framework for Acetylene Ultra-Fast Diffusion and Storage","authors":"Yuejiang Han, Chunqing Ji, Mingyao He, Yuning Lou, Pengbo Duanmu, Lin Liu, Daqiang Yuan, Zhengbo Han","doi":"10.1002/anie.8460951","DOIUrl":"https://doi.org/10.1002/anie.8460951","url":null,"abstract":"Ultra-microporous molecular sieving materials offer exceptional size- and shape-selective gas separation, yet their practical use is often limited by slow diffusion kinetics and low adsorption capacities. Here, we report a low-cost manganese-based metal-organic framework (MOF), Mn-dcbp, featuring an adaptive “corner-pocket” channel structure. While retaining C<sub>2</sub>H<sub>2</sub>/C<sub>2</sub>H<sub>4</sub> sieving selectivity, the material successfully integrates a high acetylene (C<sub>2</sub>H<sub>2</sub>) uptake (126.3 cm<sup>3</sup>/cm<sup>3</sup>) with ultrafast diffusion kinetics (k = 0.01863 s<sup>−1</sup>). In situ single-crystal x-ray diffraction reveals a sub-angstrom-level structural adaptation mechanism induced by C<sub>2</sub>H<sub>2</sub>, leading to ordered, high-density packing of C<sub>2</sub>H<sub>2</sub> within the channels and achieving a record storage density of 1.02 g/mL. Strong host–guest interactions enable the material to maintain excellent C<sub>2</sub>H<sub>2</sub> adsorption capacity (110.6 cm<sup>3</sup>/cm<sup>3</sup>) even at elevated temperatures (75 °C), while also demonstrating superior separation performance for C<sub>2</sub>H<sub>2</sub>/C<sub>2</sub>H<sub>4</sub> and C<sub>2</sub>H<sub>2</sub>/CO<sub>2</sub> gas mixtures. Furthermore, Mn-dcbp can be produced on a large scale via an environmentally friendly route and exhibits excellent, water, thermal, and cycling stability, which is crucial for potential industrial implementation.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"18 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507659","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}
Wide-bandgap mixed-halide perovskites generally used as front cell absorber play great importance for manufacturing high-performance tandem perovskite solar cells. However, the deviation in coordination strength between solvent molecule and lead halide always induces inhomogeneous halogen-phase crystallization and distribution, which inevitably degrades the device efficiency and durability. Herein, we propose a strategy to precisely regulate the dielectric constant (εr) and Gutmann donor number (DN) of popularly-used dimethylsulfoxide (DMSO) by incorporation of water molecule, which significantly weakens the binding energy of DMSO-PbI2, i.e., the solubility, and improves the PbBr2 counterpart. With the balance of interaction energies between DMSO and PbI2 or PbBr2, concurrent nucleation of mixed-halide perovskite phase is realized, benefiting the fabrication of high-quality wide-bandgap perovskite film with homogeneous halogen distribution. Consequently, a champion efficiency of 15.42% for all-air-processed carbon-based all-inorganic CsPbI2Br cell is achieved, one cutting-edge value among congeneric devices, with excellent reproducibility by controlling the water dosage via a hydrophobic solvent encapsulation strategy. Together with the enhanced stability, this work provides a new path for engineering perovskite solution and promoting the scalable photovoltaics in air.
{"title":"Concurrent Nucleation of Mixed-Halide Perovskite Phase via Balancing Solvent-PbX2 Interaction for Efficient Solar Cells in Air","authors":"Chenlong Zhang, Jialong Duan, Naimin Liu, Kunye Li, Guoxing Zhang, Li Li, Shengkai Wang, Jiajun Liu, Wenhao Tang, Jie Dou, Linzheng Ma, Qiyao Guo, Benlin He, Xiya Yang, Qunwei Tang","doi":"10.1002/anie.5296449","DOIUrl":"https://doi.org/10.1002/anie.5296449","url":null,"abstract":"Wide-bandgap mixed-halide perovskites generally used as front cell absorber play great importance for manufacturing high-performance tandem perovskite solar cells. However, the deviation in coordination strength between solvent molecule and lead halide always induces inhomogeneous halogen-phase crystallization and distribution, which inevitably degrades the device efficiency and durability. Herein, we propose a strategy to precisely regulate the dielectric constant (<i>ε</i><sub>r</sub>) and Gutmann donor number (<i>D</i><sub>N</sub>) of popularly-used dimethylsulfoxide (DMSO) by incorporation of water molecule, which significantly weakens the binding energy of DMSO-PbI<sub>2</sub>, i.e., the solubility, and improves the PbBr<sub>2</sub> counterpart. With the balance of interaction energies between DMSO and PbI<sub>2</sub> or PbBr<sub>2</sub>, concurrent nucleation of mixed-halide perovskite phase is realized, benefiting the fabrication of high-quality wide-bandgap perovskite film with homogeneous halogen distribution. Consequently, a champion efficiency of 15.42% for all-air-processed carbon-based all-inorganic CsPbI<sub>2</sub>Br cell is achieved, one cutting-edge value among congeneric devices, with excellent reproducibility by controlling the water dosage via a hydrophobic solvent encapsulation strategy. Together with the enhanced stability, this work provides a new path for engineering perovskite solution and promoting the scalable photovoltaics in air.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"15 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507661","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}
Biswa P. Mishra, Ben Cristofori-Armstrong, Elena Budusan, Mimi Golder, Neville J. Butcher, Junyu Liu, Theo Crawford, Yanni K.-Y. Chin, Anneka Pereira Schmidt, Xinying Jia, Taylor B. Smallwood, Richard J. Clark, Jan P. Wurm, Lachlan D. Rash, Mehdi Mobli
Proton-gated acid-sensing ion channels (ASICs) are emerging therapeutic targets for ischemia-related conditions such as stroke and myocardial infarction. Although structural data exist for ASIC1a, key aspects of ligand recognition and modulation remain unresolved. Using multidimensional solution-state NMR spectroscopy, we show that the principal ligand-binding region of ASICs, the thumb domain, forms an independently folded unit that at neutral pH adopts a native-like conformation resembling the resting state of the channel. By integrating high-resolution biophysical analyses of ligand binding to the isolated thumb domain with electrophysiological measurements on full-length ASIC1a, we distinguished molecular interactions that determine binding affinity from those governing functional efficacy. This approach revealed that dynorphin A acts as a competitive antagonist of ASIC1a. Furthermore, NMR-based pKa determination of individual acidic residues demonstrated generally elevated values across the isolated thumb domain, supporting the presence of an extended acid-sensing network rather than a single dominant pH sensor. These findings establish the isolated thumb domain as a powerful model for dissecting ASIC ligand interactions and pH sensitivity in solution, providing mechanistic insights and enabling structure-based drug discovery of therapeutic modulators for ASICs and related ion channels.
{"title":"The Isolated Thumb Domain of Acid-Sensing Ion Channels Forms a Minimal Folding Unit Enabling Ligand Binding Studies","authors":"Biswa P. Mishra, Ben Cristofori-Armstrong, Elena Budusan, Mimi Golder, Neville J. Butcher, Junyu Liu, Theo Crawford, Yanni K.-Y. Chin, Anneka Pereira Schmidt, Xinying Jia, Taylor B. Smallwood, Richard J. Clark, Jan P. Wurm, Lachlan D. Rash, Mehdi Mobli","doi":"10.1002/anie.202523977","DOIUrl":"https://doi.org/10.1002/anie.202523977","url":null,"abstract":"Proton-gated acid-sensing ion channels (ASICs) are emerging therapeutic targets for ischemia-related conditions such as stroke and myocardial infarction. Although structural data exist for ASIC1a, key aspects of ligand recognition and modulation remain unresolved. Using multidimensional solution-state NMR spectroscopy, we show that the principal ligand-binding region of ASICs, the thumb domain, forms an independently folded unit that at neutral pH adopts a native-like conformation resembling the resting state of the channel. By integrating high-resolution biophysical analyses of ligand binding to the isolated thumb domain with electrophysiological measurements on full-length ASIC1a, we distinguished molecular interactions that determine binding affinity from those governing functional efficacy. This approach revealed that dynorphin A acts as a competitive antagonist of ASIC1a. Furthermore, NMR-based p<i>K</i><sub>a</sub> determination of individual acidic residues demonstrated generally elevated values across the isolated thumb domain, supporting the presence of an extended acid-sensing network rather than a single dominant pH sensor. These findings establish the isolated thumb domain as a powerful model for dissecting ASIC ligand interactions and pH sensitivity in solution, providing mechanistic insights and enabling structure-based drug discovery of therapeutic modulators for ASICs and related ion channels.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"17 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506941","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}
Xiyun Ye, Yichao Chen, Xiaojuan Song, Tingwei Ren, Jinfeng Wang, Yujun Xie, Dongge Ma, Jishan Wu, Zhen Li
Deep blue circularly polarized organic light-emitting diodes (CP-OLEDs) remain scarce due to the stringent requirement of simultaneously achieving a wide bandgap and strong chiroptical activity. Herein, we report DC-TRZ, a C2-symmetric chiral emitter comprising a dimeric carbazole donor and a triphenyltriazine acceptor, which exhibits deep-blue emission at 433 nm with the high emission efficiency of up to 79%. Its enantiopure (R)- and (S)-isomers display pronounced Cotton effects and distinct circularly polarized luminescence (CPL). Notably, CP-OLEDs based on (R)- and (S)-DC-TRZ deliver deep-blue electroluminescence with Commission Internationale de L'Eclairage (CIE) coordinates of (0.14, 0.07), achieving a maximum external quantum efficiency of 4.58% and record-high luminescence dissymmetry factors of +2.7 × 10−2 and −2.2 × 10−2, respectively, representing the highest values reported to date for blue CP-OLEDs employing small organic molecules. These results demonstrate that DC-TRZ functions as an efficient deep-blue chiral emitter and highlights C2-symmetric axial chirality as a promising molecular design strategy for high-performance CP-OLED materials.
{"title":"A C2-Symmetric Chiral Emitter for Deep-Blue Circularly Polarized Electroluminescence With High Dissymmetry Factors","authors":"Xiyun Ye, Yichao Chen, Xiaojuan Song, Tingwei Ren, Jinfeng Wang, Yujun Xie, Dongge Ma, Jishan Wu, Zhen Li","doi":"10.1002/anie.5815007","DOIUrl":"https://doi.org/10.1002/anie.5815007","url":null,"abstract":"Deep blue circularly polarized organic light-emitting diodes (CP-OLEDs) remain scarce due to the stringent requirement of simultaneously achieving a wide bandgap and strong chiroptical activity. Herein, we report <b>DC-TRZ</b>, a <i>C</i><sub>2</sub>-symmetric chiral emitter comprising a dimeric carbazole donor and a triphenyltriazine acceptor, which exhibits deep-blue emission at 433 nm with the high emission efficiency of up to 79%. Its enantiopure (<i>R</i>)- and (<i>S</i>)-isomers display pronounced Cotton effects and distinct circularly polarized luminescence (CPL). Notably, CP-OLEDs based on (<i>R</i>)- and (<i>S</i>)-<b>DC-TRZ</b> deliver deep-blue electroluminescence with Commission Internationale de L'Eclairage (CIE) coordinates of (0.14, 0.07), achieving a maximum external quantum efficiency of 4.58% and record-high luminescence dissymmetry factors of +2.7 × 10<sup>−2</sup> and −2.2 × 10<sup>−2</sup>, respectively, representing the highest values reported to date for blue CP-OLEDs employing small organic molecules. These results demonstrate that <b>DC-TRZ</b> functions as an efficient deep-blue chiral emitter and highlights <i>C</i><sub>2</sub>-symmetric axial chirality as a promising molecular design strategy for high-performance CP-OLED materials.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"98 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506945","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}
Despite active research on N-heterocyclic carbene (NHC)-protected metal nanoclusters, their development faces challenges due to limited structural and property control. Especially, the precise manipulation of structure and property of NHC-ligated alloy nanoclusters remains unexplored. Here, we present an atomistic-level model system demonstrating single-atom control in NHC-stabilized alloy nanoclusters. By varying a single copper atom with silver in Au3Cu(iPrNHCiPr)(PhC≡C)4 (Au3Cu, where iPrNHCiPr is a bidentate NHC ligand and PhC≡C is phenylacetylide), we reveal how one atomic change dramatically alters the structure, properties, and catalytic behavior of these clusters. The newly synthesized Au3Ag(iPrNHCiPr)(PhC≡C)4 retains a tetrahedral metal framework and surface coordination pattern similar to Au3Cu, yet the single-atom variation (Ag for Cu) triggers profound differences. Notably, while Au3Cu exists as a monomer, the Au3Ag clusters spontaneously dimerize, forming [Au3Ag(iPrNHCiPr)(PhC≡C)4]2 (denoted as (Au3Ag)2). Single-cluster junction conductance measurements reveal a colossal conductance difference of up to 30-fold of magnitude between the two systems. Furthermore, the (Au3Ag)2 dimer exhibits exceptional catalytic selectivity in electrocatalytic CO2 reduction, achieving a CO Faradaic efficiency of 70%—more than double that of the Au3Cu monomer. Density functional theory calculations and experimental data elucidate the origin of these dramatic structural and functional disparities induced by a single-atom change.
{"title":"One Atom Makes a Big Difference in NHC-Ligated Alloy Nanoclusters: From Structure and Properties to Catalysis","authors":"Dongjie Zuo, Chaochao Pan, Zhimin Chen, Yanli Gao, Huifang Guo, Ayisha He, Simin Li, Shuai Liu, Zhibing Tan, Qing Tang, Nanfeng Zheng, Hui Shen","doi":"10.1002/anie.8667223","DOIUrl":"https://doi.org/10.1002/anie.8667223","url":null,"abstract":"Despite active research on N-heterocyclic carbene (NHC)-protected metal nanoclusters, their development faces challenges due to limited structural and property control. Especially, the precise manipulation of structure and property of NHC-ligated alloy nanoclusters remains unexplored. Here, we present an atomistic-level model system demonstrating single-atom control in NHC-stabilized alloy nanoclusters. By varying a single copper atom with silver in Au<sub>3</sub>Cu(<sup>iPr</sup>NHC<sup>iPr</sup>)(PhC≡C)<sub>4</sub> (Au<sub>3</sub>Cu, where <sup>iPr</sup>NHC<sup>iPr</sup> is a bidentate NHC ligand and PhC≡C is phenylacetylide), we reveal how one atomic change dramatically alters the structure, properties, and catalytic behavior of these clusters. The newly synthesized Au<sub>3</sub>Ag(<sup>iPr</sup>NHC<sup>iPr</sup>)(PhC≡C)<sub>4</sub> retains a tetrahedral metal framework and surface coordination pattern similar to Au<sub>3</sub>Cu, yet the single-atom variation (Ag for Cu) triggers profound differences. Notably, while Au<sub>3</sub>Cu exists as a monomer, the Au<sub>3</sub>Ag clusters spontaneously dimerize, forming [Au<sub>3</sub>Ag(<sup>iPr</sup>NHC<sup>iPr</sup>)(PhC≡C)<sub>4</sub>]<sub>2</sub> (denoted as (Au<sub>3</sub>Ag)<sub>2</sub>). Single-cluster junction conductance measurements reveal a colossal conductance difference of up to 30-fold of magnitude between the two systems. Furthermore, the (Au<sub>3</sub>Ag)<sub>2</sub> dimer exhibits exceptional catalytic selectivity in electrocatalytic CO<sub>2</sub> reduction, achieving a CO Faradaic efficiency of 70%—more than double that of the Au<sub>3</sub>Cu monomer. Density functional theory calculations and experimental data elucidate the origin of these dramatic structural and functional disparities induced by a single-atom change.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"17 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507691","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}
Federica Pedrini, Luca Capelli, Alessandro Bertucci, Erica Del Grosso
We report here a novel strategy to achieve enzyme-mediated dissipative control over hybridization chain reaction (HCR). To achieve this, we have rationally re-engineered a reversible HCR approach so that the assembly and disassembly of DNA polymers can be transiently regulated by RNA/DNA fuel strands in combination with specific enzymatic fuel-consuming units. This strategy enables regulation over multiple cycles with precisely programmable lifetimes. Finally, we demonstrate two applications: a multi-input dissipative HCR simultaneously controlled by two different enzymes, and the transient control of a DNA-based polymeric scaffold functionalized with a light-up aptamer.
{"title":"Enzyme-Mediated Dissipative Hybridization Chain Reaction (HCR)","authors":"Federica Pedrini, Luca Capelli, Alessandro Bertucci, Erica Del Grosso","doi":"10.1002/anie.202524421","DOIUrl":"https://doi.org/10.1002/anie.202524421","url":null,"abstract":"We report here a novel strategy to achieve enzyme-mediated dissipative control over hybridization chain reaction (HCR). To achieve this, we have rationally re-engineered a reversible HCR approach so that the assembly and disassembly of DNA polymers can be transiently regulated by RNA/DNA fuel strands in combination with specific enzymatic fuel-consuming units. This strategy enables regulation over multiple cycles with precisely programmable lifetimes. Finally, we demonstrate two applications: a multi-input dissipative HCR simultaneously controlled by two different enzymes, and the transient control of a DNA-based polymeric scaffold functionalized with a light-up aptamer.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"20 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507662","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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