Jiaming Yi, Zhiwei Xing, Zhuozhi Lai, Qing Guo, Huixia Lv, Sai Wang, Qi Sun
Precise modulation of ion permselectivity in synthetic membranes is crucial for advancing separation and energy conversion technologies. Here, we demonstrate that neutral substituents can reprogram the intrinsic ion selectivity of cationic covalent organic framework (COF) membranes by introducing secondary local interactions that compete with long‐range Coulombic forces. Using triaminoguanidinium‐based COFs as a model system, we systematically varied both the number and type of substituents on 1,3,5‐trialdehyde linkers. The introduced substituents generated secondary interactions that modulated the primary Coulombic interactions between guanidinium cations and Cl – counterions. When two or more hydroxyl groups were present on the aldehyde linkers, these interactions immobilized anions and inverted the effective surface potential from positive to negative, thereby switching the transport polarity from anion‐ to cation‐selective behavior. In contrast, methoxy substitution weakened Coulombic interactions, enhancing anion selectivity. This tunable control over the local chemical microenvironment enabled programmable and reversible ion permselectivity without altering the permanent framework charge. Leveraging this mechanism, we achieved record‐high ionic thermoelectric performance, 25.9 W m −2 for a single membrane and 39.1 W m −2 for a stacked configuration under a 50 K temperature gradient. This work establishes substituent‐mediated secondary interactions as a general and powerful strategy for programming ion transport, bridging biological selectivity principles with the design of adaptive COF‐based membranes for energy harvesting and separation.
合成膜中离子选择性的精确调节对于推进分离和能量转换技术至关重要。在这里，我们证明了中性取代基可以通过引入与远程库仑力竞争的二次局部相互作用，重新编程阳离子共价有机框架（COF）膜的固有离子选择性。使用基于三胺胍的COFs作为模型系统，我们系统地改变了1,3,5 -三醛连接体上取代基的数量和类型。引入的取代基产生了二级相互作用，调节了胍离子和Cl -反离子之间的初级库仑相互作用。当两个或两个以上的羟基存在于醛连接体上时，这些相互作用固定了阴离子，并将有效表面电位从正极反转为负极，从而将传输极性从阴离子选择行为转变为阳离子选择行为。相反，甲氧基取代削弱了库仑相互作用，增强了阴离子的选择性。这种对局部化学微环境的可调控制在不改变永久框架电荷的情况下实现了可编程和可逆的离子选择性。利用这一机制，我们实现了创纪录的高离子热电性能，在50 K温度梯度下，单膜为25.9 W m−2，堆叠配置为39.1 W m−2。这项工作建立了取代基介导的二级相互作用作为一种通用的、强大的离子传输编程策略，将生物选择性原理与自适应COF基膜的设计连接起来，用于能量收集和分离。
{"title":"Substituent‐Induced Secondary Interactions Reprogram Ion Permselectivity in Cationic Covalent Organic Framework Membranes","authors":"Jiaming Yi, Zhiwei Xing, Zhuozhi Lai, Qing Guo, Huixia Lv, Sai Wang, Qi Sun","doi":"10.1002/anie.202523731","DOIUrl":"https://doi.org/10.1002/anie.202523731","url":null,"abstract":"Precise modulation of ion permselectivity in synthetic membranes is crucial for advancing separation and energy conversion technologies. Here, we demonstrate that neutral substituents can reprogram the intrinsic ion selectivity of cationic covalent organic framework (COF) membranes by introducing secondary local interactions that compete with long‐range Coulombic forces. Using triaminoguanidinium‐based COFs as a model system, we systematically varied both the number and type of substituents on 1,3,5‐trialdehyde linkers. The introduced substituents generated secondary interactions that modulated the primary Coulombic interactions between guanidinium cations and Cl <jats:sup>–</jats:sup> counterions. When two or more hydroxyl groups were present on the aldehyde linkers, these interactions immobilized anions and inverted the effective surface potential from positive to negative, thereby switching the transport polarity from anion‐ to cation‐selective behavior. In contrast, methoxy substitution weakened Coulombic interactions, enhancing anion selectivity. This tunable control over the local chemical microenvironment enabled programmable and reversible ion permselectivity without altering the permanent framework charge. Leveraging this mechanism, we achieved record‐high ionic thermoelectric performance, 25.9 W m <jats:sup>−2</jats:sup> for a single membrane and 39.1 W m <jats:sup>−</jats:sup> <jats:sup>2</jats:sup> for a stacked configuration under a 50 K temperature gradient. This work establishes substituent‐mediated secondary interactions as a general and powerful strategy for programming ion transport, bridging biological selectivity principles with the design of adaptive COF‐based membranes for energy harvesting and separation.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"90 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098158","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}
Lu Gao, Chaofan Yuan, Wenying Yu, Sheng Guo, Na Tian, Xiaolei Zhang, Yihe Zhang, Hongwei Huang
The simultaneous production of hydrogen (H 2 ) and hydrogen peroxide (H 2 O 2 ) from pure water represents an ideal solar‐to‐chemical pathway for sustainable fuel and oxidant generation. However, conventional photocatalysts face intrinsic limitations, including sluggish carrier dynamics and insufficient power for water oxidation. Herein, we unveil an intramolecular electron transfer pathway from cyano groups to hydroxyl groups in C 3 N 5 that creates a high‐performance piezo‐photocatalyst for water splitting. The hydroxyl/cyano groups direct electron‐hole flow, optimizing the surface potential and dipole moment (DM) for a stronger piezoelectric response. Interestingly, the piezoelectric polarization induced by mechanical strain in MCN‐8 enhances its H + desorption ability to facilitate a rapid adsorption‐reaction‐desorption process. In situ infrared spectroscopy results indicate that MCN‐8 generates key substances such as ·O 2− and ·OOH, clarifying the water oxidation process. Thus, the rates of H 2 and H 2 O 2 release by its piezo‐photocatalysis were 4.14 mmol g −1 h −1 and 1.39 mmol g −1 h −1 , respectively. Under simulated outdoor sunlight and ultrasonic conditions, the as‐fabricated MCN‐8/PVDF‐HFP composite film retains its ability to produce H 2 and H 2 O 2 . This strategy of enhancing the piezo‐photocatalytic performance through surface group modulation provides a new idea for the development of highly efficient and multifunctional water decomposition catalysts.
{"title":"Piezoelectric Polarization Optimized Photocharge Separation and Surface Proton Cycling for Efficient Pure Water Splitting","authors":"Lu Gao, Chaofan Yuan, Wenying Yu, Sheng Guo, Na Tian, Xiaolei Zhang, Yihe Zhang, Hongwei Huang","doi":"10.1002/anie.202525592","DOIUrl":"https://doi.org/10.1002/anie.202525592","url":null,"abstract":"The simultaneous production of hydrogen (H <jats:sub>2</jats:sub> ) and hydrogen peroxide (H <jats:sub>2</jats:sub> O <jats:sub>2</jats:sub> ) from pure water represents an ideal solar‐to‐chemical pathway for sustainable fuel and oxidant generation. However, conventional photocatalysts face intrinsic limitations, including sluggish carrier dynamics and insufficient power for water oxidation. Herein, we unveil an intramolecular electron transfer pathway from cyano groups to hydroxyl groups in C <jats:sub>3</jats:sub> N <jats:sub>5</jats:sub> that creates a high‐performance piezo‐photocatalyst for water splitting. The hydroxyl/cyano groups direct electron‐hole flow, optimizing the surface potential and dipole moment (DM) for a stronger piezoelectric response. Interestingly, the piezoelectric polarization induced by mechanical strain in MCN‐8 enhances its H <jats:sup>+</jats:sup> desorption ability to facilitate a rapid adsorption‐reaction‐desorption process. In situ infrared spectroscopy results indicate that MCN‐8 generates key substances such as ·O <jats:sub>2</jats:sub> <jats:sup>−</jats:sup> and ·OOH, clarifying the water oxidation process. Thus, the rates of H <jats:sub>2</jats:sub> and H <jats:sub>2</jats:sub> O <jats:sub>2</jats:sub> release by its piezo‐photocatalysis were 4.14 mmol g <jats:sup>−1</jats:sup> h <jats:sup>−1</jats:sup> and 1.39 mmol g <jats:sup>−1</jats:sup> h <jats:sup>−1</jats:sup> , respectively. Under simulated outdoor sunlight and ultrasonic conditions, the as‐fabricated MCN‐8/PVDF‐HFP composite film retains its ability to produce H <jats:sub>2</jats:sub> and H <jats:sub>2</jats:sub> O <jats:sub>2</jats:sub> . This strategy of enhancing the piezo‐photocatalytic performance through surface group modulation provides a new idea for the development of highly efficient and multifunctional water decomposition catalysts.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098159","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}
Christiane Huhn, Clémence Mille, Sheng-Yang Ho, Felix Lützenkirchen, Vladimir Khayenko, Melanie Hein, Christian Werner, Matthias Kneussel, Johannes W. Hell, Christian G. Specht, Hans M. Maric
Direct visualization of postsynaptic scaffolds in living neurons is essential for dissecting synaptic dynamics and plasticity. Existing methods for live synapse visualization have major constraints, relying on genetic engineering or multistep application of live-cell incompatible antibodies or nanobodies. Available affinity probes and delivery strategies lack the required contrast due to incomplete or excess delivery. Here, we introduce Sylives, a set of compact, synthetic fluorescent peptides that enable high-contrast live imaging of inhibitory (gephyrin) and excitatory (PSD-95) postsynaptic scaffolds in native neurons. Critically, by pre-purification of the redox-cleavable CPP-probe conjugate we overcome side-product formation of in-situ coupling strategies, achieving reliable cytosolic delivery and restored scaffold binding after intracellular reduction. The Sylive design addresses the need for nanomolar probe levels versus micromolar CPP for clean labelling and efficient delivery by decoupling targeting and uptake. Through quantitative evaluation of uptake and off-target binding, we defined a transferrable parameter space for effective intracellular delivery. Near traceless Sylive uptake and target specificity are validated by direct comparison to transiently expressed proteins and immunolabeling in fixed neurons. The reduction-sensitive Sylive conjugates enable high-contrast, specificity-restored labelling of endogenous postsynaptic sites without genetic modification and offer a modular platform for targeting alternative intracellular proteins in living primary neurons.
{"title":"Redox-Activated Probes Enable High-Contrast Live Imaging of Native Postsynaptic Scaffolds","authors":"Christiane Huhn, Clémence Mille, Sheng-Yang Ho, Felix Lützenkirchen, Vladimir Khayenko, Melanie Hein, Christian Werner, Matthias Kneussel, Johannes W. Hell, Christian G. Specht, Hans M. Maric","doi":"10.1002/anie.202519933","DOIUrl":"https://doi.org/10.1002/anie.202519933","url":null,"abstract":"Direct visualization of postsynaptic scaffolds in living neurons is essential for dissecting synaptic dynamics and plasticity. Existing methods for live synapse visualization have major constraints, relying on genetic engineering or multistep application of live-cell incompatible antibodies or nanobodies. Available affinity probes and delivery strategies lack the required contrast due to incomplete or excess delivery. Here, we introduce Sylives, a set of compact, synthetic fluorescent peptides that enable high-contrast live imaging of inhibitory (gephyrin) and excitatory (PSD-95) postsynaptic scaffolds in native neurons. Critically, by pre-purification of the redox-cleavable CPP-probe conjugate we overcome side-product formation of in-situ coupling strategies, achieving reliable cytosolic delivery and restored scaffold binding after intracellular reduction. The Sylive design addresses the need for nanomolar probe levels versus micromolar CPP for clean labelling and efficient delivery by decoupling targeting and uptake. Through quantitative evaluation of uptake and off-target binding, we defined a transferrable parameter space for effective intracellular delivery. Near traceless Sylive uptake and target specificity are validated by direct comparison to transiently expressed proteins and immunolabeling in fixed neurons. The reduction-sensitive Sylive conjugates enable high-contrast, specificity-restored labelling of endogenous postsynaptic sites without genetic modification and offer a modular platform for targeting alternative intracellular proteins in living primary neurons.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"41 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098246","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 (PE) materials are indispensable to modern infrastructure due to their exceptional thermal, mechanical, and chemical resilience. However, the same properties that make these materials durable also render them environmentally persistent and unrecyclable by conventional means, posing a critical sustainability challenge. Here, we report a mechanochemically triggered, chemically recyclable PE-like system that enables the closed-loop recycling of cross-linked polyethylene (XLPE). Through palladium-catalyzed coordination copolymerization of ethylene with the cyclobutene-fused ester (CBE) comonomer, polar PE-like materials with tunable properties are achieved. Upon optimal mechanical activation in the presence of a radical inhibitor, the CBE units undergo ring opening, installing ester linkages into the polymer backbone. Notably, the high crystallinity of copolymers with low CBE content enables ball-milling to achieve activation efficiency comparable to cryo-milling. Subsequent ethanolysis of ester linkages cleanly converts the initial copolymer into multifunctional oligomers, which can be repolymerized after hydrogenation via transesterification to yield a recyclable XLPE with properties comparable to a commercial analogue. This work demonstrates a robust platform for reconciling the durability and recyclability of polyethylene, offering a transformative route toward sustainable polyolefins.
{"title":"Mechanically Triggered Chemical Recyclable Polyethylene-Like Materials","authors":"Menghe Xu, Peng Liu, Changle Chen, Tae-Lim Choi","doi":"10.1002/anie.202522618","DOIUrl":"https://doi.org/10.1002/anie.202522618","url":null,"abstract":"Polyethylene (PE) materials are indispensable to modern infrastructure due to their exceptional thermal, mechanical, and chemical resilience. However, the same properties that make these materials durable also render them environmentally persistent and unrecyclable by conventional means, posing a critical sustainability challenge. Here, we report a mechanochemically triggered, chemically recyclable PE-like system that enables the closed-loop recycling of cross-linked polyethylene (XLPE). Through palladium-catalyzed coordination copolymerization of ethylene with the cyclobutene-fused ester (CBE) comonomer, polar PE-like materials with tunable properties are achieved. Upon optimal mechanical activation in the presence of a radical inhibitor, the CBE units undergo ring opening, installing ester linkages into the polymer backbone. Notably, the high crystallinity of copolymers with low CBE content enables ball-milling to achieve activation efficiency comparable to cryo-milling. Subsequent ethanolysis of ester linkages cleanly converts the initial copolymer into multifunctional oligomers, which can be repolymerized after hydrogenation via transesterification to yield a recyclable XLPE with properties comparable to a commercial analogue. This work demonstrates a robust platform for reconciling the durability and recyclability of polyethylene, offering a transformative route toward sustainable polyolefins.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"253 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098270","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}
Wanting Yu, Chenzi Li, Xiaoya Zhao, Man Zhang, Wenyan Ye, Yulong Shi, Bo Wu, Hao Sun, Liangliang Zhu
Time-dependent multicolor afterglow enables temporal encoding of naked-eye distinguishable optical signals that cannot be achieved with static luminescence. However, available strategies to control the wavelength and color of time-dependent multicolor afterglow remain highly limited. Herein, we propose a conformation-resolved molecular design that successfully unlocks intrinsic dual-phosphorescence characteristics in single-luminogen systems, enabling dynamically color-tunable afterglow within the polymer matrix. Our strategy integrates flexible C–S–C rotors into a rigid pyrene core, allowing simultaneous stabilization of distinct emissive conformers with different triplet energy levels, specifically, a parallel conformer that can produce red phosphorescence and a perpendicular one yielding green phosphorescence. The asynchronous decay of these phosphorescent afterglows results in a visually perceptible emission color transition from red to yellow, and finally to green over a naked-eye distinguishable time scale, representing a rare paradigm of intrinsic, conformation-mediated dual-phosphorescence. Moreover, our systems are able to exhibit remarkable resistance to water, acids/bases, and organic solvents, as well as intrinsic UV-shielding capabilities, demonstrating that the time-dependent multicolor afterglow can readily integrate with diverse material functionalities, and is thus well suited for a wide range of application scenarios.
{"title":"Conformation-Resolved Single-Luminogen Systems for Time-Dependent Multicolor Afterglow","authors":"Wanting Yu, Chenzi Li, Xiaoya Zhao, Man Zhang, Wenyan Ye, Yulong Shi, Bo Wu, Hao Sun, Liangliang Zhu","doi":"10.1002/anie.1607487","DOIUrl":"https://doi.org/10.1002/anie.1607487","url":null,"abstract":"Time-dependent multicolor afterglow enables temporal encoding of naked-eye distinguishable optical signals that cannot be achieved with static luminescence. However, available strategies to control the wavelength and color of time-dependent multicolor afterglow remain highly limited. Herein, we propose a conformation-resolved molecular design that successfully unlocks intrinsic dual-phosphorescence characteristics in single-luminogen systems, enabling dynamically color-tunable afterglow within the polymer matrix. Our strategy integrates flexible C–S–C rotors into a rigid pyrene core, allowing simultaneous stabilization of distinct emissive conformers with different triplet energy levels, specifically, a parallel conformer that can produce red phosphorescence and a perpendicular one yielding green phosphorescence. The asynchronous decay of these phosphorescent afterglows results in a visually perceptible emission color transition from red to yellow, and finally to green over a naked-eye distinguishable time scale, representing a rare paradigm of intrinsic, conformation-mediated dual-phosphorescence. Moreover, our systems are able to exhibit remarkable resistance to water, acids/bases, and organic solvents, as well as intrinsic UV-shielding capabilities, demonstrating that the time-dependent multicolor afterglow can readily integrate with diverse material functionalities, and is thus well suited for a wide range of application scenarios.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"96 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098272","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The design of dual organic room-temperature phosphorescence (RTP) from both the host and guest remains a significant challenge, as most organic doping systems generally enable either the guest or the host to serve as a single static phosphorescent emitter. Here we report a host–guest dual RTP system featuring dynamically tunable colors, controllable host-to-guest phosphorescence ratios, and widely tunable lifetimes of 18.8–472 ms. This unique performance is enabled by bidirectional triplet energy transfer processes between host and guest, which not only activates RTP of the host molecules but also induces a blue shift of the phosphorescence from 673 to 528 nm, with CIE chromaticity coordinates ranging from (0.51, 0.45) to (0.40, 0.57). More importantly, alkyl ring groups effectively modulate the triplet energy levels of the identical π-conjugated host molecules at the aggregate level, resulting in the lowest triplet energy levels of host crystals ranging from 2.88 to 2.53 eV. This work provides a unique insight into achieving dual RTP in organic doping systems and holds great potential for applications in multilevel information encryption and optoelectronics research.
{"title":"Dynamic Color-Tunable Dual Room Temperature Phosphorescence via Activation of Both Host and Guest Triplet States","authors":"Yin Zhou, Chenxu Xia, Gaolin Li, Yong Liu, Ting Xiang, Fengyun Xie, Zhan Yang, Wenbin Zhong, Zhenguo Chi, Chengjian Chen","doi":"10.1002/anie.5567761","DOIUrl":"https://doi.org/10.1002/anie.5567761","url":null,"abstract":"The design of dual organic room-temperature phosphorescence (RTP) from both the host and guest remains a significant challenge, as most organic doping systems generally enable either the guest or the host to serve as a single static phosphorescent emitter. Here we report a host–guest dual RTP system featuring dynamically tunable colors, controllable host-to-guest phosphorescence ratios, and widely tunable lifetimes of 18.8–472 ms. This unique performance is enabled by bidirectional triplet energy transfer processes between host and guest, which not only activates RTP of the host molecules but also induces a blue shift of the phosphorescence from 673 to 528 nm, with CIE chromaticity coordinates ranging from (0.51, 0.45) to (0.40, 0.57). More importantly, alkyl ring groups effectively modulate the triplet energy levels of the identical π-conjugated host molecules at the aggregate level, resulting in the lowest triplet energy levels of host crystals ranging from 2.88 to 2.53 eV. This work provides a unique insight into achieving dual RTP in organic doping systems and holds great potential for applications in multilevel information encryption and optoelectronics research.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"17 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098274","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}
Liang Ren, Jinrui Song, Nan Zhang, Yafei Guo, Nelson Belzile, Tianlong Deng
Biological ion channels can achieve high ion discrimination through the synergy between pore structure and microenvironment. However, constructing biomimetic ion-sieving membranes with precise recognition capabilities for target ions remains challenging. Herein, we propose a rotaxane-induced stacking method for constructing COF membranes integrated with ion-recognition sub-nanoscale channels. The dibenzo-crown ether rotaxane COF (CRCOF) nanosheets are fabricated and subsequently stacked into membranes. Driven by π–π interactions between rotaxane moieties and CRCOF nanosheets, as well as the specific ion-recognition ability of rotaxanes, the nanosheets undergo oriented stacking, yielding well-defined sub-nanoscale channels equipped with recognition sites. The angstrom-scale pore size and specific binding channels synergistically enhance selectivity and minimize transport energy penalties of target ions. By modulating the ion recognition capability of channels, the obtained CRCOF membrane demonstrates an exceptional Li+ permeation rate of 0.04 mol m−2 h−1 (approximately five times higher than reported polymer membranes) and high Li+ selectivity (Li+/Mg2+ selectivity of 315 and Li+/Na+ selectivity of 12) in a mixture solution. This work provides a new avenue for the accurate construction of biomimetic ion-sieving membranes and offers new insights into the mechanisms of high-efficiency ion separation in sub-nanoscale confined recognition channels.
{"title":"Crown Ether Rotaxane-Induced Construction of COF Membranes With Recognition Channels for High-Efficiency Ion Sieving","authors":"Liang Ren, Jinrui Song, Nan Zhang, Yafei Guo, Nelson Belzile, Tianlong Deng","doi":"10.1002/anie.202525413","DOIUrl":"https://doi.org/10.1002/anie.202525413","url":null,"abstract":"Biological ion channels can achieve high ion discrimination through the synergy between pore structure and microenvironment. However, constructing biomimetic ion-sieving membranes with precise recognition capabilities for target ions remains challenging. Herein, we propose a rotaxane-induced stacking method for constructing COF membranes integrated with ion-recognition sub-nanoscale channels. The dibenzo-crown ether rotaxane COF (CRCOF) nanosheets are fabricated and subsequently stacked into membranes. Driven by π–π interactions between rotaxane moieties and CRCOF nanosheets, as well as the specific ion-recognition ability of rotaxanes, the nanosheets undergo oriented stacking, yielding well-defined sub-nanoscale channels equipped with recognition sites. The angstrom-scale pore size and specific binding channels synergistically enhance selectivity and minimize transport energy penalties of target ions. By modulating the ion recognition capability of channels, the obtained CRCOF membrane demonstrates an exceptional Li<sup>+</sup> permeation rate of 0.04 mol m<sup>−2</sup> h<sup>−1</sup> (approximately five times higher than reported polymer membranes) and high Li<sup>+</sup> selectivity (Li<sup>+</sup>/Mg<sup>2+</sup> selectivity of 315 and Li<sup>+</sup>/Na<sup>+</sup> selectivity of 12) in a mixture solution. This work provides a new avenue for the accurate construction of biomimetic ion-sieving membranes and offers new insights into the mechanisms of high-efficiency ion separation in sub-nanoscale confined recognition channels.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"80 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098235","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}
Damien W. Chen, Tejas Deshpande, Sybille Collignon, Farzaneh Fadaei-Tirani, Sascha Feldmann, Kay Severin
A metal-organic cage was obtained by combining acridone-based dipyridyl ligands with Pd2+ ions. The cage acts as a potent receptor for squaraine dyes, with a pronounced preference for guests with 2,6-dihydroxyphenyl substituents. This selectivity profile differs from that of previously reported receptors for squaraine dyes. The acridone-based cage itself is non-emissive. Upon its photoexcitation, ultrafast (sub-ps) dark resonance energy transfer (DRET) to the encapsulated squaraine dyes was observed, resulting in bright, near-infrared guest emission, with pseudo-Stokes shifts of up to 440 nm. Upon binding of a chiral dye, chirality transfer to the host could be evidenced by circular dichroism spectroscopy.
{"title":"A Metallosupramolecular Receptor for Squaraine Dyes Enabling Ultrafast Dark Resonance Energy Transfer","authors":"Damien W. Chen, Tejas Deshpande, Sybille Collignon, Farzaneh Fadaei-Tirani, Sascha Feldmann, Kay Severin","doi":"10.1002/anie.2203782","DOIUrl":"https://doi.org/10.1002/anie.2203782","url":null,"abstract":"A metal-organic cage was obtained by combining acridone-based dipyridyl ligands with Pd<sup>2+</sup> ions. The cage acts as a potent receptor for squaraine dyes, with a pronounced preference for guests with 2,6-dihydroxyphenyl substituents. This selectivity profile differs from that of previously reported receptors for squaraine dyes. The acridone-based cage itself is non-emissive. Upon its photoexcitation, ultrafast (sub-ps) dark resonance energy transfer (DRET) to the encapsulated squaraine dyes was observed, resulting in bright, near-infrared guest emission, with pseudo-Stokes shifts of up to 440 nm. Upon binding of a chiral dye, chirality transfer to the host could be evidenced by circular dichroism spectroscopy.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"5 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098248","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 Pan, Chunxiang Li, Pengwei Huo, Yubao Zhao, Weidong Shi, Yifan Zhang, Yongxian Guo, Yan Yan
Hydrogen-bonded water clusters (H2O)n obscure the intrinsic reactivity of monomeric H2O (n = 1) by restricting molecular reorientation. Elucidating the catalytic behavior of isolated water remains a key challenge in aqueous-phase chemistry. Here, we address this by designing a molecular crystal that uniformly confines single water molecules in identical tetrahedral cavities. This platform, CB-H2O, exhibits exceptional activity for photocatalytic H2O-to-H2O2 conversion, achieving 7.03 mmol g−1 h−1 with pure water, representing an 11.6-fold enhancement over cavity-deficient controls and being markedly superior to existing photocatalytic systems. This performance advantage is directly attributed to the crystallographically defined monomeric water, as verified by isotopic labelling and in-situ spectroscopy. Theoretical calculations further demonstrate that cavity confinement eliminates hydrogen-bond reorganization penalties, substantially lowering the activation barrier for water oxidation. Our work establishes monomeric-water catalysis as a distinct and efficient paradigm, showcasing molecular crystal engineering as a versatile approach to tailoring water-involved reactions for sustainable catalysis.
{"title":"Confining a Single Water Molecule Through Molecular Crystal Engineering for Water Oxidation","authors":"Long Pan, Chunxiang Li, Pengwei Huo, Yubao Zhao, Weidong Shi, Yifan Zhang, Yongxian Guo, Yan Yan","doi":"10.1002/anie.202525362","DOIUrl":"https://doi.org/10.1002/anie.202525362","url":null,"abstract":"Hydrogen-bonded water clusters (H<sub>2</sub>O)<sub>n</sub> obscure the intrinsic reactivity of monomeric H<sub>2</sub>O (n = 1) by restricting molecular reorientation. Elucidating the catalytic behavior of isolated water remains a key challenge in aqueous-phase chemistry. Here, we address this by designing a molecular crystal that uniformly confines single water molecules in identical tetrahedral cavities. This platform, <b>CB-H<sub>2</sub>O</b>, exhibits exceptional activity for photocatalytic H<sub>2</sub>O-to-H<sub>2</sub>O<sub>2</sub> conversion, achieving 7.03 mmol g<sup>−</sup><sup>1</sup> h<sup>−</sup><sup>1</sup> with pure water, representing an 11.6-fold enhancement over cavity-deficient controls and being markedly superior to existing photocatalytic systems. This performance advantage is directly attributed to the crystallographically defined monomeric water, as verified by isotopic labelling and in-situ spectroscopy. Theoretical calculations further demonstrate that cavity confinement eliminates hydrogen-bond reorganization penalties, substantially lowering the activation barrier for water oxidation. Our work establishes monomeric-water catalysis as a distinct and efficient paradigm, showcasing molecular crystal engineering as a versatile approach to tailoring water-involved reactions for sustainable catalysis.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"285 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098249","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}
Nikita I. Kolomoets, Daniil A. Boiko, Leonid V. Romashov, Kirill S. Kozlov, Evgeniy G. Gordeev, Alexey S. Galushko, Valentine P. Ananikov
The discovery of new chemical transformations is central to advancing modern chemistry, yet conventional approaches often require months or years of extensive experimental screening. Here, we present a machine-learning-assisted and expert-guided pipeline for reaction discovery applied to the search for atom-economic cycloaddition reactions. Candidate reactions were generated from publicly available quantum chemical data, filtered through unsupervised machine learning, and clustered to reduce redundancy. A digital co-expert then enabled rapid prioritization, after which human expertise provided final selection and experimental validation. This hybrid workflow is fully compatible with current laboratory infrastructure and addresses the most time-consuming stage of reaction discovery, accelerating the expert screening bottleneck by approximately 180-fold (from > 1200 days to 7 days). Within ∼1 week, two novel cycloaddition reactions were identified and experimentally confirmed, yielding previously undescribed products. While fully autonomous robotic platforms represent a long-term vision, their high cost and limited availability restrict immediate application. In contrast, our approach demonstrates the practicality of human-AI collaboration for reaction discovery, combining computational screening, machine learning and expert knowledge to efficiently expand the accessible chemical space.
{"title":"Reaction Discovery Involving Digital co-Expert with a Practical Application in Atom-Economic Cycloaddition","authors":"Nikita I. Kolomoets, Daniil A. Boiko, Leonid V. Romashov, Kirill S. Kozlov, Evgeniy G. Gordeev, Alexey S. Galushko, Valentine P. Ananikov","doi":"10.1002/anie.202523905","DOIUrl":"https://doi.org/10.1002/anie.202523905","url":null,"abstract":"The discovery of new chemical transformations is central to advancing modern chemistry, yet conventional approaches often require months or years of extensive experimental screening. Here, we present a machine-learning-assisted and expert-guided pipeline for reaction discovery applied to the search for atom-economic cycloaddition reactions. Candidate reactions were generated from publicly available quantum chemical data, filtered through unsupervised machine learning, and clustered to reduce redundancy. A digital co-expert then enabled rapid prioritization, after which human expertise provided final selection and experimental validation. This hybrid workflow is fully compatible with current laboratory infrastructure and addresses the most time-consuming stage of reaction discovery, accelerating the expert screening bottleneck by approximately 180-fold (from > 1200 days to 7 days). Within ∼1 week, two novel cycloaddition reactions were identified and experimentally confirmed, yielding previously undescribed products. While fully autonomous robotic platforms represent a long-term vision, their high cost and limited availability restrict immediate application. In contrast, our approach demonstrates the practicality of human-AI collaboration for reaction discovery, combining computational screening, machine learning and expert knowledge to efficiently expand the accessible chemical space.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"37 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098271","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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