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}
Jie Zhang, Yuehui Li, Liman Huo, Bing Yin, Yudi Wang, Qingshun Dong, Guozhen Liu, Xin Lu, Wenqi Han, Wenrui Li, Yilin Gao, Zheng Lv, Zhiyong Wang, Lida Liu, Yantao Shi
Self-assembled monolayers (SAM) have demonstrated significant potential for enhancing the performance of perovskite solar cells (PSCs). However, their incomplete surface coverage exposes defect sites on the NiOx surface, leading to detrimental non-radiative recombination and exacerbating the perovskite degradation. To overcome these limitations, we developed a strategy of area-selective atomic layer deposition (AS-ALD) that precisely deposits an ultrathin AlOx layer on exposed NiOx surfaces while preserving SAM-covered areas. This approach effectively suppresses charge recombination by blocking direct contact between NiOx and the perovskite while leveraging the intrinsic negative fixed charges in AlOx to attract holes and repel electrons. Importantly, the SAM-covered areas remain unaffected, ensuring unhindered carrier extraction. Additionally, the deposited AlOx reduces the deleterious Ni4+ content, which can readily trigger perovskite decomposition, thereby significantly enhancing device performance and stability. As a result, the PCE of PSCs increased to 26.41%, with perovskite modules achieving 20.88% efficiency over a 64.68 cm2 active area. Device stability significantly improved with ∼ 95% initial PCE retained after 1500 h dark storage (ISOS-D-1), ∼ 80% after 800 h at 85°C (ISOS-D-2), ∼ 85% after 48 thermal cycles (ISOS-T-1), and ∼ 90% after 1300 h continuous 1-sun illumination (ISOS-L-1, MPPT).
自组装单层膜（SAM）在提高钙钛矿太阳能电池（PSCs）性能方面表现出了巨大的潜力。然而，它们不完全的表面覆盖暴露了NiOx表面的缺陷位点，导致有害的非辐射重组并加剧了钙钛矿的降解。为了克服这些限制，我们开发了一种区域选择性原子层沉积（AS-ALD）策略，可以在暴露的NiOx表面上精确沉积超薄AlOx层，同时保留sam覆盖的区域。这种方法通过阻断NiOx与钙钛矿之间的直接接触，有效地抑制了电荷重组，同时利用AlOx中固有的负固定电荷吸引空穴和排斥电子。重要的是，地对空导弹覆盖的区域不受影响，确保了不受阻碍的载体提取。此外，沉积的AlOx降低了有害的Ni4+含量，Ni4+很容易引发钙钛矿分解，从而显著提高了器件的性能和稳定性。结果，PSCs的PCE提高到26.41%，钙钛矿组件在64.68 cm2的活性面积上达到20.88%的效率。器件稳定性显著提高，在1500小时暗储存后初始PCE保留了~ 95% (iso - d -1)，在85°C下800小时后保留了~ 80% (iso - d -2)，在48个热循环后保留了~ 85% (iso - t -1)，在1300小时连续1个太阳照射后保留了~ 90% （iso - l -1， MPPT）。
{"title":"Area-Selective Atomic Layer Deposition of AlOx at the Buried Interface for High-Performance Perovskite Solar Cells","authors":"Jie Zhang, Yuehui Li, Liman Huo, Bing Yin, Yudi Wang, Qingshun Dong, Guozhen Liu, Xin Lu, Wenqi Han, Wenrui Li, Yilin Gao, Zheng Lv, Zhiyong Wang, Lida Liu, Yantao Shi","doi":"10.1002/anie.202516537","DOIUrl":"https://doi.org/10.1002/anie.202516537","url":null,"abstract":"Self-assembled monolayers (SAM) have demonstrated significant potential for enhancing the performance of perovskite solar cells (PSCs). However, their incomplete surface coverage exposes defect sites on the NiO<sub>x</sub> surface, leading to detrimental non-radiative recombination and exacerbating the perovskite degradation. To overcome these limitations, we developed a strategy of area-selective atomic layer deposition (AS-ALD) that precisely deposits an ultrathin AlO<sub>x</sub> layer on exposed NiO<sub>x</sub> surfaces while preserving SAM-covered areas. This approach effectively suppresses charge recombination by blocking direct contact between NiO<sub>x</sub> and the perovskite while leveraging the intrinsic negative fixed charges in AlO<sub>x</sub> to attract holes and repel electrons. Importantly, the SAM-covered areas remain unaffected, ensuring unhindered carrier extraction. Additionally, the deposited AlO<sub>x</sub> reduces the deleterious Ni<sup>4+</sup> content, which can readily trigger perovskite decomposition, thereby significantly enhancing device performance and stability. As a result, the PCE of PSCs increased to 26.41%, with perovskite modules achieving 20.88% efficiency over a 64.68 cm<sup>2</sup> active area. Device stability significantly improved with ∼ 95% initial PCE retained after 1500 h dark storage (ISOS-D-1), ∼ 80% after 800 h at 85°C (ISOS-D-2), ∼ 85% after 48 thermal cycles (ISOS-T-1), and ∼ 90% after 1300 h continuous 1-sun illumination (ISOS-L-1, MPPT).","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"2 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098273","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}
Catalysis of the conversion of CO2 from industrial exhaust gases to methanol at dynamically varying concentrations using renewable electrical energy is crucial for reducing CO2 emissions and producing valuable chemical feedstocks. However, the challenges associated with the weak activation of linear nonpolar CO2 molecules and the high energy difference of key proton-coupled electron transfer steps make it difficult for existing catalysts to simultaneously achieve a high current density and a high selectivity. Herein, we report a strategy for regulating electron polarization in a Cu single-atom catalyst (CuN3-C) to achieve efficient electrocatalytic reduction of high- and low-concentration CO2 to CH3OH. For both high-concentration or low-concentration CO2 used as the feedstock, the CuN3-C catalyst achieves a current density exceeding -450 mA cm-2, a Faradaic efficiency of 80% for methanol production, and record-high production rate of 0.57 µmol s-1 cm-2. In situ characterization and theoretical calculations jointly show that strong electron polarization of the CuN3-C catalyst facilitates more effective CO2 activation and preferential *CO hydrogenation toward *CHO and *CHOH. This study provides a strategy for designing highly efficient catalysts for the conversion of CO2 to methanol via electronic polarization modulation.
利用可再生电能催化工业废气中二氧化碳以动态变化的浓度转化为甲醇，对于减少二氧化碳排放和生产有价值的化学原料至关重要。然而，线性非极性CO2分子的弱活化和关键质子耦合电子转移步骤的高能量差带来的挑战使得现有催化剂难以同时实现高电流密度和高选择性。在此，我们报道了一种调节Cu单原子催化剂（CuN3-C）中电子极化的策略，以实现高效的电催化将高浓度和低浓度CO2还原为CH3OH。对于高浓度或低浓度的CO2作为原料，CuN3-C催化剂的电流密度都超过-450 mA cm-2，甲醇生产的法拉第效率达到80%，产量达到创纪录的0.57µmol s-1 cm-2。原位表征和理论计算共同表明，CuN3-C催化剂的强电子极化有利于更有效的CO2活化，有利于*CO向*CHO和*CHOH加氢。本研究为设计通过电子极化调制将二氧化碳转化为甲醇的高效催化剂提供了一种策略。
{"title":"Electron Cloud Polarization of Single-Atom Cu Boosts Electrocatalytic Reduction of High- and Low-Concentration CO2 to Methanol.","authors":"Guodong Sun,Yingfei Ma,Yanan Cao,Hsiao-Tsu Wang,Deqing Li,Mengchen Sun,Chi-Feng Lee,Chieh-Kai Hsu,Ying-Rui Lu,Wei Zhang,Lili Han","doi":"10.1002/anie.202523844","DOIUrl":"https://doi.org/10.1002/anie.202523844","url":null,"abstract":"Catalysis of the conversion of CO2 from industrial exhaust gases to methanol at dynamically varying concentrations using renewable electrical energy is crucial for reducing CO2 emissions and producing valuable chemical feedstocks. However, the challenges associated with the weak activation of linear nonpolar CO2 molecules and the high energy difference of key proton-coupled electron transfer steps make it difficult for existing catalysts to simultaneously achieve a high current density and a high selectivity. Herein, we report a strategy for regulating electron polarization in a Cu single-atom catalyst (CuN3-C) to achieve efficient electrocatalytic reduction of high- and low-concentration CO2 to CH3OH. For both high-concentration or low-concentration CO2 used as the feedstock, the CuN3-C catalyst achieves a current density exceeding -450 mA cm-2, a Faradaic efficiency of 80% for methanol production, and record-high production rate of 0.57 µmol s-1 cm-2. In situ characterization and theoretical calculations jointly show that strong electron polarization of the CuN3-C catalyst facilitates more effective CO2 activation and preferential *CO hydrogenation toward *CHO and *CHOH. This study provides a strategy for designing highly efficient catalysts for the conversion of CO2 to methanol via electronic polarization modulation.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"81 1","pages":"e23844"},"PeriodicalIF":16.6,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089058","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}
Ansalna K Rasheed,Rinsha Cholasseri,Shahna Mysin K,Joel G Reji,Kethavath Hemanth Naik,Fathima Salah,K R Krishnadas,Susmita De,Jerry A Fereiro
Protein-templated metal nanoclusters (MNCs) offer a unique strategy for integrating the structural precision of biological scaffolds with the quantum electronic characteristics of atomically precise metallic cores. Despite this promise, the fundamental principles governing charge transport in such biohybrid systems remain limited. Here, we report a systematic investigation of electron transport in Au/BSA-MNCs/Au Nanowire junctions incorporating a series of bovine serum albumin (BSA)-templated metal nanoclusters of copper, silver, and gold (CuNC, AgNC, and AuNC). Incorporation of MNCs yields up to a 17-fold increase in current relative to native BSA junctions. The conductivity follows the trend AuNC > AgNC > CuNC, a disparity that fragment-level Density Functional Theory (DFT) analysis attributes to the greater structural robustness and enhanced orbital delocalization of AuNC and AgNC, which together facilitate stronger electronic coupling with proximal protein residues. Temperature-dependent charge transport measurements (I-V-T) further reveal a systematic evolution from tunneling-dominated to increasingly band-like transport across the BSA-MNC series, governed by the extent of electronic delocalization imparted by the metal core. Collectively, these findings provide molecular-level insight into charge transport in protein-templated MNCs and establish structure-property design principles for the next-generation bioelectronic materials.
{"title":"Deciphering the Transition From Tunneling to Band-Like Transport in Protein-Templated Biohybrid Junctions.","authors":"Ansalna K Rasheed,Rinsha Cholasseri,Shahna Mysin K,Joel G Reji,Kethavath Hemanth Naik,Fathima Salah,K R Krishnadas,Susmita De,Jerry A Fereiro","doi":"10.1002/anie.202525930","DOIUrl":"https://doi.org/10.1002/anie.202525930","url":null,"abstract":"Protein-templated metal nanoclusters (MNCs) offer a unique strategy for integrating the structural precision of biological scaffolds with the quantum electronic characteristics of atomically precise metallic cores. Despite this promise, the fundamental principles governing charge transport in such biohybrid systems remain limited. Here, we report a systematic investigation of electron transport in Au/BSA-MNCs/Au Nanowire junctions incorporating a series of bovine serum albumin (BSA)-templated metal nanoclusters of copper, silver, and gold (CuNC, AgNC, and AuNC). Incorporation of MNCs yields up to a 17-fold increase in current relative to native BSA junctions. The conductivity follows the trend AuNC > AgNC > CuNC, a disparity that fragment-level Density Functional Theory (DFT) analysis attributes to the greater structural robustness and enhanced orbital delocalization of AuNC and AgNC, which together facilitate stronger electronic coupling with proximal protein residues. Temperature-dependent charge transport measurements (I-V-T) further reveal a systematic evolution from tunneling-dominated to increasingly band-like transport across the BSA-MNC series, governed by the extent of electronic delocalization imparted by the metal core. Collectively, these findings provide molecular-level insight into charge transport in protein-templated MNCs and establish structure-property design principles for the next-generation bioelectronic materials.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"8 1","pages":"e25930"},"PeriodicalIF":16.6,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089199","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}
Yu Ma,Wenjing Li,Yi Liu,Liwei Tang,Qingshun Fan,Rui Xiao,Junhua Luo,Zhihua Sun
Single crystals with tunable birefringence hold an exciting position in optical and photonic devices due to their exceptional ability of light manipulation. Although ferroelectric domains have been utilized to regulate physical properties, studies on tuning their birefringence by virtue of domain structure remain largely scarce. Herein, we have demonstrated the modulation of in-plane birefringence through manipulating domain structures in a 2D metal halide ferroelectric, (2-MBA)2PbCl4 (1, 2-MBA = 2-methylbutylamine), which exhibits a phase transition at 314 K with spontaneous polarization of 1.6 µC/cm2. Crystal 1 exhibits controllable birefringence that can be modified by thermal and optical stimuli; this behavior directly involves with its ferroelectric properties. Notably, we have achieved unusual in-plane birefringence tuning via domain structure, which is further modulated by coupling domain manipulation with heat, light, and mechanical pressure. This work provides a new strategy for controlling birefringence, and advances the development of ferroelectric-based photonic devices for data storage and integrated optoelectronics.
具有可调双折射的单晶由于其特殊的光操纵能力，在光学和光子器件中占有令人兴奋的地位。虽然铁电畴已经被用来调节物理性质，但利用畴结构调节其双折射的研究仍然很少。在此，我们通过操纵二维金属卤化物铁电体（2-MBA）2PbCl4 （1,2 - mba = 2-甲基丁胺）的畴结构，证明了平面内双折射的调制，该铁电体在314 K时表现出相变，自发极化为1.6µC/cm2。晶体1表现出可控制的双折射，可通过热和光学刺激进行修改；这种行为直接关系到它的铁电性质。值得注意的是，我们已经通过域结构实现了不寻常的平面内双折射调谐，该结构通过与热、光和机械压力耦合的域操作进一步调制。这项工作为控制双折射提供了一种新的策略，并推动了用于数据存储和集成光电子学的铁电光子器件的发展。
{"title":"Distinct Tunable In-Plane Birefringence via Domain Manipulation in a 2D Metal Halide Ferroelectric.","authors":"Yu Ma,Wenjing Li,Yi Liu,Liwei Tang,Qingshun Fan,Rui Xiao,Junhua Luo,Zhihua Sun","doi":"10.1002/anie.1510753","DOIUrl":"https://doi.org/10.1002/anie.1510753","url":null,"abstract":"Single crystals with tunable birefringence hold an exciting position in optical and photonic devices due to their exceptional ability of light manipulation. Although ferroelectric domains have been utilized to regulate physical properties, studies on tuning their birefringence by virtue of domain structure remain largely scarce. Herein, we have demonstrated the modulation of in-plane birefringence through manipulating domain structures in a 2D metal halide ferroelectric, (2-MBA)2PbCl4 (1, 2-MBA = 2-methylbutylamine), which exhibits a phase transition at 314 K with spontaneous polarization of 1.6 µC/cm2. Crystal 1 exhibits controllable birefringence that can be modified by thermal and optical stimuli; this behavior directly involves with its ferroelectric properties. Notably, we have achieved unusual in-plane birefringence tuning via domain structure, which is further modulated by coupling domain manipulation with heat, light, and mechanical pressure. This work provides a new strategy for controlling birefringence, and advances the development of ferroelectric-based photonic devices for data storage and integrated optoelectronics.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"40 1","pages":"e1510753"},"PeriodicalIF":16.6,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073361","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}
Sandhya Jaiswal,Surendar R Jakka,Satish Kumar,Kusaji Pundlik Raul,Rahul Kumar,Govindasamy Mugesh
Expanding the genetic code with unnatural amino acids (UAAs) offers powerful opportunities to engineer proteins with novel redox and catalytic functions, but is often limited by the need for multistep UAA synthesis and inefficient cellular uptake. Here, we report an integrated biosynthetic-genetic incorporation strategy for chalcogen-containing proteins from the respective phenols. Structure-guided engineering of tyrosine phenol lyase (TPL) enabled the enzymatic production of 3-methoxy-, 3-methylthio-, and 3-methylseleno-L-tyrosine (MeSeY) directly in living cells. Using evolved orthogonal aminoacyl-tRNA synthetases, these analogues were site-specifically incorporated into green fluorescent protein (GFP), as confirmed by fluorescence assays, spectroscopy, and mass spectrometry. We further established a one-pot in vivo system that unifies analogue biosynthesis with translation, reducing precursor requirements and cellular toxicity. This work introduces selenium as a genetically encoded handle for protein engineering and establishes a scalable strategy that couples biocatalysis with genetic code expansion to access redox-active designer proteins. Importantly, installation of MeSeY at the GFP chromophore residue Tyr66 provides redox-responsive fluorescence. In a circularly permuted GFP (cpGFP) scaffold, improved chromophore accessibility enables reversible redox switching under H2O2/thiol cycling.
利用非天然氨基酸（UAAs）扩展遗传密码为设计具有新型氧化还原和催化功能的蛋白质提供了强大的机会，但通常受到多步骤UAA合成和低效细胞摄取的限制。在这里，我们报道了一种综合的生物合成-遗传结合策略，用于从各自的酚中提取含硫蛋白质。酪氨酸酚裂解酶（TPL）的结构引导工程使3-甲氧基-、3-甲基硫代-和3-甲基硒- l -酪氨酸（MeSeY）在活细胞中直接产生成为可能。利用进化的正交氨基酰基- trna合成酶，这些类似物被位点特异性地结合到绿色荧光蛋白（GFP）中，荧光分析、光谱分析和质谱分析证实了这一点。我们进一步建立了一锅体内系统，将模拟生物合成与翻译结合起来，减少了前体需求和细胞毒性。这项工作介绍了硒作为蛋白质工程的遗传编码手柄，并建立了一种可扩展的策略，将生物催化与遗传密码扩展相结合，以获得氧化还原活性设计蛋白。重要的是，在GFP发色团残基Tyr66上安装MeSeY可提供氧化还原响应荧光。在循环排列的GFP （cpGFP）支架中，改善的发色团可及性使H2O2/硫醇循环下的可逆氧化还原开关成为可能。
{"title":"From Phenols to Proteins: One-Pot Biosynthesis and Genetic Encoding of Chalcogen-Containing Tyrosine Analogues.","authors":"Sandhya Jaiswal,Surendar R Jakka,Satish Kumar,Kusaji Pundlik Raul,Rahul Kumar,Govindasamy Mugesh","doi":"10.1002/anie.202520166","DOIUrl":"https://doi.org/10.1002/anie.202520166","url":null,"abstract":"Expanding the genetic code with unnatural amino acids (UAAs) offers powerful opportunities to engineer proteins with novel redox and catalytic functions, but is often limited by the need for multistep UAA synthesis and inefficient cellular uptake. Here, we report an integrated biosynthetic-genetic incorporation strategy for chalcogen-containing proteins from the respective phenols. Structure-guided engineering of tyrosine phenol lyase (TPL) enabled the enzymatic production of 3-methoxy-, 3-methylthio-, and 3-methylseleno-L-tyrosine (MeSeY) directly in living cells. Using evolved orthogonal aminoacyl-tRNA synthetases, these analogues were site-specifically incorporated into green fluorescent protein (GFP), as confirmed by fluorescence assays, spectroscopy, and mass spectrometry. We further established a one-pot in vivo system that unifies analogue biosynthesis with translation, reducing precursor requirements and cellular toxicity. This work introduces selenium as a genetically encoded handle for protein engineering and establishes a scalable strategy that couples biocatalysis with genetic code expansion to access redox-active designer proteins. Importantly, installation of MeSeY at the GFP chromophore residue Tyr66 provides redox-responsive fluorescence. In a circularly permuted GFP (cpGFP) scaffold, improved chromophore accessibility enables reversible redox switching under H2O2/thiol cycling.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"82 1","pages":"e20166"},"PeriodicalIF":16.6,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073362","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Bo-Bo Gou,Wen-Jie Shen,Qing Gu,Yuan-Jun Gao,Shu-Li You
De novo formation of the aromatic ring is an attractive strategy for atroposelective synthesis, but its application to planar-chiral macrocycles remains challenging. Herein, we report a rhodium-catalyzed enantioselective synthesis of planar-chiral macrocycles via de novo isoquinoline construction. This method is characterized by high levels of enantioselectivity (up to 96% ee), regioselectivity (up to >20:1 rr), and functional group tolerance, providing a series of isoquinoline-based macrocyclic atropisomers. Furthermore, the synthetic utility of this protocol is validated via a mmol-scale reaction and post-modification process of the product. Mechanistic studies, including deuterium labeling, kinetic isotope effect, and DFT calculations, support C─H bond cleavage as the rate-determining step and elucidate the origin of the stereoselectivity.
{"title":"Rhodium-Catalyzed Enantioselective Synthesis of Planar-Chiral Macrocycles via De Novo Isoquinoline Formation.","authors":"Bo-Bo Gou,Wen-Jie Shen,Qing Gu,Yuan-Jun Gao,Shu-Li You","doi":"10.1002/anie.202525396","DOIUrl":"https://doi.org/10.1002/anie.202525396","url":null,"abstract":"De novo formation of the aromatic ring is an attractive strategy for atroposelective synthesis, but its application to planar-chiral macrocycles remains challenging. Herein, we report a rhodium-catalyzed enantioselective synthesis of planar-chiral macrocycles via de novo isoquinoline construction. This method is characterized by high levels of enantioselectivity (up to 96% ee), regioselectivity (up to >20:1 rr), and functional group tolerance, providing a series of isoquinoline-based macrocyclic atropisomers. Furthermore, the synthetic utility of this protocol is validated via a mmol-scale reaction and post-modification process of the product. Mechanistic studies, including deuterium labeling, kinetic isotope effect, and DFT calculations, support C─H bond cleavage as the rate-determining step and elucidate the origin of the stereoselectivity.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"40 1","pages":"e25396"},"PeriodicalIF":16.6,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089197","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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