Wassilios Papawassiliou, José P. Carvalho, Subhradip Paul, Aizuddin Sultan, Michael Fardis, Georgios Papavassiliou, Grace G. Morgan, Katharina Märker, Gaël De Paëpe
Electron spin‐state changes in transition‐metal (TM) complexes underpin many biochemical processes and molecular spin‐control technologies. Such transitions, triggered by external stimuli like temperature, light, or pressure, alter both the molecular structure and electron spin density (ESD) distribution. Paramagnetic NMR offers atomic‐scale insights into these changes, yet traditional solution‐state measurements bear limitations due to solvent effects, unaccounted lattice cooperativity, and inaccessibility at cryogenic temperatures. We overcome these limitations by extending the approach to spinning solids at cryogenic temperatures. Specifically, we report high‐resolution 13 C and 1 H magic‐angle spinning (MAS) NMR spectra of a mononuclear spin‐crossover (SCO) Mn(III) complex across the SCO transition at 130 K. Such low‐temperature experiments are particularly challenging because paramagnetic shift and shift anisotropy are inversely proportional to the temperature. The experimental findings are supported by advanced quantum chemical calculations of the NMR and EPR parameters to assign and rationalize the observed paramagnetic shifts. Additionally, monitoring selected 1 H resonances upon heating and cooling through the transition provides access to the order parameter (), revealing hysteresis behavior similar to the magnetic susceptibility measurements. This work demonstrates that paramagnetic NMR combined with quantum chemical calculations provides a unique route to probing SCO at the atomic level.
{"title":"Tracking Structural and Electron Spin Density Changes in a Cooperative Mn 3+ Spin Crossover Complex at Atomic Scale via Low Temperature Solid‐State NMR","authors":"Wassilios Papawassiliou, José P. Carvalho, Subhradip Paul, Aizuddin Sultan, Michael Fardis, Georgios Papavassiliou, Grace G. Morgan, Katharina Märker, Gaël De Paëpe","doi":"10.1002/anie.202517466","DOIUrl":"https://doi.org/10.1002/anie.202517466","url":null,"abstract":"Electron spin‐state changes in transition‐metal (TM) complexes underpin many biochemical processes and molecular spin‐control technologies. Such transitions, triggered by external stimuli like temperature, light, or pressure, alter both the molecular structure and electron spin density (ESD) distribution. Paramagnetic NMR offers atomic‐scale insights into these changes, yet traditional solution‐state measurements bear limitations due to solvent effects, unaccounted lattice cooperativity, and inaccessibility at cryogenic temperatures. We overcome these limitations by extending the approach to spinning solids at cryogenic temperatures. Specifically, we report high‐resolution <jats:sup>13</jats:sup> C and <jats:sup>1</jats:sup> H magic‐angle spinning (MAS) NMR spectra of a mononuclear spin‐crossover (SCO) Mn(III) complex across the SCO transition at 130 K. Such low‐temperature experiments are particularly challenging because paramagnetic shift and shift anisotropy are inversely proportional to the temperature. The experimental findings are supported by advanced quantum chemical calculations of the NMR and EPR parameters to assign and rationalize the observed paramagnetic shifts. Additionally, monitoring selected <jats:sup>1</jats:sup> H resonances upon heating and cooling through the transition provides access to the order parameter (), revealing hysteresis behavior similar to the magnetic susceptibility measurements. This work demonstrates that paramagnetic NMR combined with quantum chemical calculations provides a unique route to probing SCO at the atomic level.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"35 1","pages":"e17466"},"PeriodicalIF":16.6,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711080","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}
{"title":"Correction to “Macrocyclic Peptide Probes for Immunomodulatory Protein CD 59 : Potent Modulators of Bacterial Toxin Activity and Antibody‐Dependent Cytotoxicity”","authors":"","doi":"10.1002/anie.202526119","DOIUrl":"https://doi.org/10.1002/anie.202526119","url":null,"abstract":"","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"142 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711383","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}
Haisong Xu, Tingting Du, Jiali Lin, Feiying You, Yingbo Shao, Qi Yang, Xin Li
Atropisomers play a vital role in asymmetric synthesis, drug discovery, and the development of functional materials. However, the rational design of atropisomers is challenging due to the difficulty in predicting their configurational stability, which depends on the rotational barrier (Δ G‡ ). Here, we introduce ACSD‐GAT, a deep learning framework that addresses this issue. Our approach comprises a newly curated benchmark dataset of 1015 experimentally measured rotational barrier, along with a physicochemically informed axial chirality structure descriptor (ACSD) that explicitly quantifies both static and dynamic steric repulsion during rotation. By integrating the ACSD with a graph attention network (GAT), our model accurately predicts the rotational barrier, achieving an R2 of 0.91 and a RMSE of 2.02 kcal mol −1 on test datasets. The robustness and real‐world applicability of the model are also demonstrated through rigorous validation with complex pharmaceuticals, molecular switches, and newly synthesized atropisomers.
{"title":"Physicochemically Informed Axial Chirality Descriptors Enable Accurate Prediction of Atropisomeric Stability","authors":"Haisong Xu, Tingting Du, Jiali Lin, Feiying You, Yingbo Shao, Qi Yang, Xin Li","doi":"10.1002/anie.202521349","DOIUrl":"https://doi.org/10.1002/anie.202521349","url":null,"abstract":"Atropisomers play a vital role in asymmetric synthesis, drug discovery, and the development of functional materials. However, the rational design of atropisomers is challenging due to the difficulty in predicting their configurational stability, which depends on the rotational barrier (Δ <jats:italic>G</jats:italic> <jats:sup>‡</jats:sup> ). Here, we introduce ACSD‐GAT, a deep learning framework that addresses this issue. Our approach comprises a newly curated benchmark dataset of 1015 experimentally measured rotational barrier, along with a physicochemically informed axial chirality structure descriptor (ACSD) that explicitly quantifies both static and dynamic steric repulsion during rotation. By integrating the ACSD with a graph attention network (GAT), our model accurately predicts the rotational barrier, achieving an <jats:italic>R</jats:italic> <jats:sup>2</jats:sup> of 0.91 and a RMSE of 2.02 kcal mol <jats:sup>−1</jats:sup> on test datasets. The robustness and real‐world applicability of the model are also demonstrated through rigorous validation with complex pharmaceuticals, molecular switches, and newly synthesized atropisomers.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"13 1","pages":"e21349"},"PeriodicalIF":16.6,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711079","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}
Bram Daelman, Jonas Debuyck, Vincent Scholiers, Johan M. Winne, Filip E. Du Prez
Amides are robust chemical linkages of interest in the field of dynamic covalent polymer networks (DCPNs), but their activation towards dynamic exchange remains an outstanding challenge. Herein, we introduce γ‐hydroxy amides as a versatile motif for the design of creep resistant, yet fully reprocessable crosslinked polyamide‐based materials. This was achieved by the reversible ring‐opening of γ‐lactones with primary amines. Small molecule kinetic studies showed that temperatures exceeding 120 °C are required for the ring‐closure to occur at a significant rate. Thus, efficient exchange of the γ‐hydroxy amide bonds was expected upon heating, while essentially non‐dynamic covalent amide bonds should prevail at lower temperatures. γ‐Hydroxy amides were then introduced into DCPNs, for which a newly prepared bifunctional γ‐lactone monomer was cured with amine hardeners. A marked thermal response was observed in the rheological behavior, while creep resistance comparable to that of a non‐dynamic epoxy‐amine network was maintained up to 120 °C. Finally, we could also demonstrate the thermal resilience of γ‐hydroxy amides after multiple compression molding cycles for a material with a glass transition temperature above 80 °C. Consequently, we expect that this simple chemistry platform has high potential for application in reprocessable thermoset materials.
{"title":"Creep Resistant and Reprocessable Polyamide Networks Based on Reversible Lactone Ring‐Opening","authors":"Bram Daelman, Jonas Debuyck, Vincent Scholiers, Johan M. Winne, Filip E. Du Prez","doi":"10.1002/anie.202519828","DOIUrl":"https://doi.org/10.1002/anie.202519828","url":null,"abstract":"Amides are robust chemical linkages of interest in the field of dynamic covalent polymer networks (DCPNs), but their activation towards dynamic exchange remains an outstanding challenge. Herein, we introduce γ‐hydroxy amides as a versatile motif for the design of creep resistant, yet fully reprocessable crosslinked polyamide‐based materials. This was achieved by the reversible ring‐opening of γ‐lactones with primary amines. Small molecule kinetic studies showed that temperatures exceeding 120 °C are required for the ring‐closure to occur at a significant rate. Thus, efficient exchange of the γ‐hydroxy amide bonds was expected upon heating, while essentially non‐dynamic covalent amide bonds should prevail at lower temperatures. γ‐Hydroxy amides were then introduced into DCPNs, for which a newly prepared bifunctional γ‐lactone monomer was cured with amine hardeners. A marked thermal response was observed in the rheological behavior, while creep resistance comparable to that of a non‐dynamic epoxy‐amine network was maintained up to 120 °C. Finally, we could also demonstrate the thermal resilience of γ‐hydroxy amides after multiple compression molding cycles for a material with a glass transition temperature above 80 °C. Consequently, we expect that this simple chemistry platform has high potential for application in reprocessable thermoset materials.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"203 1","pages":"e19828"},"PeriodicalIF":16.6,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711082","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 development of lithium–sulfur (Li−S) batteries is hindered by the polysulfide dissolving, cross-over and the inherent lithium metal anode instability. We herein instead describe a lithiated silicon−sulfur (LiSi−S) battery enabled by molecular engineering of highly solvating nitrile electrolytes toward weakly solvating to fundamentally decouple the reactions of the two electrodes and eliminate their cross-talk. Specifically, by controlled fluorination of the ethoxy-nitrile base solvent, the charge distribution on the solvent is manipulated which suppresses the solvation for polysulfides promoting a quasi-solid-state sulfur reaction (QSSSR) mechanism. The promoted anion participation in Li+ solvation, along with the fluoroethylene carbonate additive, further stabilizes the interphases at both sulfur cathode and LiSi anode mitigating the mechanical degradations. The QSSSR-based LiSi−S cell shows a high capacity of 1499.0 mA h gsulfur−1 at 0.1C, and achieves a high capacity retention of 90.2% over 100 cycles at 0.2C with an average Coulombic efficiency of 99.9%. This work highlights the essence of molecular engineering for manipulating the primary reactions and interphasial behaviors at both electrodes toward high performance sulfur batteries.
锂硫（Li−S）电池的发展受到多硫化物溶解、交叉和锂金属阳极固有的不稳定性的阻碍。我们在此描述了一种锂化硅硫电池（LiSi - S），该电池通过分子工程将高溶剂化的腈电解质转变为弱溶剂化，从根本上解耦两个电极的反应并消除它们的串扰。具体来说，通过控制乙氧基-腈基溶剂的氟化，控制了溶剂上的电荷分布，抑制了多硫化物的溶剂化，促进了准固态硫反应（QSSSR）机制。促进阴离子参与Li+溶剂化，以及氟乙烯碳酸酯添加剂，进一步稳定了硫阴极和锂阳极的界面相，减轻了机械降解。基于qsssr的锂离子电池在0.1C下的容量为1499.0 mA h g硫−1，在0.2C下的100次循环中容量保持率为90.2%，平均库仑效率为99.9%。这项工作突出了分子工程的本质，即操纵两个电极上的初级反应和相间行为，以实现高性能硫电池。
{"title":"Molecular Design of Nitrile Electrolytes Enabling Lithiated Silicon–Sulfur Batteries with Quasi-Solid-State Sulfur Reaction","authors":"Mengxue He, Yunpeng Fu, Lujun Zhu, Yue Ma, Chenxi Zheng, Guo Ye, Zhitong Xiao, Yongfeng Jia, Xin Gao, Mingchuan Luo, Kenneth Ozoemena, Mohammadhosein Safari, Shaojun Qiu, Jinglun Wang, Quanquan Pang","doi":"10.1002/anie.202518760","DOIUrl":"https://doi.org/10.1002/anie.202518760","url":null,"abstract":"The development of lithium–sulfur (Li−S) batteries is hindered by the polysulfide dissolving, cross-over and the inherent lithium metal anode instability. We herein instead describe a lithiated silicon−sulfur (LiSi−S) battery enabled by molecular engineering of highly solvating nitrile electrolytes toward weakly solvating to fundamentally decouple the reactions of the two electrodes and eliminate their cross-talk. Specifically, by controlled fluorination of the ethoxy-nitrile base solvent, the charge distribution on the solvent is manipulated which suppresses the solvation for polysulfides promoting a quasi-solid-state sulfur reaction (QSSSR) mechanism. The promoted anion participation in Li<sup>+</sup> solvation, along with the fluoroethylene carbonate additive, further stabilizes the interphases at both sulfur cathode and LiSi anode mitigating the mechanical degradations. The QSSSR-based LiSi−S cell shows a high capacity of 1499.0 mA h g<sub>sulfur</sub><sup>−1</sup> at 0.1C, and achieves a high capacity retention of 90.2% over 100 cycles at 0.2C with an average Coulombic efficiency of 99.9%. This work highlights the essence of molecular engineering for manipulating the primary reactions and interphasial behaviors at both electrodes toward high performance sulfur batteries.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"139 1","pages":"e18760"},"PeriodicalIF":16.6,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711193","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}
Modulating the excited states of coinage metal clusters can effectively improve their photophysical properties, and significant progress has been realized through ligand modification and heterometallic doping. However, precise substitution of individual atoms within the kernel remains a formidable challenge. Herein, we present three copper cluster analogs, namely Cu4S, Cu4Se, and Cu4P, displaying distinct thermally activated delayed fluorescence (TADF), wherein Cu4S and Cu4Se display yellow luminescence with QYs of 99.2% and 89.0% respectively, while Cu4P with the first HP2− unit in copper clusters exhibits near-infrared (NIR) emission with a QY of 22.2%. Theoretical calculations have verified that the energy levels of excited states in copper clusters are modulated by substituting the central coordinating atoms. The spin-orbit coupling of Cu4P, Cu4S, and Cu4Se, as well as the structural deformation differences between the excited state and the ground state, leads to the different luminescence quantum yields. This study not only reports the first HP2−-involved copper cluster but also establishes a platform for investigation on single-site modulation directed luminescence of copper clusters.
{"title":"Excited State Modulation of Copper Clusters Realized by Single-Site Alteration Achieving Near-Infrared Luminescence","authors":"Wei-Miao He, Ya-Xuan Liu, Jing Li, Zhao-Yang Wang, Shuang-Quan Zang","doi":"10.1002/anie.202518017","DOIUrl":"https://doi.org/10.1002/anie.202518017","url":null,"abstract":"Modulating the excited states of coinage metal clusters can effectively improve their photophysical properties, and significant progress has been realized through ligand modification and heterometallic doping. However, precise substitution of individual atoms within the kernel remains a formidable challenge. Herein, we present three copper cluster analogs, namely <b>Cu<sub>4</sub>S</b>, <b>Cu<sub>4</sub>Se</b>, and <b>Cu<sub>4</sub>P</b>, displaying distinct thermally activated delayed fluorescence (TADF), wherein <b>Cu<sub>4</sub>S</b> and <b>Cu<sub>4</sub>Se</b> display yellow luminescence with QYs of 99.2% and 89.0% respectively, while <b>Cu<sub>4</sub>P</b> with the first HP<sup>2−</sup> unit in copper clusters exhibits near-infrared (NIR) emission with a QY of 22.2%. Theoretical calculations have verified that the energy levels of excited states in copper clusters are modulated by substituting the central coordinating atoms. The spin-orbit coupling of <b>Cu<sub>4</sub>P</b>, <b>Cu<sub>4</sub>S</b>, and <b>Cu<sub>4</sub>Se</b>, as well as the structural deformation differences between the excited state and the ground state, leads to the different luminescence quantum yields. This study not only reports the first HP<sup>2−</sup>-involved copper cluster but also establishes a platform for investigation on single-site modulation directed luminescence of copper clusters.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"7 1","pages":"e18017"},"PeriodicalIF":16.6,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711194","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}
Francis Millward, Michał Kulczykowski, Jay Badland‐Shaw, Sara Szymkuc, Rajan Suraksha, Aniket Kumar Srivastawa, Violaine Manet, Máire Griffin, Megan Bryden, Thomas Comerford, Lea Hämmerling, Aminata Mariko, Bartosz A. Grzybowski, Eli Zysman‐Colman
Utilizing an extensive library of literature on photocatalytic transformations, we disclose the development of a machine learning (ML) model for the recommendation of photocatalysts most suitable for reactions of interest. The model is trained on > 36 000 such literature examples and uses an architecture inspired by the Bidirectional Encoder Representations from Transformer (BERT) large language model. Under cross‐validation, it can suggest the “correct” photocatalysts with ∼90% accuracy. When experimentally tested on five out‐of‐box reactions, this algorithm consistently suggested photocatalysts that gave yields competitive to those chosen by human researchers and frequently suggested alternative photocatalysts that are potentially more appealing than the originally selected photocatalyst. Altogether, this platform serves as a valuable tool for researchers undertaking reaction optimization programs. The model is free to use at https://photocatals.grzybowskigroup.pl/predict/ .
{"title":"Design and Experimental Validation of a Photocatalyst Recommender Based on a Large Language Model","authors":"Francis Millward, Michał Kulczykowski, Jay Badland‐Shaw, Sara Szymkuc, Rajan Suraksha, Aniket Kumar Srivastawa, Violaine Manet, Máire Griffin, Megan Bryden, Thomas Comerford, Lea Hämmerling, Aminata Mariko, Bartosz A. Grzybowski, Eli Zysman‐Colman","doi":"10.1002/anie.202514544","DOIUrl":"https://doi.org/10.1002/anie.202514544","url":null,"abstract":"Utilizing an extensive library of literature on photocatalytic transformations, we disclose the development of a machine learning (ML) model for the recommendation of photocatalysts most suitable for reactions of interest. The model is trained on > 36 000 such literature examples and uses an architecture inspired by the Bidirectional Encoder Representations from Transformer (BERT) large language model. Under cross‐validation, it can suggest the “correct” photocatalysts with ∼90% accuracy. When experimentally tested on five out‐of‐box reactions, this algorithm consistently suggested photocatalysts that gave yields competitive to those chosen by human researchers and frequently suggested alternative photocatalysts that are potentially more appealing than the originally selected photocatalyst. Altogether, this platform serves as a valuable tool for researchers undertaking reaction optimization programs. The model is free to use at <jats:ext-link xmlns:xlink=\"http://www.w3.org/1999/xlink\" xlink:href=\"https://photocatals.grzybowskigroup.pl/predict/\">https://photocatals.grzybowskigroup.pl/predict/</jats:ext-link> .","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"58 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145703842","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}
Di Yin, Yun‐Dong Cao, Hong Liu, Guang‐Gang Gao, Shuang‐Quan Zang
The identification of isomeric organic compounds poses a significant challenge due to their structurally and chemically analogous features. This research introduces an innovative methodology for the detection of chlorotoluene isomers through the utilization of Surface‐Enhanced Raman Spectroscopy (SERS). The approach utilizes an exceptionally efficient SERS substrate, namely (Ag 02 Ag I Mpy) n @ h ‐ZIF (where Mpy denotes p ‐mercaptopyridine), characterized by its hollow Zeolitic Imidazolate Frameworks ( h ‐ZIFs) interwoven with silver thiolate nanowires. The porous channels within h ‐ZIFs stably adsorb various chlorotoluene isomers, subsequently exposing them to the electromagnetic field generated by Ag 0 species. In addition to coordinating with silver ions, the Mpy component within the silver nanowires functions as a highly stable SERS probe, which improves detection accuracy by serving as an internal standard. This study introduces a novel Ag‐ZIF model as a highly efficient SERS substrate and presents a distinctive methodology for differentiating organic isomers or analogous small molecules.
由于同分异构体有机化合物具有结构和化学相似的特征，因此对其鉴定提出了重大挑战。本研究介绍了一种利用表面增强拉曼光谱（SERS）检测氯甲苯异构体的创新方法。该方法利用了一种非常高效的SERS底物，即（Ag 0 2 Ag I Mpy） n @ h‐ZIF（其中Mpy表示对巯基吡啶），其特点是其中空的沸石咪唑酸框架（h‐ZIF）与硫酸银纳米线交织在一起。h‐zif内的多孔通道稳定地吸附各种氯甲苯异构体，随后将其暴露于Ag - 0物质产生的电磁场中。除了与银离子协调外，银纳米线内的Mpy成分还可以作为高度稳定的SERS探针，通过作为内部标准来提高检测精度。本研究引入了一种新的Ag - ZIF模型作为高效的SERS底物，并提出了一种独特的方法来区分有机异构体或类似的小分子。
{"title":"Interwoven Porous ZIF Polyhedra Threaded with Silver Thiolate Nanowires for Ultrasensitive SERS Detection of Chlorotoluene Isomers","authors":"Di Yin, Yun‐Dong Cao, Hong Liu, Guang‐Gang Gao, Shuang‐Quan Zang","doi":"10.1002/anie.202513584","DOIUrl":"https://doi.org/10.1002/anie.202513584","url":null,"abstract":"The identification of isomeric organic compounds poses a significant challenge due to their structurally and chemically analogous features. This research introduces an innovative methodology for the detection of chlorotoluene isomers through the utilization of Surface‐Enhanced Raman Spectroscopy (SERS). The approach utilizes an exceptionally efficient SERS substrate, namely (Ag <jats:sup>0</jats:sup> <jats:sub>2</jats:sub> Ag <jats:sup>I</jats:sup> Mpy) <jats:sub>n</jats:sub> @ <jats:italic>h</jats:italic> ‐ZIF (where Mpy denotes <jats:italic>p</jats:italic> ‐mercaptopyridine), characterized by its hollow Zeolitic Imidazolate Frameworks ( <jats:italic>h</jats:italic> ‐ZIFs) interwoven with silver thiolate nanowires. The porous channels within <jats:italic>h</jats:italic> ‐ZIFs stably adsorb various chlorotoluene isomers, subsequently exposing them to the electromagnetic field generated by Ag <jats:sup>0</jats:sup> species. In addition to coordinating with silver ions, the Mpy component within the silver nanowires functions as a highly stable SERS probe, which improves detection accuracy by serving as an internal standard. This study introduces a novel Ag‐ZIF model as a highly efficient SERS substrate and presents a distinctive methodology for differentiating organic isomers or analogous small molecules.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"11 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704294","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}
Uththara M.C. Rathnaweera, Olivia Sam, Karolis Norvaisa, Sarah R. Marshall, Randima D. De Silva Weerakonda Arachchige, Matúš Chvojka, Hennie Valkenier, Nathalie Busschaert
Nucleotides such as cAMP (cyclic adenosine monophosphate) and AMP (adenosine monophosphate) are central to many cellular processes, but their highly hydrophilic and charged nature prevents passive permeation across lipid bilayers. Here, we report the first example of facilitated transport of cAMP and AMP across liposome membranes using a neutral two-component system at physiological pH. This system pairs a synthetic anionophore targeting the phosphate group with a thymine derivative to boost transport efficiency. Liposome-based fluorescence and 31P NMR experiments confirmed transmembrane transport, supported by control experiments. A fluorinated squaramide proved to be the best transporter and was able to transport cAMP even without the help of a thymine derivative, as well as AMP in the presence of a lipophilic thymine derivative. These findings show that carefully designed small molecules can enable direct nucleotide translocation, with potential applications in drug delivery and synthetic biology.
{"title":"Transmembrane Transport of cAMP and AMP Using a Two Component Small Molecule Transport System","authors":"Uththara M.C. Rathnaweera, Olivia Sam, Karolis Norvaisa, Sarah R. Marshall, Randima D. De Silva Weerakonda Arachchige, Matúš Chvojka, Hennie Valkenier, Nathalie Busschaert","doi":"10.1002/anie.202524663","DOIUrl":"https://doi.org/10.1002/anie.202524663","url":null,"abstract":"Nucleotides such as cAMP (cyclic adenosine monophosphate) and AMP (adenosine monophosphate) are central to many cellular processes, but their highly hydrophilic and charged nature prevents passive permeation across lipid bilayers. Here, we report the first example of facilitated transport of cAMP and AMP across liposome membranes using a neutral two-component system at physiological pH. This system pairs a synthetic anionophore targeting the phosphate group with a thymine derivative to boost transport efficiency. Liposome-based fluorescence and <sup>31</sup>P NMR experiments confirmed transmembrane transport, supported by control experiments. A fluorinated squaramide proved to be the best transporter and was able to transport cAMP even without the help of a thymine derivative, as well as AMP in the presence of a lipophilic thymine derivative. These findings show that carefully designed small molecules can enable direct nucleotide translocation, with potential applications in drug delivery and synthetic biology.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":"e24663"},"PeriodicalIF":16.6,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711195","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}
Pengpeng Zhang, Zhuangfei Tian, Congcong Li, Runze Meng, Bowen Zhang, Xinzhuo Liu, Junkuan Li, Ge Qu, Nicholas J. Turner, Bo Yuan, Haigen Fu, Zhoutong Sun
Enzymatic synthesis of atropisomers has recently attracted considerable research attention, with most studies focusing on axially chiral biaryls. We report a less explored atroposelective dynamic kinetic resolution (DKR) of nonbiaryl styrenes catalyzed by imine reductases (IREDs) and alcohol dehydrogenases (ADHs). The IR189 wild type enzyme was identified to be highly active and selective; furthermore, the inversion of atroposelectivity was achieved with protein engineering. Additionally, two ADHs with enantio-complementary selectivity for the reductive DKR were identified and applied in the synthesis of axially chiral styrenes. Both IREDs and ADHs exhibited broad substrate scope, affording up to 99:1 e.r. and 99% yields for up to 29 examples. Scaled-up reactions and derivatization of optically pure products demonstrated the synthetic utility of these axially chiral styrenes. Molecular recognition mechanisms were elucidated by molecular dynamics (MD) simulations. The current strategy expands the scope of enzymatic DKR of atropisomeric compounds and significantly advances the field of biocatalytic synthesis of axially chiral compounds.
{"title":"Biocatalytic Atroposelective Synthesis of Axially Chiral Styrenes via Dynamic Kinetic Resolution","authors":"Pengpeng Zhang, Zhuangfei Tian, Congcong Li, Runze Meng, Bowen Zhang, Xinzhuo Liu, Junkuan Li, Ge Qu, Nicholas J. Turner, Bo Yuan, Haigen Fu, Zhoutong Sun","doi":"10.1002/anie.202521538","DOIUrl":"https://doi.org/10.1002/anie.202521538","url":null,"abstract":"Enzymatic synthesis of atropisomers has recently attracted considerable research attention, with most studies focusing on axially chiral biaryls. We report a less explored atroposelective dynamic kinetic resolution (DKR) of nonbiaryl styrenes catalyzed by imine reductases (IREDs) and alcohol dehydrogenases (ADHs). The IR189 wild type enzyme was identified to be highly active and selective; furthermore, the inversion of atroposelectivity was achieved with protein engineering. Additionally, two ADHs with enantio-complementary selectivity for the reductive DKR were identified and applied in the synthesis of axially chiral styrenes. Both IREDs and ADHs exhibited broad substrate scope, affording up to 99:1 e.r. and 99% yields for up to 29 examples. Scaled-up reactions and derivatization of optically pure products demonstrated the synthetic utility of these axially chiral styrenes. Molecular recognition mechanisms were elucidated by molecular dynamics (MD) simulations. The current strategy expands the scope of enzymatic DKR of atropisomeric compounds and significantly advances the field of biocatalytic synthesis of axially chiral compounds.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"5 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711196","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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