Angewandte Chemie (International ed. in English)最新文献_第8页

Predicting Reaction Feasibility and Selectivity of Aromatic C─H Thianthrenation with a QM-ML Hybrid Approach. 用QM-ML杂交方法预测芳香族C─H硫代蒽醌化反应的可行性和选择性。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-14 DOI: 10.1002/anie.202510533

Lukas M Sigmund, Tina Seifert, Riya Halder, Giulia Bergonzini, Magnus J Johansson, Per-Ola Norrby, Kjell Jorner, Mikhail Kabeshov

{"title":"Predicting Reaction Feasibility and Selectivity of Aromatic C─H Thianthrenation with a QM-ML Hybrid Approach.","authors":"Lukas M Sigmund, Tina Seifert, Riya Halder, Giulia Bergonzini, Magnus J Johansson, Per-Ola Norrby, Kjell Jorner, Mikhail Kabeshov","doi":"10.1002/anie.202510533","DOIUrl":"https://doi.org/10.1002/anie.202510533","url":null,"abstract":"The direct thianthrenation of aromatic C─H bonds is a valuable late-stage functionalization strategy that can assist, for example, the development of new drugs. We herein present a predictive computational model for this reaction, denoted PATTCH, which is based on semiempirical quantum mechanics and machine learning. It classifies each Caromatic-H unit either as reactive or not with an accuracy of above 90%. It can address both the site-selectivity and reaction feasibility question associated with the thianthrenation protocol. First, this was achieved by selecting carefully engineered features, which take into account the electronic and steric influence on the site-selectivity. Second, parallel experimentation was used to supplement the available literature data with 54 new negative reactions (unsuccessful thianthrenation), which we show was instrumental for developing the PATTCH tool. Ultimately, we successfully applied the model to a challenging test set encompassing the differentiation between carbocycle versus heterocycle functionalization, the identification of substrates that were reported to result in a mixture of isomeric products, and to molecules that could not be thianthrenated. The computational predictions were experimentally validated. The PATTCH tool can be obtained free of charge from https://github.com/MolecularAI/thianthrenation_prediction.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202510533"},"PeriodicalIF":16.9,"publicationDate":"2025-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145067587","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Multidentate Macrocyclic Salphen-Based 2D Conjugated Metal-Organic Framework. 多齿大环沙芬基二维共轭金属有机骨架。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-13 DOI: 10.1002/anie.202511048

Pei Chen, Mingxuan Liu, Ruofan Li, Xi Su, Guolong Xing, Xiao-Rui Ren, Dong Wang, Jian Zhang, Long Chen

{"title":"Multidentate Macrocyclic Salphen-Based 2D Conjugated Metal-Organic Framework.","authors":"Pei Chen, Mingxuan Liu, Ruofan Li, Xi Su, Guolong Xing, Xiao-Rui Ren, Dong Wang, Jian Zhang, Long Chen","doi":"10.1002/anie.202511048","DOIUrl":"https://doi.org/10.1002/anie.202511048","url":null,"abstract":"Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) represent an emerging class of crystalline porous materials with promising electrochemical applications. The design of novel organic ligands for constructing 2D c-MOFs remains a crucial research frontier. While the incorporation of macrocycle blocks into 2D c-MOFs can introduce intrinsic cavities with advantageous properties, most existing reports are limited to coordinating with only one equivalent metal ion per macrocyclic cavity. In this work, we developed a triangular-shaped Salphen macrocycle-based 2D c-MOF (SM-MOF-Cu) featuring multidentate internal coordination sites. SM-MOF-Cu exhibits high crystallinity, permanent porosity, and abundant accessible metal sites. Remarkably, this material demonstrates exceptional performance in the electrocatalytic hydrogenation of acetylene to ethylene (E-HAE), achieving a Faradaic efficiency of 96.6% for ethylene production at -0.85 V versus the reversible hydrogen electrode (RHE) under continuous pure acetylene feed. This study not only broadens the family of macrocycle-based 2D c-MOFs but also provides new insights into their potential for advanced electrocatalysis.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202511048"},"PeriodicalIF":16.9,"publicationDate":"2025-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145056457","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Can Charge Transfer Across C─H⋅⋅⋅O Hydrogen Bonds Stabilize Oil Droplets in Water? 通过C─H⋅⋅⋅⋅O氢键的电荷转移能稳定水中油滴吗？

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-13 DOI: 10.1002/anie.202508145

Ruoqi Zhao, Hengyuan Shen, R Allen LaCour, Joseph P Heindel, Martin Head-Gordon, Teresa Head-Gordon

{"title":"Can Charge Transfer Across C─H⋅⋅⋅O Hydrogen Bonds Stabilize Oil Droplets in Water?","authors":"Ruoqi Zhao, Hengyuan Shen, R Allen LaCour, Joseph P Heindel, Martin Head-Gordon, Teresa Head-Gordon","doi":"10.1002/anie.202508145","DOIUrl":"https://doi.org/10.1002/anie.202508145","url":null,"abstract":"Oil-water emulsions resist aggregation due to the presence of negative charges at their surface that leads to mutual repulsion between droplets, but the molecular origin of oil charge is currently under debate. Although much evidence has suggested that ionic species must accumulate at the interface, an alternative perspective attributes the negative charge on the oil droplet to charge transfer of electron density from water to oil molecules. Although the charge transfer mechanism is consistent with the correct sign of oil charge, it is just as important to provide good estimates of the charge magnitude to explain emulsion stability and electrophoresis experiments. Here, we show using energy decomposition analysis that the amount of net flow of charge from water to oil is negligibly small due to nearly equal forward and backward charge transfer through weak oil-water interactions, such that oil droplets would be unstable and coalesce, contrary to experiment. The lack of charge transfer also explains why vibrational sum frequency scattering reports a blue shift in the oil C-H frequency when forming emulsions with water, which arises from Pauli repulsion due to localized confinement at the interface. Finally, unlike ions, neither charge transfer nor dynamic polarization can produce a finite conductivity needed to couple to electric fields that would explain electrophoretic mobility.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202508145"},"PeriodicalIF":16.9,"publicationDate":"2025-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145056495","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Ignacio Funes-Ardoiz.

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-13 DOI: 10.1002/anie.202519166

Ignacio Funes-Ardoiz

引用次数: 0

Development of Indolo-Bicyclo[3.1.1]Heptane as a Carbazole Isostere Through Radical Indolization of Bicyclo[1.1.0]Butanes. 吲哚-双环[1.1.0]丁烷自由基吲哚-双环[3.1.1]庚烷作为咔唑异戊酯的研究

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-12 DOI: 10.1002/anie.202513774

Yuan Liu, Jun-Yunzi Wu, Shuang Lin, Qi Fan, Yifan Yang, Ya-Jie Tang, Yin Li, Jiang-Hao Xue, Qingjiang Li, Honggen Wang

引用次数: 0

Fully-Functionalized Natural Product Probes to Expand the Chemical Tractability of the Human Proteome. 全功能化天然产物探针扩展人类蛋白质组的化学可追溯性。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-12 DOI: 10.1002/anie.202502648

Christian M Chaheine, Junchen Tang, Louis P Conway, Christopher G Parker

{"title":"Fully-Functionalized Natural Product Probes to Expand the Chemical Tractability of the Human Proteome.","authors":"Christian M Chaheine, Junchen Tang, Louis P Conway, Christopher G Parker","doi":"10.1002/anie.202502648","DOIUrl":"https://doi.org/10.1002/anie.202502648","url":null,"abstract":"Photoaffinity (PA)-based chemoproteomic methods have emerged as a powerful means for proteome-wide mapping of ligandable proteins directly in cells, as well as the concatenated discovery of small molecule chemical probes. However, due to the relatively low throughput of screening small molecule libraries by proteomics and the synthetic burden incurred in installing the requisite photoactivatable functionality on each member, great priority must be placed on library design to maximize efficient exploration of biologically relevant chemical space and to ensure the identification of authentic binding interactions. To address this challenge, here we leverage the inherent complexity of natural products (NPs) to access a structurally unique series of diastereo/regioisomeric PA probes for ligand discovery in cells. Through semi-synthesis, we exploit sp3-rich NP scaffolds and employ mass spectrometry (MS)-based chemoproteomics to identify and quantify their interactions in human cells, uncovering topology, regio-, and stereoselective ligands for functionally diverse proteins that currently lack reported chemical probes. Collectively, our findings highlight the potential of NP-inspired chemoproteomic libraries to expand the boundaries of the ligandable proteome.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202502648"},"PeriodicalIF":16.9,"publicationDate":"2025-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145042905","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Ahmed M. El-Zohry. 艾哈迈德·m·佐里。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-11 DOI: 10.1002/anie.202519182

Ahmed M El-Zohry

引用次数: 0

Tailoring the Magnetic Properties of 2D Metal-Organic Networks by Harnessing the Coordination Sphere. 利用配位球剪裁二维金属-有机网络的磁性。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-10 DOI: 10.1002/anie.202509199

Shanmugasibi K Mathialagan, Sofia O Parreiras, José Santos, Cristina Martín-Fuentes, Daniel Moreno, Lenka Černa, Maria Tenorio, Beatriz Muñiz-Cano, Koen Lauwaet, Manuel Valvidares, Miguel A Valbuena, José I Urgel, Wolfgang Kuch, Pierluigi Gargiani, Rodolfo Miranda, José I Martínez, José M Gallego, Nazario Martín, David Écija

{"title":"Tailoring the Magnetic Properties of 2D Metal-Organic Networks by Harnessing the Coordination Sphere.","authors":"Shanmugasibi K Mathialagan, Sofia O Parreiras, José Santos, Cristina Martín-Fuentes, Daniel Moreno, Lenka Černa, Maria Tenorio, Beatriz Muñiz-Cano, Koen Lauwaet, Manuel Valvidares, Miguel A Valbuena, José I Urgel, Wolfgang Kuch, Pierluigi Gargiani, Rodolfo Miranda, José I Martínez, José M Gallego, Nazario Martín, David Écija","doi":"10.1002/anie.202509199","DOIUrl":"https://doi.org/10.1002/anie.202509199","url":null,"abstract":"Achieving magnetic ordering in low-dimensional materials remains a key objective in the field of magnetism. Herein, coordination chemistry emerges as a powerful discipline to promote the stabilization of magnetism at the nanoscale. We present a thorough study of exemplary two-dimensional metal-organic nanoarchitectures synthesized on a Au(111) substrate, which are rationalized by using surface-science techniques and theoretical calculations. By tuning the stoichiometry, two distinct phases based on the same molecular linker coordinated with Co atoms are obtained, though featuring a different coordination sphere. Remarkably, our combined experimental and theoretical results suggest that for one phase the Co centers have an out-of-plane antiferromagnetic ground state, whereas for the other the Co atoms display in-plane antiferromagnetism. These results pave new avenues for designing two-dimensional (2D) metal-organic magnets and tailoring their inherent magnetic properties.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202509199"},"PeriodicalIF":16.9,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145034463","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Long-Lived Charge-Transfer State and Interfacial Lock in Double-Cable Conjugated Polymers Enable Efficient and Stable Organic Solar Cells. 双缆共轭聚合物的长寿命电荷转移态和界面锁定使有机太阳能电池高效稳定。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-10 DOI: 10.1002/anie.202514735

Haisheng Fang, Chengyi Xiao, Shijie Liang, Linhu Liu, Jiaming Huang, Yuwen Wang, Andong Zhang, Yang Li, Christopher R McNeill, He Cheng, Gang Li, Weiwei Li

{"title":"Long-Lived Charge-Transfer State and Interfacial Lock in Double-Cable Conjugated Polymers Enable Efficient and Stable Organic Solar Cells.","authors":"Haisheng Fang, Chengyi Xiao, Shijie Liang, Linhu Liu, Jiaming Huang, Yuwen Wang, Andong Zhang, Yang Li, Christopher R McNeill, He Cheng, Gang Li, Weiwei Li","doi":"10.1002/anie.202514735","DOIUrl":"https://doi.org/10.1002/anie.202514735","url":null,"abstract":"The donor/acceptor (D/A) interfaces in bulk heterojunction (BHJ) organic solar cells (OSCs) critically govern exciton dissociation and molecular diffusion, determining both efficiency and stability. Herein, we design a double-cable conjugated polymer, SC-1F, to insert into a physically-blended D/A system to optimize the interface. We have found that SC-1F spontaneously segregates to the interface through favorable miscibility and heterogeneous nucleation with the acceptor. Its long-lived charge-transfer (CT) state with a lifetime of >3 ns enhances charge generation efficiency in the PM6:BTP-eC9 blend, boosting the power conversion efficiency (PCE) from 19.00% to 20.12%. More importantly, the double-cable nature of SC-1F enables it to be simultaneously miscible with donor and acceptor so as to act as the interfacial lock to prevent their self-aggregation under thermal treatment. Therefore, the PM6:BTP-eC9:SC-1F-based solar cells provided a high T80 of 2175 h compared to a T80 of 530 h based on PM6:BTP-eC9 under 65 °C treatment. Notably, SC-1F-based device demonstrates exceptional storage and thermal stability, with a T80 lifetime exceeding 10 000 h. These results demonstrate the superior advantage of double-cable conjugated polymers as the third component to achieve efficient and stable OSCs.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202514735"},"PeriodicalIF":16.9,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145034485","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

One-Pot Sequential Coordination-Covalent Construction of Symmetry-Broken MN₂O₂ Catalytic Sites in Cobalt-Polyimide Polymers for Nitrate Electroreduction. 钴-聚酰亚胺聚合物中对称断裂MN2O2催化位点的一锅顺序配位共价构建

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-10 DOI: 10.1002/anie.202513738

Qinghao Liu, Zeying Yang, Shuai Yang, Ming Gao, Bin Chen, Xianzhe Wei, Shaohui Xiong, Ping Wang, Qing Xu, Zaoming Wang, Ziqian Xue, Cheng Gu

{"title":"One-Pot Sequential Coordination-Covalent Construction of Symmetry-Broken MN2O2 Catalytic Sites in Cobalt-Polyimide Polymers for Nitrate Electroreduction.","authors":"Qinghao Liu, Zeying Yang, Shuai Yang, Ming Gao, Bin Chen, Xianzhe Wei, Shaohui Xiong, Ping Wang, Qing Xu, Zaoming Wang, Ziqian Xue, Cheng Gu","doi":"10.1002/anie.202513738","DOIUrl":"https://doi.org/10.1002/anie.202513738","url":null,"abstract":"The metal-nitrogen chelated species, MN4, have shown promise as efficient electrocatalysts for nitrate reduction, yet the symmetric arrangement of N atoms results in suboptimal adsorption affinity toward reaction substrates and intermediates. The current approaches to breaking the symmetry of MN4 suffer from inaccuracy and inhomogeneity because of the lack of strategies stemming from molecular design aspects. Herein, we report the construction of symmetry-broken MN2O2 sites in coordination polymers via sequential coordination-covalent control in a one-pot reaction. The dehydrogenating coordination preferentially occurs prior to the covalent imide-formation reaction, allowing the two reactions to be completely separated to afford molecularly precise polymer electrocatalysts that feature near-unity coordination degree and monodispersed atomic MN2O2 species with lowered symmetry, facilitating efficient nitrate reduction. Our study provides a design rationale to integrate diverse coordination and covalent chemistries into coordination polymers for electrocatalysis.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202513738"},"PeriodicalIF":16.9,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145034456","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0