Angewandte Chemie (International ed. in English)最新文献

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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
{"title":"Development of Indolo-Bicyclo[3.1.1]Heptane as a Carbazole Isostere Through Radical Indolization of Bicyclo[1.1.0]Butanes.","authors":"Yuan Liu, Jun-Yunzi Wu, Shuang Lin, Qi Fan, Yifan Yang, Ya-Jie Tang, Yin Li, Jiang-Hao Xue, Qingjiang Li, Honggen Wang","doi":"10.1002/anie.202513774","DOIUrl":"https://doi.org/10.1002/anie.202513774","url":null,"abstract":"<p><p>Semisaturated ring systems with a balanced fraction of C(sp3) have garnered increasing attention in drug development. In this study, we propose indolo-bicyclo[3.1.1]heptane as a potential carbazole isostere and present a novel strategy for synthesizing this new semisaturated polycyclic scaffold. The synthesis involves using bicyclo[1.1.0]butanes (BCBs) as radical precursors/terminators in the Fukuyama radical indolization reaction with 2-alkenylarylisocyanides, providing a highly efficient approach to construct a tricyclic system in a single step. These reactions represent a rare example of two functional groups (isonitrile and alkene) being sequentially involved in the cyclization process within BCB chemistry.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202513774"},"PeriodicalIF":16.9,"publicationDate":"2025-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145042933","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
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":"<p><p>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 sp<sup>3</sup>-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.</p>","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
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":"<p><p>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.</p>","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":"<p><p>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 T<sub>80</sub> of 2175 h compared to a T<sub>80</sub> 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 T<sub>80</sub> 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.</p>","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 MN<sub>2</sub>O<sub>2</sub> 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":"<p><p>The metal-nitrogen chelated species, MN<sub>4</sub>, 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 MN<sub>4</sub> suffer from inaccuracy and inhomogeneity because of the lack of strategies stemming from molecular design aspects. Herein, we report the construction of symmetry-broken MN<sub>2</sub>O<sub>2</sub> 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 MN<sub>2</sub>O<sub>2</sub> 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.</p>","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
Ni-Mediated High-Spin Iron(III) for Boosting Electrocatalytic NO to Oxime Conversion. 镍介导的高自旋铁(III)促进电催化NO转化为肟。
IF 16.9
Angewandte Chemie (International ed. in English) Pub Date : 2025-09-10 DOI: 10.1002/anie.202515660
Runan Xiang, Jiawei Kang, Lu Zhang, Xupeng Qin, Peisen Liao, Sijia Zhan, Qinghua Liu, Zheng Liu, Song Gao, Guangqin Li
{"title":"Ni-Mediated High-Spin Iron(III) for Boosting Electrocatalytic NO to Oxime Conversion.","authors":"Runan Xiang, Jiawei Kang, Lu Zhang, Xupeng Qin, Peisen Liao, Sijia Zhan, Qinghua Liu, Zheng Liu, Song Gao, Guangqin Li","doi":"10.1002/anie.202515660","DOIUrl":"https://doi.org/10.1002/anie.202515660","url":null,"abstract":"<p><p>Oximes serve as indispensable intermediates in synthetic chemistry, owing to their distinctive C═N─OH structure, conferring highly versatile reactivity. Synthesis of oxime via the electrochemical method has potential advantages, accompanied by the upgrading of industrialization. Herein, we propose a novel strategy by introducing nickel (Ni) mediation to obtain high-spin iron (Fe)(III) in phthalocyanine structure for synthesizing glyoxylate oxime via electrocatalytic nitric oxide (NO) coupling with keto acid. The optimized pFeNiPc catalyst achieved a Faradaic efficiency of 84.3% and a long-term stability for glyoxylate oxime electrosynthesis. Moreover, the oxime could be directly cyclized to synthesize a gram-level agrochemical isoxazoline molecule. The enriched amounts of high-spin Fe(III) sites promote the accumulation of NO on the catalyst surface and further accelerate reduction, which enables the efficient adsorption-conversion of NO to oxime. This work devises an innovative strategy to selectively engineer the activation of catalytic sites by tailoring electronic configuration and presents a method to facilitate NO valorization in organonitrogen synthesis.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202515660"},"PeriodicalIF":16.9,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145034465","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
Temperature-Driven Conformational Switching of Binaphthalene-Based Tetraimidazolium Macrocycles to Enhance Sequence-Selective Recognition of Dinucleotides in Water. 温度驱动的双萘基四咪唑大环构象开关增强对水中二核苷酸的序列选择性识别。
IF 16.9
Angewandte Chemie (International ed. in English) Pub Date : 2025-09-10 DOI: 10.1002/anie.202516534
Tianci He, Mengxin Huo, Pingxia Wang, Haoyang Huo, Ting Yang, Fan Cao, Lingyu Zhao, Yanxia Yang, Lin Cheng, Liping Cao
{"title":"Temperature-Driven Conformational Switching of Binaphthalene-Based Tetraimidazolium Macrocycles to Enhance Sequence-Selective Recognition of Dinucleotides in Water.","authors":"Tianci He, Mengxin Huo, Pingxia Wang, Haoyang Huo, Ting Yang, Fan Cao, Lingyu Zhao, Yanxia Yang, Lin Cheng, Liping Cao","doi":"10.1002/anie.202516534","DOIUrl":"https://doi.org/10.1002/anie.202516534","url":null,"abstract":"<p><p>Developing artificial hosts with temperature-driven conformational switching behaviors facilitates our understanding of the temperature-dependent allostery and adaptation mechanisms in natural recognition systems. Herein, we report the design and synthesis of three pairs of water-soluble, enantiomeric binaphthalene-based tetraimidazolium macrocycles (SS/RR-1•4Cl- - SS/RR-3•4Cl-) as artificial hosts for exploring sequence-selective recognition of dinucleotides in aqueous media. Owing to the reversible rotational conformation of axially chiral binaphthyl units, SS-1•4Cl- demonstrates the conformational switching, converting from cis-conformation (SS-1<sub>cis</sub>) to trans-conformation (SS-1<sub>trans</sub>) by increasing temperature, thereby causing the recognition cavity to transition from a closed to an open state. Given its ability for temperature-driven conformational switching, SS-1•4Cl- exhibits temperature-cooperative enhanced binding behavior with d(TpA), with association constants (K<sub>a</sub>) increasing to ∼10<sup>6</sup> M<sup>-1</sup> at 323 K, up from ∼10<sup>4</sup> M<sup>-1</sup> at 288 K. In contrast, its affinity for other dinucleotides, including d(ApT), d(GpC), and d(CpG), decreases to varying extents with increasing temperature. As a result, SS-1•4Cl-, with an ability of temperature-driven conformational switching, achieves an unexpected sequence-selective recognition for the sequence-complementary dinucleotide pair d(TpA) and d(ApT), with high sequence selectivity factors (K<sub>rel</sub> = K<sub>a[d(TpA)]</sub>/K<sub>a[d(ApT)]</sub>) reaching up to ∼118.8 at 323 K, increased from ∼1.1 at 288 K, in water.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202516534"},"PeriodicalIF":16.9,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145034492","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
Heavyweight Champion: Caesium Diorganophosphides Outperform Lighter Congeners in the Catalytic Hydrophosphination of Alkenes and Alkynes. 重量级冠军:重有机磷化铯在烯烃和炔的催化氢磷化反应中优于较轻的同系物。
IF 16.9
Angewandte Chemie (International ed. in English) Pub Date : 2025-09-10 DOI: 10.1002/anie.202516376
Felix Krämer, Michelle H Crabbe, Israel Fernández, Robert E Mulvey
{"title":"Heavyweight Champion: Caesium Diorganophosphides Outperform Lighter Congeners in the Catalytic Hydrophosphination of Alkenes and Alkynes.","authors":"Felix Krämer, Michelle H Crabbe, Israel Fernández, Robert E Mulvey","doi":"10.1002/anie.202516376","DOIUrl":"https://doi.org/10.1002/anie.202516376","url":null,"abstract":"<p><p>We present a study of the ability of our recently reported well-defined crown ether-coordinated alkali metal phosphides 1<sup>AM</sup> to catalyze hydrophosphination (HP) of alkynes and alkenes. In a comparative study including reaction monitoring by <sup>1</sup>H NMR spectroscopy, we show that the activity of caesium compound 1<sup>Cs</sup> greatly exceeds that of its lighter congeners, enabling us to solve some reported challenges of catalytic hydrophosphination. Through the rarely used application of dialkyl phosphines, we were able to produce trialkyl phosphines from HP of styrene derivatives and activated as well as non-activated alkynes by catalytic HP with <sup>n</sup>Bu<sub>2</sub>PH and <sup>t</sup>Bu<sub>2</sub>PH. Using <sup>t</sup>BuPhPH, P-chiral products were obtained, still in racemic mixtures showcasing this system's potential. We also proved the method is suited for preparing unsymmetrical ethylene-bridged bisphosphines by HP of Ph<sub>2</sub>P(vinyl) isolable in high yields. These advances hint that well-defined organocaesium compounds could make a long-term impact in chemistry.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202516376"},"PeriodicalIF":16.9,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145035062","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
Hetero-Hydrazone Photoswitches. Hetero-Hydrazone光电开关。
IF 16.9
Angewandte Chemie (International ed. in English) Pub Date : 2025-09-09 DOI: 10.1002/anie.202515136
Daniil Sosnin, Syed Ali Abbas Abedi, Mohammad Izadyar, Yağmur Ünal, Xiaogang Liu, Ivan Aprahamian
{"title":"Hetero-Hydrazone Photoswitches.","authors":"Daniil Sosnin, Syed Ali Abbas Abedi, Mohammad Izadyar, Yağmur Ünal, Xiaogang Liu, Ivan Aprahamian","doi":"10.1002/anie.202515136","DOIUrl":"https://doi.org/10.1002/anie.202515136","url":null,"abstract":"<p><p>The fine-tuning of the (photo)physical properties of molecular photoswitches remains an active area of research, and recently, the incorporation of heterocycles into photoswitch scaffolds has emerged as an effective strategy in this vein. To assess the influence that heterocyclic rings have on hydrazone-based systems, we synthesized a series of photoswitches and examined the impact that heterocycles have on the switching efficiency. TD-DFT calculations and structure-property analyses revealed that heterocycles with basic nitrogen and secondary hydrogen-bonding sites (e.g., imidazole) show poor switching efficiency and undergo thermal back-isomerization via an unusual mechanism involving tautomerization followed by rotation, resulting in fast thermal isomerization rates (i.e., half-lives of seconds to minutes). In contrast, less basic heterocycles such as benzoxazole and benzothiazole favor an inversion pathway, leading to improved bistability. Hydrazones lacking secondary hydrogen-bonding sites, on the other hand, exhibit significantly enhanced photostationary states, improved quantum yields, and red-shifted activation wavelengths compared to their 1st-generation phenyl-based analogs. These results showcase the importance of heterocycle basicity and electron-donating ability, in addition to secondary H-binding sites on photoswitching efficiency, features that are not fully elaborated on in other heterocycle-containing switches. These findings, based on the 2nd generation hydrazone switches, establish key design principles for tuning the bistability and efficiency of such photoswitches.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202515136"},"PeriodicalIF":16.9,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145031571","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
Visible Light-Driven Membrane-Bound Compartment for Precise Regulation of Enzyme Activity. 用于酶活性精确调控的可见光驱动膜结合隔室。
IF 16.9
Angewandte Chemie (International ed. in English) Pub Date : 2025-09-09 DOI: 10.1002/anie.202513676
Zilu Li, Jialiang Wang, Hao Zhuo, Qiushi Li, Qingqing Huang, Chenjue Tang, Wei Zhai, Yang Liu, Yu Zhao
{"title":"Visible Light-Driven Membrane-Bound Compartment for Precise Regulation of Enzyme Activity.","authors":"Zilu Li, Jialiang Wang, Hao Zhuo, Qiushi Li, Qingqing Huang, Chenjue Tang, Wei Zhai, Yang Liu, Yu Zhao","doi":"10.1002/anie.202513676","DOIUrl":"https://doi.org/10.1002/anie.202513676","url":null,"abstract":"<p><p>Photo-responsive systems provide a powerful tool to reversibly regulate enzyme activity. However, inhibitor-based strategies, though widely used, are often restricted to specific enzymes. Noninhibitor strategies, such as enzyme surface modification or genetic mutation, often compromise structural integrity or residual activity. Inspired by the gating mechanisms of biological membranes, we reported a visible light-driven membrane-bound compartment system constructed from phenylazothiazole gated lipids and phospholipids. In this design, phenylazothiazole lipids undergo reversible isomerization between trans and cis configurations under alternating purple and green light, generating continuous nanomechanical motions that transiently enhance membrane permeability. This dynamic gating behavior enables substrate diffusion across the membrane under light exposure and allows the activity of encapsulated enzymes to be switched on and off in a noninvasive, temporally defined manner. This system requires no chemical modification or mutagenesis, thus preserving the native structure and activity of encapsulated enzymes. Beyond binary regulation, precise modulation of the irradiation pattern permits graded control over enzyme activity, offering an advanced level of functional tunability. Using carbonic anhydrase, catalase, and glucose oxidase as models, we demonstrate that enzyme activity can be reversibly and quantitatively regulated via programmable light inputs. This strategy offers a broadly applicable and biocompatible platform for spatiotemporal enzyme regulation.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202513676"},"PeriodicalIF":16.9,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145031512","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
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