Angewandte Chemie International Edition最新文献_第10页

Photoelectrocatalyzed Alkylation of Phosphonites by Direct Decarboxylative C(sp3)‐P Coupling

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-01-27 DOI: 10.1002/anie.202500744

Kang-Ning Yuan, Tian Xie, Jia-Bao Wang, Dali Wang, ming shang

引用次数: 0

Polymer Ligands with Multi‐Nitrogen Heterocyclic Carbenes for Enhanced Stability and Reactivity in Nanoparticle Surface Functionalization

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-01-27 DOI: 10.1002/anie.202419640

Jing Tao, Di Zheng, Yutian Tang, Huibin He, Yan Zhang, Yanqiong Yang, Liwei Dai, Huaining Zha, Yutao Sang, Zhihong Nie

{"title":"Polymer Ligands with Multi‐Nitrogen Heterocyclic Carbenes for Enhanced Stability and Reactivity in Nanoparticle Surface Functionalization","authors":"Jing Tao, Di Zheng, Yutian Tang, Huibin He, Yan Zhang, Yanqiong Yang, Liwei Dai, Huaining Zha, Yutao Sang, Zhihong Nie","doi":"10.1002/anie.202419640","DOIUrl":"https://doi.org/10.1002/anie.202419640","url":null,"abstract":"Nitrogen heterocyclic carbenes (NHCs) are emerging as effective substitutes for conventional thiol ligands in surface functionalization of nanoparticles (NPs), offering exceptional stability to NPs under harsh conditions. However, the highly reactive feature of NHCs limits their use in introducing chemically active groups onto the NP surface. Herein, we develop a general yet robust strategy for the efficient surface functionalization of NPs with copolymer ligands bearing various functional groups. The polymer ligands consist of a multiple NHCs block, utilized for surface binding on NPs, alongside a poly(reactive ester) block intended for incorporating functional groups. The multiple NHCs block enables NPs with excellent colloidal stability across a broader range of pH values (0‐14), temperature variations (–78°C‐100°C), and electrolyte concentrations (0‐1000 mM). Through the in situ ammonolysis of the poly(reactive ester) block, various active functional groups can be individually or together introduced on the NP surface. We further demonstrate the chemical reactivity of these functionalized NPs, including addition polymerization, Diels‐Alder and Schiff base reactions. This method is applicable to various types of NPs, including metal NPs, metal oxide NPs, and even upconversion NPs, thereby paving new pathways for the design and creation of nanoparticle‐based functional materials.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"21 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044187","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}

引用次数: 0

Shifting Lithium Amide Reactivity to the Radical Domain: Regioselective Radical C-H Functionalization of 3-Iodooxetane for the Synthesis of 1,5-Dioxaspiro[2.3]hexanes

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-01-27 DOI: 10.1002/anie.202424346

Philipp Natho, Marco Colella, Annarita Vicenti, Giuseppe Romanazzi, Faizan Ullah, Nadeem Sadiq Sheikh, Andrew J. P. White, Francesco Pasca, Renzo Luisi

{"title":"Shifting Lithium Amide Reactivity to the Radical Domain: Regioselective Radical C-H Functionalization of 3-Iodooxetane for the Synthesis of 1,5-Dioxaspiro[2.3]hexanes","authors":"Philipp Natho, Marco Colella, Annarita Vicenti, Giuseppe Romanazzi, Faizan Ullah, Nadeem Sadiq Sheikh, Andrew J. P. White, Francesco Pasca, Renzo Luisi","doi":"10.1002/anie.202424346","DOIUrl":"https://doi.org/10.1002/anie.202424346","url":null,"abstract":"Strained spiro-heterocycles (SSH) have gained significant attention within the medicinal chemistry community as promising (sp3)-rich bioisosteres for their aromatic and non-spirocyclic counterparts. We herein report access to an unprecedented spiro-heterocycle - 1,5-dioxaspiro[2.3]hexane. Our synthetic approach leverages a lithium-amide induced single-electron transfer to benzophenones generating an N-centered radical and a ketyl radical anion - reminiscent of a frustrated radical pair. This pair works synergistically to selectively abstract the β-hydrogen from 3-iodooxetane, initiating an exergonic radical-radical coupling reaction. This process enables the formation of the desired bond between the oxetane core and benzophenone derivatives, ultimately yielding the novel 1,5-dioxaspiro[2.3]hexane core. The stability and synthetic utility of the novel 1,5-dioxaspiro[2.3]hexane motif are showcased. An in-depth mechanistic investigation is presented, including cyclic voltammetry studies, as well as computational calculations and experiments to support the mechanism of this new single electron synthetic tactic.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"34 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044241","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}

引用次数: 0

Tailoring molecular diffusion in core-shell zeolite imidazolate framework composites realizes efficient kinetic separation of xylene isomers

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-01-27 DOI: 10.1002/anie.202420953

Linghe Yang, Guangtong Hai, Ying Liu, Fang Zheng, Fuxing Shen, Lihang Chen, Baojian Liu, Zhiguo Zhang, Qiwei Yang, Qilong Ren, Yong Luo, Zongbi Bao

{"title":"Tailoring molecular diffusion in core-shell zeolite imidazolate framework composites realizes efficient kinetic separation of xylene isomers","authors":"Linghe Yang, Guangtong Hai, Ying Liu, Fang Zheng, Fuxing Shen, Lihang Chen, Baojian Liu, Zhiguo Zhang, Qiwei Yang, Qilong Ren, Yong Luo, Zongbi Bao","doi":"10.1002/anie.202420953","DOIUrl":"https://doi.org/10.1002/anie.202420953","url":null,"abstract":"The separation of xylene isomers is a critical and energy-intensive process in the petrochemical industry, primarily due to their closely similar molecular structures and boiling points. In this work, we report the synthesis and application of a novel core-shell zeolitic imidazolate framework (ZIF) composite, ZIF-65@ZIF-67, designed to significantly enhance the kinetic separation of xylene isomers through a synergistic \"shell-gated diffusion and core-facilitated transport\" strategy. The external ZIF-67 shell selectively restricts the diffusion of larger isomers (MX and OX), while the internal ZIF-65 core accelerates the diffusion of PX, thereby amplifying the diffusion differences among the isomers. This architecture yields remarkable improvements in both selectivity and diffusion rates, as demonstrated by vapor-phase adsorption studies and molecular dynamics simulations. The ZIF-65@ZIF-67 composite exhibits up to 12.5 times higher PX/OX selectivity in liquid-phase adsorption and 3.4 times higher dynamic selectivity in fixed-column breakthrough experiments compared to the individual ZIF components. Theoretical simulations further corroborate the heterogeneous diffusion control mechanism, revealing the time-dependent diffusion regulation within the core-shell architecture. This work underscores the great potential of core-shell MOF composites in optimizing molecular sieving processes for industrially significant separations and highlights a new route for enhancing kinetic separation efficiency in complex multicomponent systems.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"45 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044249","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}

引用次数: 0

Cyano-Modified Multi-Resonance Thermally Activated Delayed Fluorescent Emitters towards Pure-Green OLEDs with a CIE y Value of 0.74

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-01-27 DOI: 10.1002/anie.202500108

Zhuixing Xue, Yuxuan Hu, Shengbing Xiao, Jiahui Liu, Jingsheng Miao, Chuluo Yang

{"title":"Cyano-Modified Multi-Resonance Thermally Activated Delayed Fluorescent Emitters towards Pure-Green OLEDs with a CIE y Value of 0.74","authors":"Zhuixing Xue, Yuxuan Hu, Shengbing Xiao, Jiahui Liu, Jingsheng Miao, Chuluo Yang","doi":"10.1002/anie.202500108","DOIUrl":"https://doi.org/10.1002/anie.202500108","url":null,"abstract":"The development of pure-green organic emitters with ideal emission peak and ultra-narrow full-widths at half-maximum (FWHMs) remains a formidable challenge. Herein, we report two new green emitters, CNBN and MCNBN, which achieve extremely narrow FWHMs by synergistic rigid π-extension and cyano-substitution for sky-blue multi-resonance thermally activated delayed fluorescence (MR-TADF) core. The introduction of cyano groups induces red-shifts of emission to green region and dramatically minimize the FWHMs. In toluene solution, CNBN and MCNBN exhibit narrowband emission peaking at 501 nm and 510 nm with ultra-narrow FWHMs of 14 nm/0.066 eV and 15 nm/0.071 eV, respectively. Given the near-unity photoluminescence quantum yields and almost 100% horizontal dipole orientation, the electroluminescent (EL) devices based on CNBN and MCNBN deliver external quantum efficiencies (EQEs) exceeding 30% with FWHMs of 16 nm/0.072 eV and 17 nm/0.080 eV, respectively. Notably, the MCNBN-based device achieves pure-green emission peaking at 517 nm with Commission Internationale de l’Éclairage coordinates of (0.17, 0.74), closely aligning with the BT.2020 green standard.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"48 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044586","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}

引用次数: 0

Independent LUMO Reactivity in Mesoionic N-Heterocyclic Thiones: Synthesis of a Stable Radical Anion. 中离子 N-杂环硫醚的独立 LUMO 反应性：一种稳定的自由基阴离子的合成。

IF 16.1 1区化学

Angewandte Chemie International Edition Pub Date : 2025-01-27 Epub Date: 2024-11-12 DOI: 10.1002/anie.202418673

Subir Maji, Biplab Gope, Madhur Sharma, Arpan Das, Anex Jose, Amit Biswas, Kalishankar Bhattacharyya, Swadhin K Mandal

{"title":"Independent LUMO Reactivity in Mesoionic N-Heterocyclic Thiones: Synthesis of a Stable Radical Anion.","authors":"Subir Maji, Biplab Gope, Madhur Sharma, Arpan Das, Anex Jose, Amit Biswas, Kalishankar Bhattacharyya, Swadhin K Mandal","doi":"10.1002/anie.202418673","DOIUrl":"10.1002/anie.202418673","url":null,"abstract":"Mesoionic compounds, with positive and negative charges, are expected to have dual-site highest occupied molecular orbital (HOMO, donor) and lowest unoccupied molecular orbital (LUMO, acceptor) reactivity. Herein, we report a novel class of air-stable mesoionic N-heterocyclic thiones (mNHTs) synthesized from abnormal N-heterocyclic carbenes (aNHCs). DFT studies revealed a highly polarized exocyclic thione moiety and computed Fukui function analysis suggests the dual-site HOMO/LUMO reactivity of mNHTs predicting donor property at the negatively charged 'S' center while acceptor property at the cationic imidazole ring. The independent LUMO reactivity of the mNHT was realized by its chemical reduction to an elusive radical anion, which was characterized by a single crystal X-raydiffraction study. Further, we explore the reactivity of radical anion for the activation of SO2 gas, C-Br bonds of aryl bromide and photocatalytic functionalization of C-X (X = F, Br) bonds. This work unlocks the independent LUMO reactivity of a mesoionic compound.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":" ","pages":"e202418673"},"PeriodicalIF":16.1,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453869","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}

引用次数: 0

A Metal Chelation Therapy to Effectively Eliminate Breast Cancer and Intratumor Bacteria While Suppressing Tumor Metastasis by Copper Depletion and Zinc Ions Surge. 一种金属螯合疗法，通过铜耗竭和锌离子激增，有效消除乳腺癌和肿瘤内细菌，同时抑制肿瘤转移。

IF 16.1 1区化学

Angewandte Chemie International Edition Pub Date : 2025-01-27 Epub Date: 2024-11-11 DOI: 10.1002/anie.202417592

Yulin Xie, Junrong Wang, Lei Li, Man Wang, Jikai Sun, Jiaying Chang, Jun Lin, Chunxia Li

{"title":"A Metal Chelation Therapy to Effectively Eliminate Breast Cancer and Intratumor Bacteria While Suppressing Tumor Metastasis by Copper Depletion and Zinc Ions Surge.","authors":"Yulin Xie, Junrong Wang, Lei Li, Man Wang, Jikai Sun, Jiaying Chang, Jun Lin, Chunxia Li","doi":"10.1002/anie.202417592","DOIUrl":"10.1002/anie.202417592","url":null,"abstract":"The intratumor microbiota results in the immunosuppressive microenvironment and facilitates tumor growth and metastasis. However, developing a synergistic therapy with antitumor, antibacterial, and antimetastatic effects faces enormous challenges. Here, we propose an innovative metal chelation therapy to effectively eliminate tumor and intratumor bacteria and suppress tumor metastasis. Different from traditional chelation therapy that only consumes metal elements, this therapy not only eliminates the crucial metal elements for tumor metabolism but also releases new metal ions with antitumor and antibacterial properties. Based on the high demand for copper in breast cancer, we prepare a fibrous therapeutic nanoagent (Zn-PEN) by chelating the copper chelator D-Penicillamine (D-PEN) with Zn2+. Firstly, Zn-PEN achieves dual inhibition of oxidative phosphorylation (OXPHOS) and glycolysis metabolism in breast cancer through copper depletion and Zn2+ activated cGAS-STING pathway, thus inducing tumor cell death. Secondly, Zn-PEN has the capability to eradicate Fusobacterium nucleatum (F. nucleatum) in breast cancer, thereby mitigating its immunosuppressive impact on the tumor microenvironment. Finally, Zn-PEN effectively inhibits tumor metastasis through multiple routes, including the inhibition of epithelial-mesenchymal transition (EMT) process, activation of cGAS-STING pathway, and elimination with F. nucleatum. Therefore, we verify the feasibility of Zn-PEN mediated metal chelation therapy in a 4T1 model infected with F. nucleatum, providing a new therapeutic strategy for inhibiting tumor metastasis.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":" ","pages":"e202417592"},"PeriodicalIF":16.1,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142405747","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}

引用次数: 0

A Carbazole-Centered Expanded Helicene Stabilized with Hexabenzocoronene (HBC) Units. 一种以咔唑为中心、用六苯并二甲硼烯 (HBC) 单元稳定的扩展双链烯。

IF 16.1 1区化学

Angewandte Chemie International Edition Pub Date : 2025-01-27 Epub Date: 2024-11-25 DOI: 10.1002/anie.202417745

Xin-Yue Wang, Jinku Bai, Yun-Jia Shen, Zhi-Ao Li, Han-Yuan Gong

引用次数: 0

Propeller-Shaped Blatter-Based Triradicals: Distortion-Free Triangular Spin System and Spin-State-Dependent Photophysical Properties. 螺旋桨形 Blatter-Based Triradicals：无畸变三角自旋系统和自旋态相关光物理性质。

IF 16.1 1区化学

Angewandte Chemie International Edition Pub Date : 2025-01-27 Epub Date: 2024-11-29 DOI: 10.1002/anie.202418655

Takero Aoki, Hikaru Sotome, Daiki Shimizu, Hiroshi Miyasaka, Kenji Matsuda

引用次数: 0

Engineered Polymeric Carbon Nitride for Photocatalytic Diverse Functionalization of Electronic-Rich Alkenes. 用于富电子烯光催化多样化功能化的工程聚合物氮化碳。

IF 16.1 1区化学

Angewandte Chemie International Edition Pub Date : 2025-01-27 Epub Date: 2024-12-04 DOI: 10.1002/anie.202417099

Youqing Yang, Jiwei Shi, Chenguang Liu, Qiong Liu, Jian Yang, Xiaogang Tong, Jiong Lu, Jie Wu

引用次数: 0