Angewandte Chemie (International ed. in English)最新文献_第5页

Fe-O-Mo Site-Activated Nanozymes for Bienzymatic/Upconversion Synergistic Catalytic Anticancer Therapy. Fe-O-Mo位点活化纳米酶用于双酶/上转化协同催化抗癌治疗。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-16 DOI: 10.1002/anie.202511471

Qiang Wang, Shuang Liu, Chunsheng Li, Yaru Huang, Boqi An, Meng Wang, Jiawei Qu, Peiyao Wang, Jiating Xu, Ping'an Ma

{"title":"Fe-O-Mo Site-Activated Nanozymes for Bienzymatic/Upconversion Synergistic Catalytic Anticancer Therapy.","authors":"Qiang Wang, Shuang Liu, Chunsheng Li, Yaru Huang, Boqi An, Meng Wang, Jiawei Qu, Peiyao Wang, Jiating Xu, Ping'an Ma","doi":"10.1002/anie.202511471","DOIUrl":"https://doi.org/10.1002/anie.202511471","url":null,"abstract":"Single-atom nanozymes (SAzymes) hold promise for cancer therapy but suffer from low active site density and restricted intermediate adsorption/desorption capabilities. Herein, Fe/Mo dual-atom silicon-based semiconductor nanozymes (FeMoDA), encapsulated in lanthanide-doped nanoparticles (LPs) and surface-modified with hyaluronic acid (HA) (denoted as HA/FeMoDA-LPs), were developed for synergistic bienzymatic/upconversion-triggered catalytic therapy (ET/UCT) under second near-infrared (NIR-II)/magnetic resonance (MR) imaging guidance. Density functional theory calculations revealed that Fe/Mo dual-atom sites were bridged by Fe - O - Mo coordination, optimizing oxygen-containing intermediate adsorption/desorption, and improving dual-enzymatic activities. The peroxidase (POD)-like catalytic performance of HA/FeMoDA-LPs showed a Km of 11.54 mM and a Vmax of 1.14 × 10-7 M·s-1, outperforming Fe- or Mo-single-atom coated LPs. HA modification promoted endocytosis (∼5.67-fold) and microenvironmental acidification (pH from 7.21 to 6.74), further improving ET. Under 980 nm irradiation, upconversion-triggered electrons synergized with oxidase-like activity to convert O2 into superoxide (•O2 -), while holes enabled •O2 - to singlet oxygen (1O2) conversion, which combined with POD-like-produced hydroxyl radicals (•OH) to achieve synergistic ET/UCT. Tumor H+ and glutathione co-induced the specific degradation of nanozymes, resulting in tumor self-enhanced downconversion NIR-II and MR imaging. Compared with conventional SAzymes, HA/FeMoDA-LPs exhibit superior catalytic performance and dual-modal imaging, offering a synergistic and tumor-responsive platform for cancer theranostics.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202511471"},"PeriodicalIF":16.9,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145077113","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

Breaking the Deep-UV Transparency/Optical Nonlinearity Trade-Off: Three-Parameter Optimization in Oxyfluorides by Tailoring d⁰-Metal Incorporation. 打破深紫外透明度/光学非线性的权衡：通过剪裁-金属掺入来优化氟化物中的三参数。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-16 DOI: 10.1002/anie.202513438

Xiaotian T Zhang, Xingxing X Jiang, Hui Gao, Kaining N Duanmu, Chao Wu, Zheshuai S Lin, Zhipeng P Huang, Mark G Humphrey, Chi Zhang

{"title":"Breaking the Deep-UV Transparency/Optical Nonlinearity Trade-Off: Three-Parameter Optimization in Oxyfluorides by Tailoring d0-Metal Incorporation.","authors":"Xiaotian T Zhang, Xingxing X Jiang, Hui Gao, Kaining N Duanmu, Chao Wu, Zheshuai S Lin, Zhipeng P Huang, Mark G Humphrey, Chi Zhang","doi":"10.1002/anie.202513438","DOIUrl":"https://doi.org/10.1002/anie.202513438","url":null,"abstract":"Achieving an optimal balance among key optical performance parameters (i.e., bandgap, second-harmonic generation (SHG), and birefringence) is critically important for addressing application constraints and advancing the development of nonlinear optical (NLO) materials. We report herein the first examples of deep-ultraviolet (deep-UV) transparent mixed d0-metal oxyfluorides A5(NbOF4)(TaF7)2 (ANTOF: A = K, Rb, Cs, NH4), synthesized through a synergistic dual-site strategy. Our synthetic strategy enables the targeted incorporation of highly distorted d0-metal octahedra into metal fluorides, creating two distinct d0-metal polyhedra with complementary microstructural features that can reconcile trade-offs in key optical properties. By introducing 4d0-Nb-based [NbO2F4] oxyfluoride octahedra into the centrosymmetric parent 5d0-Ta-based fluorides A2TaF7, the resultant ANTOFs not only crystallize with noncentrosymmetric polar structures but, more importantly, demonstrate exceptional performance, including record-high phase-matchable SHG responses for deep-UV transparent d0-metal oxyfluorides (3.3-3.8 × KH2PO4 @ 1064 nm (visible region) and 0.33-0.38 × β-BaB2O4 @ 532 nm (UV region)), wide bandgaps (> 6.36 eV), and suitable birefringence (Δn = 0.093-0.105 @ 546 nm). Theoretical calculations and crystal structure analyses reveal that the superior linear and nonlinear optical properties of the ANTOFs originate from the dual-site synergy between the polarizable [NbO2F4] octahedra and the [TaF7] pentagonal bipyramids, in which ligand-to-metal charge transfer transitions are suppressed.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202513438"},"PeriodicalIF":16.9,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145077069","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

Sugar-Based Alternating Copolymers via Photoinduced Radical Copolymerization of Levoglucosenone and Vinyl Ethers. 左旋葡萄糖酮与乙烯基醚光诱导自由基共聚的糖基交替共聚物。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-16 DOI: 10.1002/anie.202517501

Lianqian Wu, Hongsik Kim, Tae-Lim Choi

引用次数: 0

Tetra-N-Fused Indolocarbazole Multiple Resonance Emitters Enabling Ultra-Narrowband Pure Green Emission with High Efficiency and Stability. 四氮融合吲哚咔唑多共振发射器，实现超窄带纯绿色高效稳定发射。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-16 DOI: 10.1002/anie.202517349

Dawei Zhang, Qian Wang, Jianping Zhou, Wenbo Yuan, Chuanqin Cheng, Jinbei Wei, Dongdong Zhang, Lian Duan

{"title":"Tetra-N-Fused Indolocarbazole Multiple Resonance Emitters Enabling Ultra-Narrowband Pure Green Emission with High Efficiency and Stability.","authors":"Dawei Zhang, Qian Wang, Jianping Zhou, Wenbo Yuan, Chuanqin Cheng, Jinbei Wei, Dongdong Zhang, Lian Duan","doi":"10.1002/anie.202517349","DOIUrl":"https://doi.org/10.1002/anie.202517349","url":null,"abstract":"Developing efficient narrowband emitters beyond the blue region remains challenging for indolocarbazole-based multiple resonance (ICz-MR) systems, primarily due to the inherent trade-off between spectral red-shifting and linewidth broadening. To address this, we pioneer tetra-N-fused ICz isomers (l-N4ICz and s-N4ICz) with four consecutive para-positioned nitrogen atoms, forming extended π-systems via alternating six-/five-membered ring fusion. The linear isomer l-N4ICz achieves sharp green photoluminescence peaking at 506 nm with a full width at half maxima (FWHM) of merely 14 nm-surpassing the bent analogue-alongside suppressed spectral shoulders and higher photoluminescence efficiency. Theoretical studies reveal the critical role of orbital symmetry engineering of adjacent segments in governing the optoelectronic properties of isomers. Organic light-emitting diodes with l-N4ICz deliver pure-green electroluminescence with an ultra-narrow FWHM of 19 nm and the first chromaticity y-coordinate reaching 0.7 among ICz-MR systems, alongside a peak external quantum efficiency of 30.1%, which remains at >20% even under extremely high luminance over 200 000 cd m-2. The same device also sets a benchmark long operational lifetime of 2327 h to decay to 90% of the initial luminance of 1000 cd m-2. These findings highlight the great potential of multi-N-fused ICz-MR structures for highly efficient, stable, and narrow electroluminescence.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202517349"},"PeriodicalIF":16.9,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145076982","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

Inverting the Circularly Polarized Luminescence Handedness of Chiral Supramolecular Polymers Using Temperature. 利用温度反转手性超分子聚合物的圆偏振发光手性。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-16 DOI: 10.1002/anie.202516824

Teodor-Aurelian Cucuiet, Andreas Vargas Jentzsch, Flavio Picini, Mounir Maaloum, Guillaume Raffy, Emilie Moulin, Dario M Bassani, Nicolas Giuseppone

引用次数: 0

Anionic Iminoborane as Boryl Anion Synthon. 阴离子亚氨基硼烷作为硼基阴离子合成物。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-16 DOI: 10.1002/anie.202518214

Yuyang Dai, Ping Cui, Chen-Ho Tung, Lingbing Kong

引用次数: 0

Allosteric Activation of Cas12a via PAM Topological Engineering for Direct and Rapid Detection of Nucleases. 基于PAM拓扑工程的Cas12a变构活化用于核酸酶的直接和快速检测。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-16 DOI: 10.1002/anie.202515521

Xiu-Li Tao, Yan-Mei Lei, Xue-Mei Zhou, Zhao-Peng Chen, Yue Ma, Pin-Yi Ma, Da-Qian Song, Ying Zhuo

{"title":"Allosteric Activation of Cas12a via PAM Topological Engineering for Direct and Rapid Detection of Nucleases.","authors":"Xiu-Li Tao, Yan-Mei Lei, Xue-Mei Zhou, Zhao-Peng Chen, Yue Ma, Pin-Yi Ma, Da-Qian Song, Ying Zhuo","doi":"10.1002/anie.202515521","DOIUrl":"https://doi.org/10.1002/anie.202515521","url":null,"abstract":"A contemporary question in the intensely active field of CRISPR-Cas12a-based molecular diagnostics is how to simplify the multistep conversion process for detecting nonnucleic acid targets. Herein we describe an allosteric Y-shaped DNA structure for Cas12a activation via protospacer-adjacent motif (PAM) topological engineering (Y-COPE) to achieve straightforward and diverse nuclease monitoring. The newly designed topological structure of the Y-COPE is characterized by a split PAM embedded at the three-way junction and protospacers flanking both sides. This unique spatial configuration of the PAM effectively prevents Cas12a activation. Upon target cleavage, the released truncated fragments can dynamically correct the PAM, which promptly restores the dsDNA conformation for Cas12a activation and accomplishes signal output. Theoretical calculation results revealed that, compared with the canonical dsDNA activator, in the Y-COPE, there was a 1.8 Å increase in the center distance between Lys595 of Cas12a and the PAM, which led to a 24.2 kcal mol-1 increase in binding free energy. This clearly revealed the underlying inhibition mechanism of the topological configuration of the PAM for Cas12a activation. This study advances the understanding of the dynamic response of Cas12a to topological PAM conformations and introduces the universal concept of CRISPR-based nonnucleic acid detection to benefit the next-generation molecular diagnostics.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202515521"},"PeriodicalIF":16.9,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145077127","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

Computational Study of Ignored Pericyclic Reactions: Rearrangements of 1,2-Bis(Diazo)Alkanes to 1,2,3,4-Tetrazines and Subsequent Fragmentations. 被忽略的周环反应的计算研究：1,2-双（重氮）烷烃重排到1,2,3,4-四嗪和随后的断裂。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-16 DOI: 10.1002/anie.202514598

Hans-Ulrich Reissig, Ernst-Ulrich Würthwein

{"title":"Computational Study of Ignored Pericyclic Reactions: Rearrangements of 1,2-Bis(Diazo)Alkanes to 1,2,3,4-Tetrazines and Subsequent Fragmentations.","authors":"Hans-Ulrich Reissig, Ernst-Ulrich Würthwein","doi":"10.1002/anie.202514598","DOIUrl":"https://doi.org/10.1002/anie.202514598","url":null,"abstract":"An electrocyclic ring closure of bis-1,3-dipoles can afford six-membered heterocycles. This 8π-electron process was systematically analyzed by DFT calculations with 1,2-bis(diazo)alkane derivatives as possible precursor compounds and 1,2,3,4-tetrazines as products. The C2-symmetry of the transition state of the parent system points to a conrotatory ring closing event. The subsequent (6-2-2) cycloreversions of these elusive nitrogen-rich heterocycles to alkynes or nitriles and dinitrogen were also computationally investigated. The results show that the reactions are strongly dependent on the substitution pattern, but all are kinetically easily feasible delivering products of differing stability. The calculations can therefore provide important information for experimental endeavors to generate or even isolate so far unknown 1,2,3,4-tetrazines. The feasibility of carbene or 1,2,3-triazolyl-substituted nitrene intermediates for the formation of alkynes is also discussed. The experimental evidence for the proposed processes is enclosed presenting literature known examples of the fragmentation reactions which can most convincingly be explained by the intermediacy of 1,2,3,4-tetrazine derivatives. Furthermore, the electrocyclic ring closure reactions of five other types of bis-1,3-dipoles are calculated, demonstrating that this so far ignored 8π-electrocyclization process can establish a new route to interestingly composed heterocyclic compounds.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202514598"},"PeriodicalIF":16.9,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145077139","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

Gradient Polarization Induces Three-Dimensional Asymmetric Electron Distribution in Covalent Organic Frameworks for Dramatically Enhanced Photocatalytic Overall Nitrogen Fixation. 梯度极化诱导共价有机框架中三维不对称电子分布，显著增强光催化全氮固定。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-16 DOI: 10.1002/anie.202516117

Yunxia Liu, Xiaoxu Deng, Zihe Wang, Shuang-Feng Yin, Peng Chen

{"title":"Gradient Polarization Induces Three-Dimensional Asymmetric Electron Distribution in Covalent Organic Frameworks for Dramatically Enhanced Photocatalytic Overall Nitrogen Fixation.","authors":"Yunxia Liu, Xiaoxu Deng, Zihe Wang, Shuang-Feng Yin, Peng Chen","doi":"10.1002/anie.202516117","DOIUrl":"https://doi.org/10.1002/anie.202516117","url":null,"abstract":"Constructing a donor-acceptor (D-A)-based covalent organic frameworks (COFs) is an effective approach to enhance photocatalytic efficiency, yet the spatial conformation imposes inherent trade-offs between in-plane and interplane carrier transport. Here, we present a spatial gradient polarization strategy that combines distinct electronegativities of (NH)2─C═S and C═O groups in COFs to establish a 3D asymmetric electron distribution and the gradient polarization. Mechanistic studies have shown that the gradient polarization triggers the interlayer dipole rearrangement in a nonpolar orientation, thereby constructing a cooperative in-plane and out-of-plane polarization field. This polarization field decouples the constraints on carrier transport and drives rapid charge transfer in an anisotropic manner, breaking the traditional perception of D-A intramolecular polarization within the plane. Moreover, the resulting polarized microenvironment activates N≡N bonds, optimizes hydrogen-bond networks, and stabilizes reaction intermediates, enabling the sequential conversion pathway of nitrogen. Ultimately, the covalent organic framework containing (NH)2─C═S and C═O groups (SBO) exhibited excellent photocatalytic performance with yields of NH4 + and NO3 - of 11.59 and 7.18 mg g-1 h-1, surpassing all reported systems. Additionally, under natural sunlight, SBO also achieves unprecedented NH4 + (87.17 mg m-2 h-1) and NO3 - (73.63 mg m-2 h-1) yields. Our research not only offers a strategic blueprint for modulating the 3D polarization in COFs but also bridges the gap in the relationship between the molecular structure of materials and the spatial carrier migration.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202516117"},"PeriodicalIF":16.9,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145077125","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

Correction to "Gas-Mediated Tumor Energy Remodeling for Sensitizing Mild Photothermal Therapy". 修正“气体介导的肿瘤能量重塑对轻度光热治疗的敏感性”。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-16 DOI: 10.1002/anie.202519375

引用次数: 0