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Frontispiece: Finding the Key: Binding of Metal-Oxo Clusters to the Enzyme Active Site Enabled by “Click” (Bio)Conjugation 前言:寻找关键:通过“点击”(生物)偶联使金属-氧基簇与酶活性位点结合
Pub Date : 2025-12-08 DOI: 10.1002/ange.2025-m1711050300

Achieving specific interactions of metal-oxo clusters with biological substrates becomes possible through organic functionalization. The illustration depicts a dartboard that symbolizes the enzyme's active site as the molecular target. The darts represent clusters bearing distinct organic functionalities, designed to enable selective interactions with the protein surface. This concept highlights the potential of molecular design strategies to achieve precise bioinorganic recognition. More in the Communication (e202518349) by Mhamad Aly Moussawi, Tatjana N. Parac-Vogt, and co-workers.

通过有机功能化实现金属氧簇与生物底物的特定相互作用成为可能。该图描绘了一个飞镖靶,象征着酶的活性位点作为分子靶标。这些飞镖代表了具有不同有机功能的簇,旨在与蛋白质表面进行选择性相互作用。这一概念强调了分子设计策略实现精确生物无机识别的潜力。通讯中的更多内容(e202518349),作者:mohammad Aly Moussawi, Tatjana N. Parac-Vogt及其同事。
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引用次数: 0
Frontispiece: Carbonothioate-Triggered Cascade Cyclization Enables High-Specificity Fluorescence Imaging of Hydrogen Polysulfides 前文:碳硫酸触发级联环化使多硫化氢的高特异性荧光成像
Pub Date : 2025-12-08 DOI: 10.1002/ange.2025-m1311101500

A carbonothioate-based fluorescent probe is developed that can be selectively activated by H2Sn (n > 1) through cascade cyclization reaction to liberate the phenolic fluorophore. This work for the first time demonstrates the fluorescence imaging of H2Sn dynamics in insulin-resistant cells and type 2 diabetes mellitus (T2DM) mice. Details are reported by Wei Chen and co-workers in their Research Article (e202519021).

开发了一种基于碳硫酸盐的荧光探针,该探针可以通过级联环化反应被H2Sn (n > 1)选择性激活,从而释放酚类荧光团。本工作首次证实了H2Sn在胰岛素抵抗细胞和2型糖尿病(T2DM)小鼠体内的动态荧光成像。详情由Wei Chen及其同事在其研究文章(e202519021)中报道。
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引用次数: 0
A Crystalline Bismuth(II) Radical Anion: Synthesis, Characterization, and Reactivity 晶体铋(II)自由基阴离子:合成、表征和反应性
Pub Date : 2025-12-01 DOI: 10.1002/ange.202515545
Sotirios Pavlidis, Dr. Christian Teutloff, Dr. Ana Guilherme Buzanich, Dr. Konstantin B. Krause, Dr. Franziska Emmerling, Prof. Dr. Robert Bittl, Dr. Josh Abbenseth

We report the synthesis of a planarized tris-amidobismuthane supported by a rigid, bulky NNN pincer ligand, which enforces a T-shaped geometry at the bismuth center. The Bi(NNN) complex features a low-lying LUMO with distinct Bi(6p) orbital character as shown by DFT calculations. Cyclic voltammetry reveals a fully reversible one-electron reduction at E1/2 = –1.85 V versus Fc0/+ in THF. Chemical reduction with KC8 in the presence of 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane (222-crypt) enables the isolation of an unprecedented Bi(II) radical anion in high isolated yields. Multi-frequency EPR, X-ray absorption spectroscopy and SQUID magnetometry complemented by theoretical calculations confirm localization of the unpaired electron on the bismuth center. Preliminary reactivity studies display radical reactivity as shown by single-electron transfer chemistry and radical coupling reactions.

我们报道了一种由刚性、笨重的NNN钳形配体支撑的平面化三氨基甲烷的合成,该配体在铋中心形成了t形几何结构。DFT计算表明,Bi(NNN)配合物具有明显的Bi(6p)轨道特征的低洼LUMO。循环伏安法显示,在E1/2 = -1.85 V时,与f0 /+相比,THF具有完全可逆的单电子还原。在4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8] hexocosane (222-crypt)存在下,用KC8化学还原可以分离出前所未有的Bi(II)自由基阴离子,分离收率很高。多频EPR、x射线吸收光谱和SQUID磁强计结合理论计算证实了未配对电子在铋中心的定位。初步的反应性研究显示了单电子转移化学和自由基偶联反应显示的自由基反应性。
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引用次数: 0
Frontispiece: Panchromatic Gold Alkynyl Complexes with Pyrenyl-N-Heterocyclic Carbene Ligand Displaying Anti-Kasha Behavior 扉页:与芘- n -杂环碳烯配体的全色金炔基配合物显示出抗卡沙行为
Pub Date : 2025-12-01 DOI: 10.1002/ange.2025-m1311102000

The famous French impressionist painter Claude Monet painted the portal of Rouen Cathedral many times between 1892 and 1894. Observing the same model, he attempted to capture the moment under different lighting conditions and at different times of the day. Inspired from this masterpiece, the Research Article by Hani Amouri, Andreas Steffen et al. (e202515695) illustrates a new class of carbene Au-alkynyl complexes where inorganic and organic chromphores merge in harmony to generate anti-Kasha panchromatic emitters, which emit over the entire visible spectrum under different excitation wavelengths.

著名的法国印象派画家克劳德·莫奈在1892年至1894年间多次绘制鲁昂大教堂的大门。观察同一模型,他试图在不同的光照条件下和一天中的不同时间捕捉瞬间。受这一杰作的启发,Hani Amouri, Andreas Steffen等人(e202515695)的研究文章展示了一类新的碳金炔配合物,其中无机和有机发色团和谐融合,产生反卡沙全色发射器,在不同的激发波长下发射整个可见光谱。
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引用次数: 0
Frontispiece: Chemical Synthesis of Arabinogalactans from the Mycobacterium tuberculosis Cell Wall up to the 92-mer and Structure–Conformation–Activity Relationship Studies 前言:结核分枝杆菌细胞壁中阿拉伯半乳聚糖的化学合成及结构-构象-活性关系研究
Pub Date : 2025-11-24 DOI: 10.1002/ange.202584801

One-pot assembly of arabinogalactans from the Mycobacterium tuberculosis cell wall up to the 92-mer has been achieved based on glycosyl ortho-(1-phenylvinyl)benzoates, precluding aglycone transfer issues inherent to one-pot glycan assembly with thioglycosides. Structure–conformation–activity relationship studies revealed that the surface-exposed 30-mer induced a modest NF-κB activation while preserving cell viability (e202515896).

基于糖基邻(1-苯基乙烯基)苯甲酸酯,已经实现了结核分枝杆菌细胞壁上的阿拉伯半乳聚糖的一锅组装,直至92 mer,排除了与巯基糖苷的一锅聚糖组装所固有的苷元转移问题。结构-构象-活性关系研究表明,表面暴露的30-mer在保持细胞活力的同时诱导适度的NF-κB活化(e202515896)。
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引用次数: 0
Frontispiece: Gypsum Gardens: Self-Assembled Tubular Structures of Calcium Sulfate with Relevance for the Detection of Extraterrestrial Life 前言:石膏花园:与探测外星生命相关的硫酸钙自组装管状结构
Pub Date : 2025-11-24 DOI: 10.1002/ange.202584802

Chemical gardens are self-assembled architectures with “life-like” morphologies that form in the absence of any biological activity. In their Communication (e202508098), Matthias Kellermeier et al. show that such structures can also be obtained by contacting reservoirs of calcium and sulfate ions, under conditions that plausibly emulate those prevailing on early Mars. Our results demonstrate that mineralization in purely inorganic, sulfate-rich environments can produce solid matter with biomimetic shapes and may thus lead to false-positive detection of life on the red planet.

化学花园是在没有任何生物活动的情况下形成的具有“类似生命”形态的自组装建筑。在他们的通讯(e202508098)中,Matthias Kellermeier等人表明,这种结构也可以通过接触钙和硫酸盐离子的储集层来获得,其条件似乎与早期火星上普遍存在的条件相似。我们的研究结果表明,在纯无机、富含硫酸盐的环境中,矿化可以产生具有仿生形状的固体物质,从而可能导致对这颗红色星球上生命的假阳性检测。
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引用次数: 0
Outside Front Cover: Deciphering Ball Milling Mechanochemistry via Molecular Simulations of Collision-Driven and Liquid-Assisted Reactivity (Angew. Chem. 50/2025) 外封面:通过碰撞驱动和液体辅助反应的分子模拟来解读球磨机械化学。化学50/2025)
Pub Date : 2025-11-23 DOI: 10.1002/ange.2025-m1711064300
Rupam Gayen, Leonarda Vugrin, Dr. Zehua Zhang, Dr. György Hantal, Dr. Ivan Halasz, Prof. Ana-Sunčana Smith

Mechanical activation in ball-milling mechanochemistry remains experimentally elusive, prompting the theoretical exploration in the Research Article (e202505263) by Ivan Halasz, Ana-Sunčana Smith, and co-workers. Using molecular simulations, mechanochemical impacts under neat and liquid-assisted grinding are modelled, capturing how kinetic energy from the impact drives crystal fragmentation into atoms, ions, and ion pairs, triggering product formation and agglomeration. It is shown that minimal liquid promotes reactivity, while excess stabilizes reactants. This framework enables rational optimization of catalysts and reaction conditions.

在球磨机械化学中的机械激活在实验上仍然难以捉摸,促使Ivan Halasz, ana - sunana Smith及其同事在研究文章(e202505263)中进行了理论探索。利用分子模拟,模拟了纯研磨和液体辅助研磨下的机械化学冲击,捕捉了冲击产生的动能如何驱动晶体破碎成原子、离子和离子对,从而触发产物的形成和团聚。结果表明,最少的液体能促进反应活性,而过量的液体则能稳定反应物。该框架使催化剂和反应条件的合理优化成为可能。
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引用次数: 0
Outside Back Cover: Solvent Channels and Electric Fields Guide Proton Delivery to the Active Site of Heme Peroxidases (Angew. Chem. 50/2025) 外封底:溶剂通道和电场引导质子传递到血红素过氧化物酶的活性位点。化学50/2025)
Pub Date : 2025-11-23 DOI: 10.1002/ange.2025-m1711051200
Reynier Suardíaz, Shakir Ali Siddiqui, Hanna Kwon, Marc van der Kamp, Lola González-Sánchez, Peter C. E. Moody, Emma L. Raven, Adrian J. Mulholland

Local electric fields guide protons toward the heme through two distinct electrostatic funnels at the γ- and δ-edges in heme peroxidases. Water-mediated pathways enable proton exchange with key residues such as Arg38 and His42. These findings reveal that nature pre-organizes electrostatic funnels and solvent channels to provide multiple, well-defined routes for proton delivery, conserved across heme peroxidase enzymes. More in the Research Article (e202515743) by Reynier Suardíaz, Emma L. Raven, Adrian J. Mulholland, and co-workers.

在血红素过氧化物酶中,局部电场通过γ和δ边缘的两个不同的静电通道引导质子走向血红素。水介导的途径使质子与Arg38和His42等关键残基交换。这些发现表明,自然界预先组织了静电通道和溶剂通道,为质子传递提供了多种明确的途径,这些途径在血红素过氧化物酶中是保守的。Reynier Suardíaz, Emma L. Raven, Adrian J. Mulholland及其同事的研究文章(e202515743)中的更多内容。
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引用次数: 0
Inside Back Cover: Redox Reactions with Calcium-Metal Nanoparticles (Angew. Chem. 50/2025) 内页后盖:氧化还原反应与钙金属纳米颗粒(Angew。化学50/2025)
Pub Date : 2025-11-23 DOI: 10.1002/ange.2025-m1711062400
Dr. Christian Ritschel, Anja Appenzeller, Dr. Radian Popescu, Dr. Carsten Donsbach, Dr. Ralf Köppe, Dr. Jonas O. Wenzel, Prof.Dr. Frank Breher, Prof.Dr. Yolita M. Eggeler, Prof.Dr. Wim Klopper, Prof.Dr. Claus Feldmann

Calcium metal nanoparticles (5.4 ± 1.2 nm) are realized by TMEDA-supported reduction of CaI2 with [LiNaph] in toluene. Their reactivity is exemplarily evaluated in the liquid phase and results in [{(DippNacNac)(thf)Ca}2(naph)] with a rare naphthalenide dianion, [{(DippNacNac)(thf)CaMo(Cp)H}2(fulvalene)] with unusual MoH → Ca dative bonding, and [Au9(PPh3)8](naph)(tmeda)0.5 with a non-charged body-centered cubic Au9 cluster core of zerovalent gold. More in the Research Article (e15995) by Wim Klopper, Claus Feldmann, and co-workers.

通过tmeda负载下用[LiNaph]在甲苯中还原ca2,制备了金属钙纳米颗粒(5.4±1.2 nm)。它们的反应性在液相中得到[{(DippNacNac)(thf)Ca}2(naph)]与一个稀有的萘离子,[{(DippNacNac)(thf)CaMo(Cp)H}2(fulvalene)]具有异常的MoH→Ca键,[Au9(PPh3)8](naph)(tmeda)0.5与一个非带电的零价金体心立方Au9簇核。更多的研究文章(e15995)由Wim Klopper, Claus Feldmann和同事。
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引用次数: 0
Inside Back Cover: Light-Induced Chemiluminescence Microscopy for Imaging Heterogeneous Photo-Fenton-Type Activity on Individual Hematite Photocatalysts (Angew. Chem. 49/2025) 内页后盖:光致化学发光显微镜成像单个赤铁矿光催化剂的非均相光芬顿型活性(新)。化学49/2025)
Pub Date : 2025-11-20 DOI: 10.1002/ange.2025-m1311103200
Taeyoon Kim, Prof. Joohoon Kim

The cover illustrates light-induced chemiluminescence (CL) microscopy, proposed to visualize heterogeneous photocatalytic activity on individual photocatalysts in a controlled spatiotemporal way. In their Research Article (e202509277), Taeyoon Kim and Joohoon Kim demonstrate the potential of CL microscopy by revealing the spatial heterogeneity in photo-Fenton-type activity of dendritic hematite within a single hematite photocatalyst, as well as the unique activity distribution among individual photocatalysts in a population of hematite structures of different shapes and sizes.

该封面说明了光诱导化学发光(CL)显微镜,提出了在可控的时空方式下观察单个光催化剂的异质光催化活性。在他们的研究文章(e202509277)中,Taeyoon Kim和Joohoon Kim通过揭示单一赤铁矿光催化剂中树突赤铁矿光芬顿型活性的空间异质性,以及不同形状和大小结构的赤铁矿群中单个光催化剂之间独特的活性分布,展示了CL显微镜的潜力。
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引用次数: 0
期刊
Angewandte Chemie
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