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

Regulating Solvating Sites for Stable High-voltage Lithium Metal Batteries. 稳定高压锂金属电池的调节溶剂化位点。

Angewandte Chemie (International ed. in English) Pub Date : 2025-05-28 DOI: 10.1002/anie.202506395

Zeyuan Liu, Shuoqing Zhang, Haikuo Zhang, Baochen Ma, Haotian Zhu, Tao Zhou, Long Li, Xuezhang Xiao, Ruhong Li, Lixin Chen, Tao Deng, Xiulin Fan

{"title":"Regulating Solvating Sites for Stable High-voltage Lithium Metal Batteries.","authors":"Zeyuan Liu, Shuoqing Zhang, Haikuo Zhang, Baochen Ma, Haotian Zhu, Tao Zhou, Long Li, Xuezhang Xiao, Ruhong Li, Lixin Chen, Tao Deng, Xiulin Fan","doi":"10.1002/anie.202506395","DOIUrl":"https://doi.org/10.1002/anie.202506395","url":null,"abstract":"The long-lasting stability of high-voltage lithium metal batteries (LMBs) critically rely on both the cathodic and anodic stability of electrolytes, which can be enhanced by increasing the salt-to-solvent molar ratio. However, this approach is limited by solubility constraints. In this work, we introduce a dual-anchoring strategy to regulate the solvating sites of glymes via directional atomic interactions. Specifically, Fδ--Hδ+ interactions transform the Li+-glyme coordination and induce more anion coordination within Li+ primary solvation sheath while Hδ+-Oδ- interactions reduce the electron density at free oxygen sites, thus raising the oxidational potential of glyme and enhancing the overall oxidation stabiltiy of electrolytes. This strategy results in an electrolyte with exceptional compatibility with both lithium metal anode (LMA) and high-voltage cathode, enabling LMA with an ultrahigh Coulombic efficiency (CE) of 99.76%. Furthermore, the assembled LMBs exhibit extended lifespans, retaining 80% of their capacity under aggressive conditions: 834 and 370 cycles at 4.4 V and 4.5 V, respectively, for 30-μm-Li||2.0-mAh cm-2 LiNi0.8Co0.1Mn0.1O2 cells, and 100 cycles for anode-free Cu||LiNi0.5Co0.2Mn0.3O2 pouch cells. This work offers novel insights into the advancement of next-generation LMBs based on ether-based electrolytes.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202506395"},"PeriodicalIF":0.0,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144164540","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

Protein Secondary Structure Patterns In Short-Range Cross-Link Atlas. 近程交联图谱中的蛋白质二级结构模式。

Angewandte Chemie (International ed. in English) Pub Date : 2025-05-28 DOI: 10.1002/anie.202507348

Claudio Iacobucci, Alice Vetrano, Alessio Di Ianni, Nico Di Fonte, Gianluca Dell'Orletta, Samantha Reale, Isabella Daidone

{"title":"Protein Secondary Structure Patterns In Short-Range Cross-Link Atlas.","authors":"Claudio Iacobucci, Alice Vetrano, Alessio Di Ianni, Nico Di Fonte, Gianluca Dell'Orletta, Samantha Reale, Isabella Daidone","doi":"10.1002/anie.202507348","DOIUrl":"https://doi.org/10.1002/anie.202507348","url":null,"abstract":"Cross-linking mass spectrometry (XL-MS) has become a powerful tool in structural biology for investigating protein structure, dynamics, and interactomics. However, short-range cross-links, defined as those connecting residues fewer than 20 positions apart, have traditionally been considered less informative and largely overlooked, leaving significant data unexplored in a systematic manner. Here, we present a system-wide analysis of short-range cross-links, demonstrating their intrinsic correlation with protein secondary structure. We introduce the X-SPAN (Cross-link Structural Pattern Analyzer) software, which integrates publicly available XL-MS datasets from system-wide experiments with AlphaFold-predicted protein structures. Our analysis reveals distinct cross-linking patterns that reflect the spatial constraints imposed by secondary structural elements. Specifically, α-helices exhibit periodic cross-linking patterns consistent with their characteristic helical pitch, whereas coils and β-strands display nearly monotonic distributions. A context-dependent protein grammar reinforces short-range cross-link specificity. Short-range cross-links can enhance the statistical inference of secondary structures within integrative modeling workflows. Additionally, our work establishes a framework for benchmarking AlphaFold's local prediction accuracy and provides novel quality control criteria for XL-MS experiments. We anticipate that X-SPAN and our short-range cross-link database will serve as a valuable resource for exploring local secondary structure rearrangements and their potential roles in protein function and allosteric regulation.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202507348"},"PeriodicalIF":0.0,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144164535","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

Electronically Asynchronous Transition State Tuned from Remote Site for Oxygen Atom Transfer by CuII-Nitrite Complexes. cuii -亚硝酸盐配合物对氧原子远程转移的电子异步过渡态调整。

Angewandte Chemie (International ed. in English) Pub Date : 2025-05-23 DOI: 10.1002/anie.202501338

Jyoti Devi, Anannya Saha, Suman Kumar Barman

{"title":"Electronically Asynchronous Transition State Tuned from Remote Site for Oxygen Atom Transfer by CuII-Nitrite Complexes.","authors":"Jyoti Devi, Anannya Saha, Suman Kumar Barman","doi":"10.1002/anie.202501338","DOIUrl":"https://doi.org/10.1002/anie.202501338","url":null,"abstract":"Nitrite (NO2-) reduction to nitric oxide (NO) is of paramount interest in biology. Cu-nitrite reductase reduces NO2- to NO while alternatively NO2- can be reduced to NO at copper centre via oxygen atom transfer (OAT) to electron-rich substrate like PPh3. This work demonstrates tuning of LUMO (Lowest Unoccupied Molecular Orbital) energy by remote site modification which leads to change in electrochemical property and OAT activity of CuII-NO2- involving electronically asynchronous transition state. For this purpose, we report here four CuII-NO2- complexes: [CuII(LCH2)(NO2)(ClO4)] (1), [CuII(LO)(NO2(ClO4)] (2), [CuII(LCH2Me)(NO2)(ClO4)] (3), [CuII(LOMe)(NO2)(ClO4)] (4) with similar primary coordination sphere but different substituents at remote site. In going from 1 - 4, by remote site substitution, there is systematic stabilization of LUMO energy which correlates linearly with the increased OAT to PPh3 resulting in 130 times reactivity enhancement for 4 compared to 1. This kind of significant reactivity enhancement by tuning LUMO energy from remote site is very rare. Mechanistic study involving experimental and computational study reveals asynchronous mechanism which was hitherto not reported for any OAT. The observed increase in OAT reactivity from 1 to 4 is attributed to an increase in the extent of asynchronicity in corresponding transition states controlled from remote site modification.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202501338"},"PeriodicalIF":0.0,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144133369","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

Conformational Change in a Four-Tetrad DNA G-Quadruplex upon Intercalation of a Small-Molecule Ligand PyDH2. 嵌入小分子配体PyDH2后四联体DNA g -四联体构象的变化。

Angewandte Chemie (International ed. in English) Pub Date : 2025-05-22 DOI: 10.1002/anie.202501443

Liliya A Yatsunyk, Kailey N Martin, Gwendolyn Lam, Oksana Reznichenko, Kyle E Brunner, Michael Zdilla, Sawyer E McCarthy, Anton Granzhan

{"title":"Conformational Change in a Four-Tetrad DNA G-Quadruplex upon Intercalation of a Small-Molecule Ligand PyDH2.","authors":"Liliya A Yatsunyk, Kailey N Martin, Gwendolyn Lam, Oksana Reznichenko, Kyle E Brunner, Michael Zdilla, Sawyer E McCarthy, Anton Granzhan","doi":"10.1002/anie.202501443","DOIUrl":"https://doi.org/10.1002/anie.202501443","url":null,"abstract":"G-quadruplexes (G4s) are non-canonical DNA structures implicated in a number of biological processes. Small-molecule ligands can alter stability and folding of G4s, which can potentially be exploited for therapeutic purposes. In this work, we investigate the interaction of telomeric DNA fragment from Tetrahymena thermophila (TET25, 5'-G(TTGGGG)4-3') with a G4 ligand PyDH2 belonging to the bisquinolinium family. When alone, TET25 adopts a mixture of three conformations, with the most abundant being a four-tetrad hybrid G4. In the presence of PyDH2, surprisingly, TET25 folds into an antiparallel chair G4, with PyDH2 intercalated between G-tetrads 2 and 3, according to our crystal structure. The structure represents the second example, and the first crystallo-graphic evidence, of ligand intercalation into a G4. In solution, the interaction of PyDH2 and TET25 leads to a number of complexes differing by G4 topology and binding stoichiometry, strong stabilization of G4 (∆Tm = 12.4 °C in the presence of one equiv. of PyDH2) and large hysteresis of ∼ 10 °C, suggesting that ligand binding and G4 folding processes are complex.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202501443"},"PeriodicalIF":0.0,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144130015","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

Hydrogen Bond Assisted PCET and Formation of WIII-OH in Bis-dithiolene Complex. 氢键辅助PCET及双-二硫代配合物中ii - oh的形成。

Angewandte Chemie (International ed. in English) Pub Date : 2025-05-22 DOI: 10.1002/anie.202506861

Wonjung Lee, Daeyong Um, Yujin Baek, Sugyeong Hong, Youngseob Lee, Jaeheon Lee, Jin Kim, Sun Hee Kim, Kyung-Bin Cho, Junhyeok Seo

{"title":"Hydrogen Bond Assisted PCET and Formation of WIII-OH in Bis-dithiolene Complex.","authors":"Wonjung Lee, Daeyong Um, Yujin Baek, Sugyeong Hong, Youngseob Lee, Jaeheon Lee, Jin Kim, Sun Hee Kim, Kyung-Bin Cho, Junhyeok Seo","doi":"10.1002/anie.202506861","DOIUrl":"https://doi.org/10.1002/anie.202506861","url":null,"abstract":"The redox non-innocent nature of dithiolene ligands is well known for stabilizing high-valent metal ions and facilitating proton-coupled electron transfer (PCET) processes. Until now, proton reactivity at the dithiolene site has been primarily associated with low-valent metal centers, as high-valent metal-dithiolene complexes were not considered viable for such reactivity. This study introduces high-valent bis(dithiolene) tungsten (W)-oxo complexes featuring hydrogen-bonding interactions, unveiling a novel proton reduction mechanism mediated by the dithiolene moiety. The process begins with a nucleophilic W-oxo forming a hydrogen bond, followed by a second hydrogen bond at the dithiolene-sulfur (S) site. These hydrogen-bonding interactions significantly modulate the molecular orbital energy levels, enabling the WIV→III reduction at -1.75 V (Eexp) and allowing, for the first time, the acquisition of an EPR spectrum of a WIII-OH intermediate species. In contrast, direct electron transfer into the WIV=O state would populate the dithiolene π* orbital, demanding substantially larger energy (Ecal = -3.45 V). For catalytic proton reduction, the proton transfer through the dithiolene-S site was identified as the energetically most favorable pathway for generating the WV-H catalytic species.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202506861"},"PeriodicalIF":0.0,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144130016","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

Redirecting the Peptide Cleavage Causes Protease Inactivation. 重定向肽切割导致蛋白酶失活。

Angewandte Chemie (International ed. in English) Pub Date : 2025-05-20 DOI: 10.1002/anie.202506832

Michael Gütschow, Christian Breuer, Jim Küppers, Anna-Christina Schulz-Fincke, Anna Heilos, Carina Lemke, Petra Spiwokowá, Janina Schmitz, Laura Cremer, Marta Frigolé-Vivas, Michael Lülsdorff, Matthias D Mertens, Filip Wichterle, Miloš Apeltauer, Martin Horn, Erik Gilberg, Norbert Furtmann, Jürgen Bajorath, Ulrike Bartz, Bernd Engels, Michael Mareš

{"title":"Redirecting the Peptide Cleavage Causes Protease Inactivation.","authors":"Michael Gütschow, Christian Breuer, Jim Küppers, Anna-Christina Schulz-Fincke, Anna Heilos, Carina Lemke, Petra Spiwokowá, Janina Schmitz, Laura Cremer, Marta Frigolé-Vivas, Michael Lülsdorff, Matthias D Mertens, Filip Wichterle, Miloš Apeltauer, Martin Horn, Erik Gilberg, Norbert Furtmann, Jürgen Bajorath, Ulrike Bartz, Bernd Engels, Michael Mareš","doi":"10.1002/anie.202506832","DOIUrl":"https://doi.org/10.1002/anie.202506832","url":null,"abstract":"Cysteine and serine proteases cleave peptides through covalent catalysis by generating a transient adduct with the N-terminal part of the substrate after releasing its C-terminal part. We demonstrate the unique redirection of this event leading to strong enzyme inactivation. For targeting human cathepsin B, a cysteine protease of significant therapeutic importance, we designed tailored peptidomimetics with a variety of dipeptide fragments directed towards the occluding loop and equipped with numerous N-terminal carbamate warheads. The carbamate deprotonation catalyzed by the active site thiolate initiates the redirected cleavage. The C-terminal part of the inhibitors remains covalently attached to the protease. Hydrolysis of such carbamoyl-enzyme complexes is catalytically unsupported rendering inhibition irreversible. This novel mechanism of action comprises a significant extension of the covalent drug space.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202506832"},"PeriodicalIF":0.0,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144113246","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

Anomalous Piezochromic Luminescence in Covalent Triazine Frameworks via Molecular Insertion: Blueshifted and Enhanced Emission. 通过分子插入共价三嗪框架的异常压致发光：蓝移和增强发射。

Angewandte Chemie (International ed. in English) Pub Date : 2025-05-20 DOI: 10.1002/anie.202509398

Zhenxing Yang, Chunguang Zhai, Lingyan Dang, Zhenfeng Niu, Yuchen Shang, Xinmeng Hu, Yaqi Wang, Tianzi Zhou, Mingguang Yao

{"title":"Anomalous Piezochromic Luminescence in Covalent Triazine Frameworks via Molecular Insertion: Blueshifted and Enhanced Emission.","authors":"Zhenxing Yang, Chunguang Zhai, Lingyan Dang, Zhenfeng Niu, Yuchen Shang, Xinmeng Hu, Yaqi Wang, Tianzi Zhou, Mingguang Yao","doi":"10.1002/anie.202509398","DOIUrl":"10.1002/anie.202509398","url":null,"abstract":"Piezochromic materials typically exhibit pressure-induced redshifted and quenched emission due to enhanced intermolecular π-π stacking and molecular planarization. Consequently, achieving blueshifted and enhanced emission in π-conjugated systems remains a significant challenge. Here, we report anomalous piezochromic luminescence in covalent triazine frameworks (CTFs) via molecular insertion. Upon introducing methanol into the nanopores of CTFs, a blueshift in emission from 507.0 to 485.5 nm, accompanied by enhanced intensity, is observed under compression up to 1.22 GPa, distinctly contrasting the redshifted and quenched emission typically observed in compressed pristine CTFs and other crystalline porous materials (CPMs). Combined experimental and theoretical analyses reveal that methanol can weaken the interlayer π-π stacking and intralayer conjugation of CTFs by forming weak interactions with CTFs, such as hydrogen bonding, to realize the interlayer slip and intralayer distortions of CTFs, which results in the blueshifted and enhanced emission. This strategy also proves effective with other molecular insertions, offering a general approach to achieving anomalous piezochromic luminescence in CTFs. Our findings establish molecular insertion as a robust method for engineering pressure-responsive luminescent materials and provide valuable insights for the design of advanced optical sensors and stimuli-responsive systems.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202509398"},"PeriodicalIF":0.0,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144113272","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

PCET Photodecarboxylation for SN2'-Type Alkylation of gem-Dichlorocyclobutenones. 宝石-二氯环丁烯酮SN2′型烷基化反应的PCET光脱羧反应。

Angewandte Chemie (International ed. in English) Pub Date : 2025-05-20 DOI: 10.1002/anie.202505782

Pinku Prasad Mondal, Subham Das, Sourav Das, Basudev Sahoo

引用次数: 0

Isothiourea-Catalysed Acylative Kinetic and Dynamic Kinetic Resolution of Planar Chiral Paracyclophanols. 异硫脲催化平面手性对环酚的酰化动力学和动力学拆分。

Angewandte Chemie (International ed. in English) Pub Date : 2025-05-20 DOI: 10.1002/anie.202507126

Andrew David Smith, Zhanyu Zhou, Kevin Kasten, Aidan P McKay, David B Cordes

引用次数: 0

An Organic-Inorganic-Integrated Solid Electrolyte Interphase with High Resilience and Anti-Corrosion for Sustainable Zinc Metal Anode. 一种高回弹性和耐腐蚀的有机-无机-集成固体电解质界面用于可持续锌金属阳极。

Angewandte Chemie (International ed. in English) Pub Date : 2025-05-19 DOI: 10.1002/anie.202501702

Maoyu Peng, Zhenjie Liu, Machuan Hou, Ruochen Zhang, Min Cheng, Jiangtao Yu, Yang Feng, Peixin Jiao, Tongrui Zhang, Ziheng Zhang, Chen Xi, Zhe Hu, Kai Zhang

{"title":"An Organic-Inorganic-Integrated Solid Electrolyte Interphase with High Resilience and Anti-Corrosion for Sustainable Zinc Metal Anode.","authors":"Maoyu Peng, Zhenjie Liu, Machuan Hou, Ruochen Zhang, Min Cheng, Jiangtao Yu, Yang Feng, Peixin Jiao, Tongrui Zhang, Ziheng Zhang, Chen Xi, Zhe Hu, Kai Zhang","doi":"10.1002/anie.202501702","DOIUrl":"https://doi.org/10.1002/anie.202501702","url":null,"abstract":"Aqueous zinc metal batteries are highly regarded for their exceptional safety, low cost, environmental compatibility, and potential as a sustainable alternative to lithium-ion batteries. However, Zn dendrite growth and hydrogen evolution on anode side result in limited lifespan and safety issues. Herein, an organic-inorganic-integrated solid electrolyte interphase was in-situ formed by adding 4-(Trifluoromethyl)-1H-imidazole as an electrolyte additive. The artificial SEI merited higher maximum elastic deformation energy due to relatively high resilience and toughness, which can prevent Zn dendrite penetration and anode self-cracking and pulverization. In addition, N-containing heterocyclic in SEI acts as a H+ catcher, thereby inhibiting anode corrosion and hydrogen evolution. As a result, the Zn||Zn symmetric cell has delivered stable cycling performance after 1500 h at 5 mA cm-2 with a terminated capacity of 5 mAh cm-2. And an outstanding coulombic efficiency of 99.46% at 2200th cycle was achieved for a Cu||Zn asymmetric cell. Furthermore, a Zn||PANI full battery presented a stable cycling performance with a high-capacity retention of 97.6% after 200 cycles.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202501702"},"PeriodicalIF":0.0,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144103485","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