Angewandte Chemie International Edition最新文献_第10页

Quantifying the Biodegradation of Water‐Soluble Polymer Mixtures with Diffusion NMR Spectroscopy 用扩散核磁共振光谱定量水溶性聚合物混合物的生物降解

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-09-27 DOI: 10.1002/anie.202514235

Louisa T. Brenninkmeijer, Jacob L. Golding, Arianna Brandolese, Melanie M. Britton, Andrew P. Dove

{"title":"Quantifying the Biodegradation of Water‐Soluble Polymer Mixtures with Diffusion NMR Spectroscopy","authors":"Louisa T. Brenninkmeijer, Jacob L. Golding, Arianna Brandolese, Melanie M. Britton, Andrew P. Dove","doi":"10.1002/anie.202514235","DOIUrl":"https://doi.org/10.1002/anie.202514235","url":null,"abstract":"Polymers in liquid formulations result in 36 million tons of waste each year. It is estimated that 13% of these polymers directly enter, and accumulate in, natural environments, however, their fate is poorly understood; in part as a consequence of challenges in characterizing how the polymers biodegrade. Multiple analytical techniques have been used to quantify polymer biodegradation but require extensive sample preparation and can only measure one species accurately at a time, inhibiting the measurement of water‐soluble polymer mixtures. Here, we report the application of diffusion nuclear magnetic resonance spectroscopy as an alternative method to enable the facile monitoring of polymer biodegradation. This technique uniquely aids the understanding of biodegradation mechanisms, by measuring chemical as well as molar mass changes, concurrently, for both the polymer and degradation products. Furthermore, the ability to detect and measure the molar mass of multiple separate species enables the measurement of simultaneous biodegradation of polymer mixtures, including polymers with different chemical structures but the same molar mass.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"3 1","pages":"e202514235"},"PeriodicalIF":16.6,"publicationDate":"2025-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145153645","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

Silylative Amide to Nitrile Conversion Mediated by Simple Lanthanide-Organoamides: Scope and Mechanism. 简单镧系有机酰胺介导的硅化酰胺制腈：范围和机理。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-09-26 DOI: 10.1002/anie.202513996

Zhiyu Feng,Qingheng Lai,Yuang Wang,Alessandro Motta,Yosi Kratish,Tobin J Marks

{"title":"Silylative Amide to Nitrile Conversion Mediated by Simple Lanthanide-Organoamides: Scope and Mechanism.","authors":"Zhiyu Feng,Qingheng Lai,Yuang Wang,Alessandro Motta,Yosi Kratish,Tobin J Marks","doi":"10.1002/anie.202513996","DOIUrl":"https://doi.org/10.1002/anie.202513996","url":null,"abstract":"Efficient, selective, and environmentally benign catalytic nitrile synthesis is attractive for pharmaceuticals, specialty chemicals and materials, and large-scale industrial applications. In this regard, metal-catalyzed silylative conversion of primary amides to nitriles is emerging as a promising approach. This contribution reports the utilization of readily available lanthanide-organic amido precatalysts, Ln[N(SiMe3)2]3, Ln = lanthanide, to selectively convert primary alkyl and aryl/heterocyclic amides having diverse functional groups to nitriles, including pharma building blocks, in high yields using the silane reagents PhSiH3 and TMS-O-[Si(H)(Me)-O-]n-TMS in a solvent-free process. Kinetic and mechanistic data reveal the role of lanthanide amidates as the catalytically-active species, while DFT analysis indicates a catalytic pathway unlike that found in transition metal complex-catalyzed processes. Thus, the lanthanide amidate resting state actively participates in the catalysis, where rate-determining bound amidate silylation is activated by the metal center and influenced by the bound amidate electronic and steric characteristics. DFT analysis of the catalytic cycle reveals that the relative energies of three intermediate endergonic steps, hence the rate-determining step, depends on the silane concentration.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"42 1","pages":"e202513996"},"PeriodicalIF":16.6,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140085","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

Laser-Programmed Spatial Relay Catalysis on Co─Ag Dual Heterojunctions for Efficient Nitrate-to-Ammonia Conversion via Migratory *NO2 Shuttling. Co - Ag双异质结的激光程序化空间接力催化通过迁移*NO2穿梭实现硝酸盐到氨的高效转化。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-09-26 DOI: 10.1002/anie.202515393

Jing Geng,Yaocai Wu,Sihan Ji

{"title":"Laser-Programmed Spatial Relay Catalysis on Co─Ag Dual Heterojunctions for Efficient Nitrate-to-Ammonia Conversion via Migratory *NO2 Shuttling.","authors":"Jing Geng,Yaocai Wu,Sihan Ji","doi":"10.1002/anie.202515393","DOIUrl":"https://doi.org/10.1002/anie.202515393","url":null,"abstract":"Electrocatalytic nitrate (NO3 -) reduction to ammonia (NH3) represents a sustainable strategy for wastewater treatment and green NH3 production; however, its efficiency is limited by sluggish reaction kinetics and the competing hydrogen evolution reaction (HER). Herein, we propose a laser-programmed spatial relay catalysis strategy mediated by migratory *NO2 intermediate on Co─Ag dual heterojunctions. Site-selective laser irradiation of Ag-predeposited Co foil generates spatially segregated interfaces, where hexagonal close-packed (hcp)-Co/face-centered cubic (fcc)-Co heterojunctions facilitate thermodynamically favorable NO3 - deoxygenation, and Ag/hcp-Co interfaces promote kinetically enhanced NO2 - protonation. Operando spectroscopic analysis, combined with electrochemical differential mass spectrometry (DEMS), confirms the migratory relay mechanism involving *NO2 transport between catalytic sites. Density functional theory (DFT) calculations show that interfacial charge redistribution enables distinct catalytic functions at interface sites. The phase-transformation-formed hcp-Co/fcc-Co heterojunctions enhance NO3 - adsorption and reduce deoxygenation barriers, whereas Ag/hcp-Co interfaces suppress HER and promote *NO hydrogenation by lowering the rate-determining *NO→*NOH barrier to 0.25 eV via Fermi-level d-band engineering. This collaborative spatial design reaches 94.8% ± 3.4% Faradaic efficiency (FE) for NH3 in nitrate-to-ammonia electroreduction at -0.4 V (versus RHE), with 92.5% activity retention over 50 cycles. It highlights the promise of interface-driven relay catalysis in complex electrochemical systems and enables scalable electrode fabrication.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"154 1","pages":"e202515393"},"PeriodicalIF":16.6,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140384","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

Amyloid Peptide Nanofibrils Promote Efficient Neurotransmitter Oxidation and Serve as Scaffolds for Melanin Production. 淀粉样肽纳米原纤维促进有效的神经递质氧化并作为黑色素生成的支架。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-09-26 DOI: 10.1002/anie.202510234

Inhye Kim,Liam R Marshall,Shams Aaghaz,Yang Li,Ho Yee Joyce Fung,Ivan V Korendovych

引用次数: 0

Fluorescent Peptide Tracers for Simultaneous Oxytocin Receptor Activation and Visualization. 同时催产素受体激活和可视化的荧光肽示踪剂。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-09-26 DOI: 10.1002/anie.202515180

Monika Perisic Böhm,Predrag Kalaba,Rachel S Gormal,Maja Zupančič,Alexandra Wolf,Mia Juračić,Thomas Kremsmayr,Frédéric A Meunier,Thierry Langer,Christian W Gruber,Erik Keimpema,Markus Muttenthaler

{"title":"Fluorescent Peptide Tracers for Simultaneous Oxytocin Receptor Activation and Visualization.","authors":"Monika Perisic Böhm,Predrag Kalaba,Rachel S Gormal,Maja Zupančič,Alexandra Wolf,Mia Juračić,Thomas Kremsmayr,Frédéric A Meunier,Thierry Langer,Christian W Gruber,Erik Keimpema,Markus Muttenthaler","doi":"10.1002/anie.202515180","DOIUrl":"https://doi.org/10.1002/anie.202515180","url":null,"abstract":"The oxytocin receptor (OTR) regulates critical physiological functions and has been implicated in a range of diseases, including psychiatric and neurodevelopmental disorders such as autism spectrum disorder. However, a lack of reliable molecular tools hampers the progress in understanding OTR's mechanistic roles in (patho)physiological processes. In this work, we addressed this gap and developed potent, selective, and bright fluorescent peptide tracers that enable precise spatial and functional investigations of OTR actions. Our tracers showed efficient OTR labeling, activation, and internalization in cellular bioassays in both live and fixed overexpression and primary cell systems, including those subjected to immunocytochemical protocols, highlighting their versatility as reliable new imaging tools. Additionally, they facilitated single-molecule tracking of OTR with live-cell super-resolution microscopy and were able to separate OTR-positive cells from mixed oxytocin and vasopressin receptor-containing cell populations via fluorescence-activated cell sorting, underscoring their wider scope for live-cell applications. In summary, we developed versatile fluorescent tracers based on the endogenous ligand oxytocin for both live-cell and post-hoc imaging that have additional functional capabilities beyond traditional antibody labeling, offering new avenues to explore OTR's role in health and disease.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"42 1","pages":"e202515180"},"PeriodicalIF":16.6,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140087","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

Failure Mechanism of High-Temperature Li–S Batteries in Localized High-Concentration Electrolytes 局部高浓度电解液中高温锂硫电池失效机理研究

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-09-25 DOI: 10.1002/anie.202515993

Zixiong Shi, Simil Thomas, Georgian Melinte, Dong Guo, Jehad K. El-Demellawi, Nizar Jaber, Manuel A. Quevedo-Lopez, Osman M. Bakr, Omar F. Mohammed, Husam N. Alshareef

{"title":"Failure Mechanism of High-Temperature Li–S Batteries in Localized High-Concentration Electrolytes","authors":"Zixiong Shi, Simil Thomas, Georgian Melinte, Dong Guo, Jehad K. El-Demellawi, Nizar Jaber, Manuel A. Quevedo-Lopez, Osman M. Bakr, Omar F. Mohammed, Husam N. Alshareef","doi":"10.1002/anie.202515993","DOIUrl":"https://doi.org/10.1002/anie.202515993","url":null,"abstract":"Conventional ether-based electrolytes struggle to sustain steady operation of lithium–sulfur (Li–S) batteries at high temperatures due to inferior thermal durability and aggravated parasitic reactions. Although localized high-concentration electrolyte (LHCE) has emerged as a promising strategy to enhance thermal stability, its deployment in high-temperature (HT) Li–S batteries has met with limited success. Herein, the failure mechanism of HT Li–S batteries in LHCE is revealed via probing sulfur redox reactions and electrolyte solvation chemistry. Slow reaction kinetics and high polysulfide reactivity are determined to be the dominant factors causing the rapid capacity deterioration at high temperatures. To this end, a diethylene glycol dibutyl ether-based localized medium concentration electrolyte (B-LMCE) with suitable anion concentration and weakly solvating effect is developed. The new electrolyte concurrently achieves fast cathode kinetics and stable anode/electrolyte interface. With the assistance of a tailored electrochemical voltage range of 1–3.8 V, Li–S batteries sustain a durable cycling performance over 250 cycles at 60 °C. They also showcase superior wide-temperature operation (0 °C–80 °C) while enabling feasible fabrication of Ah-level pouch cells. Our study opens a new avenue for designing extreme-temperature electrolytes toward pragmatic Li–S batteries.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"4 1","pages":"e202515993"},"PeriodicalIF":16.6,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145141083","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

Sulfinyl Aziridines as Stereoselective Covalent Destabilizing Degraders of the Oncogenic Transcription Factor MYC 亚砜酰叠氮嘧啶作为致癌转录因子MYC的立体选择性共价不稳定降解剂

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-09-25 DOI: 10.1002/anie.202508518

Hannah T. Rosen, Kelvin Li, Christian E. Stieger, Erin L. Li, Brynne Currier, Scott M. Brittain, Francisco J. Garcia, Diana C. Beard, Michael D. Jones, Sandra Haenni-Holzinger, Dustin Dovala, Jeffrey M. McKenna, Markus Schirle, Thomas J. Maimone, Daniel K. Nomura

{"title":"Sulfinyl Aziridines as Stereoselective Covalent Destabilizing Degraders of the Oncogenic Transcription Factor MYC","authors":"Hannah T. Rosen, Kelvin Li, Christian E. Stieger, Erin L. Li, Brynne Currier, Scott M. Brittain, Francisco J. Garcia, Diana C. Beard, Michael D. Jones, Sandra Haenni-Holzinger, Dustin Dovala, Jeffrey M. McKenna, Markus Schirle, Thomas J. Maimone, Daniel K. Nomura","doi":"10.1002/anie.202508518","DOIUrl":"https://doi.org/10.1002/anie.202508518","url":null,"abstract":"Although MYC is a significant oncogenic transcription factor driver of cancer, directly targeting MYC has remained challenging due to its intrinsic disorder and poorly defined structure, deeming it “undruggable.” Whether transient pockets formed within unstructured regions of proteins can be selectively targeted with small molecules remains an outstanding challenge. Here, we developed a stereochemically paired spirocyclic oxindole aziridine covalent library and screened this library for degradation of MYC. We identified a hit covalent ligand, KL2-236, bearing a unique sulfinyl aziridine warhead, that engaged MYC as a pure MYC/MAX protein complex, and in cancer cells to destabilize MYC, inhibit MYC transcriptional activity and degrade MYC in a proteasome-dependent manner through targeting intrinsically disordered C203 and D205 residues. Notably, this reactivity was most pronounced for specific stereoisomers of KL2-236 with a diastereomer, KL4-019, that was largely inactive. Mutagenesis of both C203 and D205 completely attenuated KL2-236-mediated MYC degradation. We also optimized our KL2-236 hit compound to generate a more potent, selective, and durable MYC degrader, KL4-219A. Our results reveal a novel ligandable site within MYC and indicate that certain intrinsically disordered regions within transcription factors, such as MYC, can be interrogated by isomerically unique chiral small molecules, leading to destabilization and degradation.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"107 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145141114","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

Enhanced Efficiency and Stability of Inverted Perovskite Solar Cells via Isomerization Engineering of Self-Assembled Monolayers. 通过自组装单层异构化工程提高倒置钙钛矿太阳能电池的效率和稳定性。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-09-25 DOI: 10.1002/anie.202513338

Chao Lv,Yawei Miao,Jing Wang,Jiayu Li,Zeyuan Hu,Yuexing Zhang,Ping Wu,Longlong Geng,Ying Li,Xiangchuan Meng,Fariba Tajabadi,Nima Taghavinia,Ke Gao,Qifan Xue

引用次数: 0

Synthesis of Bridge-Substituted Bicyclo[1.1.1]Pentanes by Catalytic Metal Carbene Insertion into Bicyclo[1.1.0]Butanes 催化金属卡宾插入双环[1.1.0]丁烷合成桥取代双环[1.1.1]戊烷

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-09-25 DOI: 10.1002/anie.202514232

Shaopeng Liu, Yongquan Ning, Wei Song, Paramasivam Sivaguru, Yixuan Wang, Ying Gan, Edward A Anderson, Xihe Bi

{"title":"Synthesis of Bridge-Substituted Bicyclo[1.1.1]Pentanes by Catalytic Metal Carbene Insertion into Bicyclo[1.1.0]Butanes","authors":"Shaopeng Liu, Yongquan Ning, Wei Song, Paramasivam Sivaguru, Yixuan Wang, Ying Gan, Edward A Anderson, Xihe Bi","doi":"10.1002/anie.202514232","DOIUrl":"https://doi.org/10.1002/anie.202514232","url":null,"abstract":"1,2,3-Trisubstituted bicyclo[1.1.1]pentanes (BCPs) are emerging saturated hydrocarbon bioisosteres for polysubstituted benzenes; however, their synthesis from bicyclo[1.1.0]butanes (BCBs) via direct metal carbene insertion remains unrealized. Herein, we report the first catalytic metal carbene insertion into BCBs using triftosylhydrazones as safe and stable carbene precursors, which circumvents the use of [1.1.1]propellane in the synthesis of the BCPs scaffold. This operationally straightforward method accommodates a wide range of substituted BCB esters and triftosylhydrazones, enabling the synthesis of valuable 1,2,3-trisubstituted BCPs, including those bearing a trifluoromethylated quaternary all-carbon center, in good-to-excellent yields. Selective post-synthetic transformations of the product BCP esters into other useful small-ring building blocks, as well as the preparation of the BCP analogue of a drug molecule fragment, demonstrate the versatility and utility of this chemistry. Mechanistic investigations, including density functional theory calculations, support a direct, stepwise metal carbene addition into the C─C bond of the BCB.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"95 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145134490","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

trans-Silaboration of Terminal Alkynes Enabled by Development of a New Si─B Reagent 一种新型Si─B试剂的开发促进了末端炔的反硅化反应

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-09-25 DOI: 10.1002/anie.202517688

Song Chen, Kailin Yin, Liangbo Zhu, Chunming Cui, Dongbing Zhao

引用次数: 0