Yuxin Yuan, Jianping Chen, Tianyue Qian, Bowen Zhang, Ke Ye, Ruimin Li, Xiaowei Yang
{"title":"Hydrogen Atom Capture Toward Dense Solid Electrolyte Interface for Long-Cycling Aqueous Zinc-Ion Batteries.","authors":"Yuxin Yuan, Jianping Chen, Tianyue Qian, Bowen Zhang, Ke Ye, Ruimin Li, Xiaowei Yang","doi":"10.1002/anie.202513722","DOIUrl":"https://doi.org/10.1002/anie.202513722","url":null,"abstract":"<p><p>Aqueous zinc-ion batteries (AZIBs) are promising high-safety energy storage devices, but their practical implementation has been limited by dendrite growth and hydrogen evolution reaction (HER). Solid-electrolyte interface (SEI) is expected to address these problems. Herein, we revealed that HER results in loose and porous interfacial structure, making the in situ construction of reliable SEI a challenge. Thus, a universal and effective hydrogen atom scavenging strategy is proposed to in situ construct a dense and uniform inorganic SEI by introducing potassium persulfate (PSS). PSS scavenges the adsorbed hydrogen atoms, thus inhibiting HER. Meanwhile, PSS is reduced into SO<sub>4</sub> <sup>2-</sup> and participates in the formation of zinc hydroxide sulfates (ZHS). With no interference of H<sub>2</sub> bubbles on ZHS crystallization, an ideal SEI is constructed. This ZHS-SEI exhibits superior electronic insulation, effectively suppressing further HER and Zn dendrite growth during cycling. As a result, the Zn//Zn symmetric cell with PSS can achieve stable Zn plating/stripping for 1882 h at 5 mA cm<sup>-2</sup> and 2.5 mAh cm<sup>-2</sup> and 650 h at 10 mA cm<sup>-2</sup> and 5 mAh cm<sup>-2</sup>, respectively. The cycling stability of the Zn||NVO full cell is also significantly improved at 5 A g<sup>-1</sup>. This work provides a novel perspective for stabilizing the zinc anode interface.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202513722"},"PeriodicalIF":16.9,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145180796","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}
Ying Mo, Wang Zhou, Shiru Wu, Zuqin Duan, Peng Gao, Yan Duan, Peitao Xiao, Hao Ouyang, Shi Chen, Jilei Liu
{"title":"Polarity Gradient CEI Driven Rapid Desolvation for Extreme Fast-Charging Potassium-Ion Batteries.","authors":"Ying Mo, Wang Zhou, Shiru Wu, Zuqin Duan, Peng Gao, Yan Duan, Peitao Xiao, Hao Ouyang, Shi Chen, Jilei Liu","doi":"10.1002/anie.202518712","DOIUrl":"https://doi.org/10.1002/anie.202518712","url":null,"abstract":"<p><p>Potassium-ion batteries (PIBs) offer an opportunity for superior fast-charging compared to lithium-ion batteries, owing to their faster K<sup>+</sup> transport in electrolyte. However, severe side reactions at the cathode electrolyte interphase (CEI), sluggish K<sup>+</sup> transport, and cathode structural degradation hinder the development of fast-charging PIBs. Herein, we tailor-design a polarity gradient CEI via an electrolyte additives modification strategy. Specifically, the outer B-F/B-O species assist in withdrawing solvent molecules around K<sup>+</sup> during the desolvation process, while abundant K<sub>2</sub>CO<sub>3</sub> and KF throughout the CEI facilitate K<sup>+</sup> transport and structural stability. Consequently, the KFeHCF/graphite full cell demonstrates improved charge transfer and diffusion kinetics, with suppressed Fe dissolution, enhancing stability of both the cathode bulk structure and interphase under fast-charging conditions. The full cell with optimized CEI delivers high reversible capacities of 126.5 mAh g<sup>-1</sup> at 0.02 A g<sup>-1</sup> and 95.8 mAh g<sup>-1</sup> at 1 A g<sup>-1</sup> (a charging time of 7.5 min for 80% of the capacity), and maintains 67 mAh g<sup>-1</sup> at 5 A g<sup>-1</sup> as well as good long cycle life. Moreover, it retains 85.1 mAh g<sup>-1</sup> and exhibits good rate performance even at -10 °C. Our work reveals the critical role of rationally regulating CEI components and structure for fast-charging PIBs.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202518712"},"PeriodicalIF":16.9,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145180837","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}
{"title":"London Dispersion-Induced Contraction of the Cu─O Bond in Copper(I) Phenolates.","authors":"Zhen Huan, Zong-Chang Han, Likun Dong, Han-Shi Hu, Jin-Dong Yang, Jun Li, Jin-Pei Cheng","doi":"10.1002/anie.202513210","DOIUrl":"https://doi.org/10.1002/anie.202513210","url":null,"abstract":"<p><p>Conventional chemical wisdom holds that shorter bonds of a given type generally exhibit greater strength. Here, we reveal a counterintuitive bonding mode in copper(I) phenoxides, where bulky substituents induce Cu─O bond contraction without concomitant strengthening. X-ray crystallographic analysis shows that increasing steric bulk at ortho positions of the phenolate ligand can shorten Cu─O bonds and promote symmetrical molecular geometries. Combined structural and computational studies demonstrate that London dispersion (LD) between N-heterocyclic carbene ligands and ortho-tert-butyl phenolates plays a crucial role in driving this conformational reorganization. Local energy decomposition analysis quantifies substantial dispersion stabilization (by up to 11.2 kcal mol<sup>-1</sup>). Notably, natural orbital analysis indicates that the compressed Cu─O bonds exhibit diminished σ-character despite enhanced π-interactions. This LD-induced bond contraction results in overall shorter yet weaker Cu─O bonds than those in less sterically bulk analogues, thereby establishing a different bonding paradigm from the conventional bond-length/strength correlation.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202513210"},"PeriodicalIF":16.9,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145180818","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}
Wan-Chen Cindy Lee, Luiz F T Novaes, Rojan Ali, Thomas Wirth, Song Lin
{"title":"Electrochemical ⍺-C─H Functionalization of Nitramines for Accessing Bifunctional Energetic Heterocycles.","authors":"Wan-Chen Cindy Lee, Luiz F T Novaes, Rojan Ali, Thomas Wirth, Song Lin","doi":"10.1002/anie.202515252","DOIUrl":"https://doi.org/10.1002/anie.202515252","url":null,"abstract":"<p><p>The synthesis of energetic materials (EMs) often involves hazardous reagents and harsh conditions, raising safety and environmental concerns. We herein present an electrochemical method for the ⍺-C─H azolation of nitramines, enabling the integration of nitramines and various nitrogen-rich azoles as dual energetic components within the same molecule. To enhance the practicality of the overall synthesis, we developed a tandem two-step process that transforms free amines into nitramines using stable and readily available reagents, which was complemented by subsequent electrochemical azolation to complete a streamlined, scalable preparation of bifunctional energetic compounds. Finally, a continuous flow system was employed to further improve the practicality of the electrosynthetic method, which substantially reduced electrolyte usage and increased productivity. Computational and experimental data revealed that the introduction of azoles, particularly those with additional nitro substituents, improves the energy density and thermal stability of nitramines. This work provides a proof of concept that the reported electrochemical azolation reaction may not only offer a safer and more sustainable alternative to traditional approaches for energetic material synthesis, but it will also provide a platform for the discovery of novel compounds with favorable energetic properties.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202515252"},"PeriodicalIF":16.9,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145180808","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}
Soumyamouli Pal, Arit Patra, John Kim, Sangchul Roh, Juriti Rajbangshi, Reid C Van Lehn, Joerg Lahann, Nicholas L Abbott
{"title":"Formation of Interconnected Nanofiber Sheets by Chemical Vapor Polymerization at the Free Surface of Liquid Crystalline Films.","authors":"Soumyamouli Pal, Arit Patra, John Kim, Sangchul Roh, Juriti Rajbangshi, Reid C Van Lehn, Joerg Lahann, Nicholas L Abbott","doi":"10.1002/anie.202515703","DOIUrl":"https://doi.org/10.1002/anie.202515703","url":null,"abstract":"<p><p>We report that chemical vapor polymerization (CVP) of aminomethyl[2.2]paracyclophane into nematic liquid crystal (LC) films (thicknesses of 18 µm) yields quasi-two-dimensional, sub-micron thick nanoporous polymer networks consisting of interconnected amine-functionalized nanofibers/nanowalls (widths of 30 ± 1 nm). We establish that the polymer networks form at the free surface of the LC films with thicknesses ranging from 79 ± 5 to 280 ± 14 nm and nanoscopic pores tunable via the choice of LC and monomer loading. Structural analysis using electron microscopy reveals the networks to possess morphologies ranging from open bicontinuous-like to cellular foam-like structures which, along with optical observations and molecular dynamics (MD) simulations, supports a synthesis pathway involving an interface-confined phase separation. MD simulations provide further insight into the atomic-scale processes determining the synthesis pathway, including the role of reactive precursor chemistry (e.g., hydroxymethyl[2.2]paracyclophane versus aminomethyl[2.2]paracyclophane versus [2.2]paracyclophane) in defining the nanostructure of the polymer product. Fluorescence and X-ray photoelectron spectroscopy confirm that the nanofiber sheets are decorated with primary amine groups, permitting covalent functionalization of the surfaces of the nanosheets. Finally, we show how the nanosheet synthesis can be integrated with existing membrane technology, illustrating the potential utility of the nanoporous sheets in a range of contexts, including filters, separators, and heat exchanger surfaces.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202515703"},"PeriodicalIF":16.9,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145180821","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}
{"title":"Molecular Recognition Driven Organelle Cross-Linking Induces Endoplasmic Reticulum Stress and Mitochondrial Dysfunction to Potentiate Cancer Immunotherapy.","authors":"Mian Tang, Junteng Qiu, Yunfeng Lu, Zhongke Liu, Yin Liu, Chenhui Luo, Chunhai Fan, Ruibing Wang","doi":"10.1002/anie.202514530","DOIUrl":"https://doi.org/10.1002/anie.202514530","url":null,"abstract":"<p><p>Organelles maintain cellular homeostasis through highly specialized division of labor, dynamic interactions, as well as extensive inter-organellar information exchange, thereby ensuring the physiological functions of organisms. Although functionalized polymers that target a specific organelle to modulate or disrupt their function have been developed for therapeutic applications, macromolecular systems capable of manipulating two or more types of key organelles remain rare. Here, we designed cyclodextrin and adamantane derivatives that can respectively target endoplasmic reticulum (ER) and mitochondria, to achieve precise spatial manipulation of both organelles at the subcellular organelle level via a specific molecular recognition approach. This approach selectively induced unusual junctions between the ER and mitochondria, disrupting their functional synergy, triggering multiple cellular stress responses, such as Ca<sup>2+</sup> homeostasis imbalance, reactive oxygen species (ROS) burst, energy metabolism disorder, and ultimately leading to severe immunogenic cell death (ICD). By converting \"cold\" tumors into \"hot\" tumors, this strategy provides a supramolecular perspective for tumor immunotherapy.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202514530"},"PeriodicalIF":16.9,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145180774","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}
Shivudu Godhulayyagari, Sara R Nixon, Devleena Samanta
{"title":"Single-Molecule DNA Tweezers Enable Programmable Control of Enzyme Activity via Arbitrary Molecular Cues.","authors":"Shivudu Godhulayyagari, Sara R Nixon, Devleena Samanta","doi":"10.1002/anie.202513154","DOIUrl":"https://doi.org/10.1002/anie.202513154","url":null,"abstract":"<p><p>Engineering allosteric control sites into enzymes typically requires extensive protein modification. Here, we introduce single-molecule DNA tweezers (SMDTs), which enable programmable, allosteric-like regulation of enzyme activity in response to user-defined chemical cues, without altering the enzyme itself. SMDTs consist of two aptamers connected by a tunable, stimuli-responsive DNA linker. By binding non-covalently to two distinct sites on an enzyme, the SMDT adopts a \"pinched\" conformation, reminiscent of mechanical tweezers, that inhibits enzymatic activity. Upon exposure to specific molecular triggers, the SMDT undergoes a conformational change that releases the inhibitory aptamer, restoring function. The degree of inhibition and reactivation efficiency can be finely tuned by adjusting the DNA linker's length, sequence, flexibility, and geometry. Operating at nanomolar concentrations, the system exhibits high specificity, capable of discriminating between closely related inputs, including single-base mismatches in nucleic acids. Importantly, SMDTs can be programmed to respond not only to molecular abundance but also to molecular activity. We show the versatility of this platform by regulating enzymes using diverse triggers, including nucleic acids, transcription factors (TATA-binding protein [TBP], cellular myelocytomatosis [c-Myc]), signaling proteins (platelet-derived growth factor [PDGF]), small molecules (kanamycin), and metal ions (Mn2+). These results establish a generalizable framework for designing responsive protein binders that translate molecular recognition into functional outcomes.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202513154"},"PeriodicalIF":16.9,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145180788","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}
Chi Zhang, Geng Huang, Tianxiang Gao, Yuting Liu, Wenjing Jia, Chuan Zhu, Kai Guo, Chao Feng
{"title":"Defluorinative Fluoro-Aza-Nazarov Cyclization.","authors":"Chi Zhang, Geng Huang, Tianxiang Gao, Yuting Liu, Wenjing Jia, Chuan Zhu, Kai Guo, Chao Feng","doi":"10.1002/anie.202518782","DOIUrl":"https://doi.org/10.1002/anie.202518782","url":null,"abstract":"<p><p>A highly efficient approach toward polysubstituted β-fluoropyrroles is described herein. Starting from α,α-difluoro-β,γ-unsaturated ketone, which is easily available from corresponding difluorinated silyl enol ether, an unprecedented defluorinative fluoro-aza-Nazarov cyclization mediated by TiCl<sub>4</sub> is successfully developed, which enables expedient construction of fluorine-containing tetra-/penta-substituted pyrroles in moderate to excellent yields. The protocol features the use of inexpensive Lewis acid, insensitivity to steric hindrance and compatibility with substrates of different substitution patterns. Furthermore, a two-step sequence and also a one-pot protocol were established for synthesizing tri-substituted pyrroles bearing a 3-fluorine substituent, utilizing a Pd-catalyzed defluorinative fluoro-aza-Nazarov cyclization. This methodology provides a modular solution for the rapid assembly of structurally complex β-fluoropyrrole scaffolds, which are notoriously difficult targets using previous methods. Mechanistic studies indicated a Ti-mediated allylic C─F bond activation pathway, triggering the unprecedented defluorinative Nazarov-type cyclization.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202518782"},"PeriodicalIF":16.9,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145153168","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}
{"title":"Continuous Dual Hydrogenation of Biomass Substrates in a Membrane-Free Solid Electrolyte Reactor.","authors":"Yanjie Zhai, Weisong Li, Xin Gao, Shanhe Gong, Qing Xia, Jie Wu, Shuting Wei, Yingying Zhou, Xiao Zhang","doi":"10.1002/anie.202513146","DOIUrl":"https://doi.org/10.1002/anie.202513146","url":null,"abstract":"<p><p>Production of chemicals from biomass through electrocatalytic hydrogenation shows great potential to reduce environmental impact across various applications in sustainable materials, medicine, food, and more. Particularly, dual electrocatalytic hydrogenation, leveraging concurrent reactions at both anode and cathode stand out with maximized electron efficiency (∼200%) and production yield. However, at higher voltages, anodic hydrogen atoms (H<sup>*</sup>) tend to revert to protons. This tendency results in challenges such as low conversion rates and selectivity, and difficulties in maintaining continuous production. Herein, by employing hydrazine and water as the hydrogen sources for anode and cathode reactions, respectively, we achieved efficient dual hydrogenation of maleic acid to succinic acid. This approach produces two H<sup>*</sup> atoms per electron transferred, promoting effective carbon-carbon (C-C) bond formation at both cathode and anode. We further developed a modular, membrane-free solid electrolyte reactor for continuous dual hydrogenation of maleic acid using a commercial cobalt catalyst. By leveraging the hydrazine oxidation and water reduction, the reactor consistently produces succinic acid with a Faraday efficiency of approximately 180% for over 200 h at 100 mA. Our approach shows significant potential for practical applications in green chemistry, particularly in efficient biomass conversion.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202513146"},"PeriodicalIF":16.9,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145153122","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}
Umar Rashid, Abdalghani H S Daaoub, P A Sreelakshmi, Sara Sangtarash, Hatef Sadeghi, Veerabhadrarao Kaliginedi
{"title":"Quantum Interference Effect in Saturated Systems: Effect of Anchoring Group Position on Conductance of Bipiperidines and their in-situ Derived Dithiocarbamates.","authors":"Umar Rashid, Abdalghani H S Daaoub, P A Sreelakshmi, Sara Sangtarash, Hatef Sadeghi, Veerabhadrarao Kaliginedi","doi":"10.1002/anie.202513806","DOIUrl":"https://doi.org/10.1002/anie.202513806","url":null,"abstract":"<p><p>This study investigates quantum interference in σ-only molecular systems, focusing on the impact of anchoring group nature and its position. Using a combined approach of mechanically controlled break junction experiments and quantum transport calculations, we demonstrate that meta-connected σ-conducting bipiperidine-based molecular junctions exhibit higher conductance than para-connected ones. This trend is opposite to that of the trend typically observed in π-molecular systems, indicating the existence of distinctly different quantum interference phenomenon in σ-only molecular systems. Further, we show that anchoring group modifications achieved through in-situ dithiocarbamylation significantly alters the conductance and decay factors. We also elucidate the mechanism behind multiple conductance features observed in aliphatic bipiperidines with cyclic secondary amine and dithiocarbamate anchoring groups. This work demonstrates σ-quantum interference in bipiperidine-based molecular systems and highlights how changes in junction configuration, nature of the anchoring group and its position can be used to control conductance in σ-only molecular systems.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202513806"},"PeriodicalIF":16.9,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145133280","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}