JACS Au最新文献

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Aqueous Accumulation and Co-Accumulation of Multiple Cationic Porphyrins within a Polyaromatic Capsule 多芳胶囊内多种阳离子卟啉的水富集和共富集
IF 8.5
JACS Au Pub Date : 2026-09-28 Epub Date: 2026-08-26 DOI: 10.1021/jacsau.6c00880
Kazuki Toyama, Yuya Tanaka, Yohei Haketa, Hiroki Horita, Hiromitsu Maeda, Michito Yoshizawa
{"title":"Aqueous Accumulation and Co-Accumulation of Multiple Cationic Porphyrins within a Polyaromatic Capsule","authors":"Kazuki Toyama,&nbsp;Yuya Tanaka,&nbsp;Yohei Haketa,&nbsp;Hiroki Horita,&nbsp;Hiromitsu Maeda,&nbsp;Michito Yoshizawa","doi":"10.1021/jacsau.6c00880","DOIUrl":"https://doi.org/10.1021/jacsau.6c00880","url":null,"abstract":"<p>In contrast to stable cation–anion assembliesin nonpolarsolvents, neither cations nor anions assemble themselves due to electrostaticrepulsion and/or hydration in bulk solution. Here we report the multipleaccumulation of cationic porphyrins in water using a polyaromaticcapsule formed from bent amphiphiles. Simple stirring of the aqueouscapsule with cationic Au(III)-tetraphenylporphyrins in water leadsto the efficient formation of new host–guest composites, muchmore efficiently than that with nonionic Zn(II) derivatives underthe same conditions. The detailed UV–visible, NMR, DLS, AFM,TEM, and molecular modeling studies reveal that the accumulated multicationcomposite is a ∼2 nm-sized spherical particle, consistingof stacked, three porphyrin cations in the capsule as a major product,through effective host–guest π–π and CH−πinteractions. The theoretical analysis indicates the importance oflarge dispersion force-based stabilization between the cationic porphyrins.Notably, the cationic Au(III)-porphyrins and nonionic polyaromaticcompounds such as Cu(II)-phthalocyanine and fullerene are co-accumulatedefficiently in the cavity through a stepwise grinding-stirring protocol.Otherwise unstable multicationic accumulation as well as unusual cationic-nonionicco-accumulation are demonstrated in the adaptable cavity of the polyaromaticcapsule even under hydratable aqueous conditions.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"6 9","pages":"5225–5231"},"PeriodicalIF":8.5,"publicationDate":"2026-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149067519","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
Pd-Catalyzed Regio-, Diastereo-, and Enantioselective Construction of Vicinal Tertiary Stereocenters from Cyclic Allylboronate Salts and Allyl Electrophiles 由环丙烯基硼酸盐和烯丙基亲电试剂催化的邻叔立体中心的区域、非映对和对映选择性构建
IF 8.5
JACS Au Pub Date : 2026-09-28 Epub Date: 2026-08-21 DOI: 10.1021/jacsau.6c01001
Roman Popov, Cheng Zhang, Laure Guénée, Clément Mazet
{"title":"Pd-Catalyzed Regio-, Diastereo-, and Enantioselective Construction of Vicinal Tertiary Stereocenters from Cyclic Allylboronate Salts and Allyl Electrophiles","authors":"Roman Popov,&nbsp;Cheng Zhang,&nbsp;Laure Guénée,&nbsp;Clément Mazet","doi":"10.1021/jacsau.6c01001","DOIUrl":"https://doi.org/10.1021/jacsau.6c01001","url":null,"abstract":"<p>A regio-, diastereo-,and enantioselective Pd-catalyzed allylationof the lithium salts of 6-membered cyclic allylboronates is reported.The system relies on the use of a commercially available <em>C</em><sub>2</sub>-symmetric chiral bisphosphine ligand and gives accessto borylated 1,5-dienes featuring vicinal 3,4-<em>cis</em> tertiary stereocenters. It delivers uniformly high enantiocontrolacross the series, together with high regio- and diastereoselectivityfor the majority of substrates. Furthermore, the method simplifiesthe synthesis of stereochemically complex tetrahydrofuran derivativespossessing three contiguous stereocenters after the standard oxidationand acidic treatment of the borylated products.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"6 9","pages":"5336–5343"},"PeriodicalIF":8.5,"publicationDate":"2026-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149067556","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
Photocatalytic Proximity Labeling Maps RNA and Protein Subcellular Landscapes 光催化接近标记映射RNA和蛋白质亚细胞景观
IF 8.5
JACS Au Pub Date : 2026-09-28 Epub Date: 2026-09-01 DOI: 10.1021/jacsau.6c01018
Meihan Hou, Linao Ren, Xin Xi, Rongjie Zhu, Shengda Xie, Yaqian Liu, Xiaocheng Weng, Xiang Zhou, Yuhao Du
{"title":"Photocatalytic Proximity Labeling Maps RNA and Protein Subcellular Landscapes","authors":"Meihan Hou,&nbsp;Linao Ren,&nbsp;Xin Xi,&nbsp;Rongjie Zhu,&nbsp;Shengda Xie,&nbsp;Yaqian Liu,&nbsp;Xiaocheng Weng,&nbsp;Xiang Zhou,&nbsp;Yuhao Du","doi":"10.1021/jacsau.6c01018","DOIUrl":"https://doi.org/10.1021/jacsau.6c01018","url":null,"abstract":"<p>Mapping the molecularlandscapes within subcellular compartmentsis critical for understanding cellular function. Photocatalytic proximitylabeling has emerged as an increasingly diversified chemical strategyfor interrogating biomolecular microenvironments in living systems.However, a modular small-molecule platform that can be readily retargetedand used to capture both protein and RNA neighborhoods within specificorganelles remains underdeveloped. Existing photocatalytic approacheshave employed distinct probe-activation modes for biomolecular labeling.Here, PhotoPL adopts an oxidative activation design based on establishedselenide photooxidation chemistry within a modular organelle-targetedplatform. This method employs an organelle-targeted photocatalystand an activatable selenide probe. Upon visible light irradiation,the localized catalyst generates short-lived reactive intermediatesthat covalently tag proximal biomolecules. We successfully appliedPhotoPL to profile the proteomes and transcriptomes of mitochondriaand the endoplasmic reticulum (ER), validating the high-fidelity captureof organelle-specific molecules. Unlike enzyme-based methods, PhotoPLutilizes small-molecule components, minimizing cellular perturbation.Its key advantage is a modular, “plug-and-play” designthat allows for rapid retargeting to new subcellular locations withoutlaborious genetic cloning. This modular and scalable platform expandsthe current chemical toolbox for dissecting the molecular organizationof cells and exploring the interplay between proteins and RNAs inhealth and disease.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"6 9","pages":"5351–5361"},"PeriodicalIF":8.5,"publicationDate":"2026-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149067476","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
Learning Gains in Organic Chemistry from Full and Hybrid Specifications Grading 从全面和混合规格分级中学习有机化学的收益
IF 8.5
JACS Au Pub Date : 2026-09-28 Epub Date: 2026-09-03 DOI: 10.1021/jacsau.6c00531
Joseph D. Houck, Brandon J. Yik, Eric D. Nacsa
{"title":"Learning Gains in Organic Chemistry from Full and Hybrid Specifications Grading","authors":"Joseph D. Houck,&nbsp;Brandon J. Yik,&nbsp;Eric D. Nacsa","doi":"10.1021/jacsau.6c00531","DOIUrl":"https://doi.org/10.1021/jacsau.6c00531","url":null,"abstract":"<p>In recent years, alternative grading strategies to traditionalpoints-based systems have gained popularity, particularly in STEM.Specifications grading is one type of alternative grading that focusesstudents on meeting course learning objectives rather than accumulatingpoints, sets a threshold for satisfactory work, and often includesfrequent, low-stakes assessments, feedback, and opportunities forreattempts or revision. However, the contribution of these featuresto student learning in authentic courses remains difficult to isolate.This study provides course-scale evidence that frequent, feedback-rich,reattemptable learning-target assessment is associated with higherstandardized exam performance in large-enrollment Organic ChemistryI. Students in multiple sections that adopted this assessment structure,whether embedded in full specifications grading or in a hybrid points-basedsystem, scored significantly higher on the same custom ACS OrganicChemistry Exam than students in a traditionally graded comparisonsection. Higher scores were observed in both same-instructor and cross-instructorcomparisons. Improvements were concentrated among students with lowerincoming preparation, as well as among women and students who didnot identify exclusively as white. No corresponding losses were observedamong students with higher incoming preparation, men, or studentswho identified exclusively as white. Overall, these findings suggestthat frequent, feedback-rich, reattemptable learning-target assessmentsmay be a useful mechanism within alternative grading systems for supportingstudent performance in organic chemistry.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"6 9","pages":"4956–4967"},"PeriodicalIF":8.5,"publicationDate":"2026-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149067479","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
Post-Search Validation and Curation of Site-Resolved N-Glycoproteomics Data 位点解析n -糖蛋白组学数据的搜索后验证和管理
IF 8.5
JACS Au Pub Date : 2026-09-28 Epub Date: 2026-09-09 DOI: 10.1021/jacsau.6c00875
Adam P. Urminsky, Juan C. Rojas E., Lenka Hernychova, Noortje de Haan
{"title":"Post-Search Validation and Curation of Site-Resolved N-Glycoproteomics Data","authors":"Adam P. Urminsky,&nbsp;Juan C. Rojas E.,&nbsp;Lenka Hernychova,&nbsp;Noortje de Haan","doi":"10.1021/jacsau.6c00875","DOIUrl":"https://doi.org/10.1021/jacsau.6c00875","url":null,"abstract":"<p>Given the significantrole of glycosylation in modulating proteinstructure and activity, glycoproteomics is gaining increased interestfrom the broad scientific community. Large-scale site-resolved N-glycoproteomicsrelies on automated MS<sup>2</sup>-based searches, but candidate glycopeptideassignments can remain ambiguous when isomeric or isobaric glycanstructures, adducts, chemical modifications, in-source fragments,or incomplete MS<sup>2</sup> evidence support more than one plausibleinterpretation. Here, we systematically categorize common challengesand misassignments in glycoproteomics and present a post-search validationworkflow using Skyline software to identify and correct these. Theworkflow matches search-engine-derived candidate assignments to LC–MS/MSevidence for correct precursor monoisotope assignment, retention timebehavior, and glycosite context. The workflow is demonstrated withByonic-derived glycopeptide candidate lists and converts automatedsearch results into curated, verifiable, site-resolved N-glycopeptidefeatures for downstream quantification and reporting. We applied theworkflow to data from 52 human serum samples, and reviewed 3,071 candidateN-glycopeptide IDs. From these, 1,722 MS<sup>2</sup> candidate IDswere refuted as inconsistent with chromatographic and/or precursor-levelevidence. Curation added 320 glycopeptide features, comprising 152MS<sup>1</sup>-supported composition-level assignments and 168 additionalLC-resolved isomer features, yielding a final curated feature setof 1,436 N-glycopeptides across the serum N-glycoproteome. Together,these results show that reviewing the raw LC-MS/MS data associatedwith search-engine results improves both the accuracy and comprehensivenessof detectable N-glycopeptides, supporting more transparent and reliablereporting. The curated dataset provides a resource for future methoddevelopment, benchmarking and machine–learning efforts directedat automated glycopeptide validation.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"6 9","pages":"5478–5493"},"PeriodicalIF":8.5,"publicationDate":"2026-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149067576","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
Development of a Polypeptide-Based Platform to Construct Antibody-Drug Conjugates with High Potency 构建高效抗体-药物偶联物多肽平台的研究
IF 8.5
JACS Au Pub Date : 2026-09-28 Epub Date: 2026-08-14 DOI: 10.1021/jacsau.6c01025
Ruyao Tang, Fusheng Guo, Jinyi Bai, Xiaoguang Lei
{"title":"Development of a Polypeptide-Based Platform to Construct Antibody-Drug Conjugates with High Potency","authors":"Ruyao Tang,&nbsp;Fusheng Guo,&nbsp;Jinyi Bai,&nbsp;Xiaoguang Lei","doi":"10.1021/jacsau.6c01025","DOIUrl":"https://doi.org/10.1021/jacsau.6c01025","url":null,"abstract":"<p>Antibody-drug conjugates(ADCs) represent an emergingpharmaceuticalcategory that leverages antibodies to facilitate drug delivery totarget cells. A key challenge for ADCs is increasing the drug-antibodyratio (DAR) to improve efficacy without compromising their properties,such as pharmacokinetics. Here, we present a novel polypeptide-basedplatform that substantially increases the DAR of antibody-payloadADCs while minimally compromising the ADCs’ inherent characteristics.A polypeptide-based antibody-drug conjugate lead (polypeptide ADC <strong>6c</strong>), capable of achieving a DAR of up to 61, was synthesizedusing the versatile click reaction method based on our polypeptide-basedplatform. <strong>6c</strong> could efficiently recognize antigens, besubsequently endocytosed, and achieve subnanomolar activity at thecellular level. Moreover, <strong>6c</strong> exhibited excellent pharmacokineticparameters and potent antitumor efficacy in mice. Collectively, thisstudy provides and characterizes a highly variable polypeptide backboneplatform that can be used to efficiently develop innovative ADCs withhigh payloads for the treatment of various cancers</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"6 9","pages":"5362–5369"},"PeriodicalIF":8.5,"publicationDate":"2026-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149071053","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
All-in-one Photoelectrochromic Device Enabling Designable Coloration and Real-Time Light Adaptation 一体机光电致变色器件,实现可设计的颜色和实时光适应
IF 8.5
JACS Au Pub Date : 2026-09-28 Epub Date: 2026-08-20 DOI: 10.1021/jacsau.6c00768
Xin Guo, Rui Zhang, Huaihai Jin, Ruoshi Li, Yanan Li, Hmbat Batelbek, Fan Yang, Yinglin Wang, Xintong Zhang, Yichun Liu, Akira Fujishima
{"title":"All-in-one Photoelectrochromic Device Enabling Designable Coloration and Real-Time Light Adaptation","authors":"Xin Guo,&nbsp;Rui Zhang,&nbsp;Huaihai Jin,&nbsp;Ruoshi Li,&nbsp;Yanan Li,&nbsp;Hmbat Batelbek,&nbsp;Fan Yang,&nbsp;Yinglin Wang,&nbsp;Xintong Zhang,&nbsp;Yichun Liu,&nbsp;Akira Fujishima","doi":"10.1021/jacsau.6c00768","DOIUrl":"https://doi.org/10.1021/jacsau.6c00768","url":null,"abstract":"<p>Solar-powered electrochromic devices (SP-ECDs) are promisingforzero-energy smart optical systems, holding potential applicationsin energy-saving windows, augmented reality displays, and adaptivecamouflage. State-of-the-art SP-ECDs typically rely on the physicalstacking of solar cells and electrochromic components. This approachinevitably introduces multiple heterogeneous interfaces, which severelylimit the switching speed, operational stability, and color diversityof integrated devices. Herein, we introduce an all-in-one photoelectrochromicdevice that molecularly integrates dye-sensitized photoanodes andviologen electrochromic molecules within a single redox electrolyte.This innovative device achieves a record switching time of ∼7s under optical, electrical, or hybrid stimuli, enabling real-timelight adaptation to various dynamic illumination situations. The devicepresents high operational stability, enduring over 10<sup>3</sup> cyclesunder continuous AM 1.5G illumination. Furthermore, it offers a widerange of designable color palette (red, green, blue, purple, and cyan)with uniform, full-frame coloring appearance, facilitating furtheraesthetic and functional designs. Our strategy establishes a monolithicarchitecture that overcomes the integration complexity in conventionalSP-ECDs, inspiring the creation of customized material platforms andthe advancement of self-adaptive optoelectronics.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"6 9","pages":"5093–5101"},"PeriodicalIF":8.5,"publicationDate":"2026-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149067550","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
Structural Basis of a High-Affinity Antibody Binding to Glycoprotein with Glycocalyx Decay 一种结合糖萼衰变糖蛋白的高亲和力抗体的结构基础
IF 8.5
JACS Au Pub Date : 2026-09-28 Epub Date: 2026-08-21 DOI: 10.1021/jacsau.6c00598
Yun Bin Han, Jun Niu, Deng Pan, Chunchao Feng, Ke Song, Bing Meng, Shengyan Zhu, Sandra Behren, Ulrika Westerlind, Yan Zhang, Haiguang Liu, Lan Xu, Dapeng Zhou
{"title":"Structural Basis of a High-Affinity Antibody Binding to Glycoprotein with Glycocalyx Decay","authors":"Yun Bin Han,&nbsp;Jun Niu,&nbsp;Deng Pan,&nbsp;Chunchao Feng,&nbsp;Ke Song,&nbsp;Bing Meng,&nbsp;Shengyan Zhu,&nbsp;Sandra Behren,&nbsp;Ulrika Westerlind,&nbsp;Yan Zhang,&nbsp;Haiguang Liu,&nbsp;Lan Xu,&nbsp;Dapeng Zhou","doi":"10.1021/jacsau.6c00598","DOIUrl":"https://doi.org/10.1021/jacsau.6c00598","url":null,"abstract":"<p>Cancer-associateddefects in mucin-type O-glycosylation exposetruncated glycans on cell-surface glycoproteins and create tumor-associatedglycopeptide epitopes. However, the structural principles by whichantibodies recognize specific MUC1 glycopeptide sequences remain incompletelydefined. Here, we report the molecular basis of MUC1 recognition by16A, a high-affinity antibody isolated against hypoglycosylated MUC1.Co-crystal structures of 16A Fab bound to site-selectively glycosylatedMUC1 peptides revealed that 16A recognizes an STAPPAHG-centered epitopewithin the MUC1 variable number tandem repeat region. Surface plasmonresonance analysis showed that GalNAc modification at the threoninesite in this sequence increased Fab binding affinity by 30.6-foldrelative to the nonglycosylated peptide. Structural and mutationalanalyses identified a hydrogen bond between the threonine-linked GalNAcand Trp34 in heavy-chain CDR1 as a key contributor to this affinityenhancement. Cell-based binding assays further showed that COSMC deficiencyenhanced 16A recognition of MUC1-expressing cells, while moleculardynamics simulations suggested that Ser-linked Core 1 extension cancreate local steric incompatibility near CDRH1 Arg32. Together, theseresults define a peptide-register-driven recognition mode in whichthe MUC1 peptide backbone determines specificity, whereas a site-compatibleGalNAc acts as an affinity-enhancing element at the edge of the paratope.This structural framework may guide the design of MUC1 glycopeptide-basedvaccines and antibody therapeutics.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"6 9","pages":"5025–5036"},"PeriodicalIF":8.5,"publicationDate":"2026-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149067554","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
Harnessing Vinyl Cation Reactivity Enables Oxime Ether Formation and an Unusual Base-Promoted Rearrangement to Esters 利用乙烯基阳离子反应性使肟醚形成和不寻常的碱促进酯重排
IF 8.5
JACS Au Pub Date : 2026-09-28 Epub Date: 2026-09-15 DOI: 10.1021/jacsau.6c00532
Wenhua Lin, Djamila Azrou, Shanshan Zhang, Régis Guillot, Marie Vayer, Aurélien Alix, Vincent Gandon, Christophe Bour
{"title":"Harnessing Vinyl Cation Reactivity Enables Oxime Ether Formation and an Unusual Base-Promoted Rearrangement to Esters","authors":"Wenhua Lin,&nbsp;Djamila Azrou,&nbsp;Shanshan Zhang,&nbsp;Régis Guillot,&nbsp;Marie Vayer,&nbsp;Aurélien Alix,&nbsp;Vincent Gandon,&nbsp;Christophe Bour","doi":"10.1021/jacsau.6c00532","DOIUrl":"https://doi.org/10.1021/jacsau.6c00532","url":null,"abstract":"<p>Harnessing vinylcation reactivity under controlled conditionsremains a longstanding challenge in carbocation chemistry, as theionization of vinyl triflates and related precursors is often slow,limiting the development of general and selective reaction manifoldsinvolving vinyl cations. Here, we report an aluminum-catalyzed strategythat generates and intercepts vinyl cation intermediates from vinyltriflates, enabling direct access to oxime ethers using readily availablenitroalkanes. Oxime ether formation often exhibits a pronounced <em>Z</em> selectivity (up to <em>Z</em>/<em>E</em> = 93:7, depending on the substrate), affording geometrically definedproducts. Mechanistic studies supported by DFT calculations suggestthe intermediacy of an N-oxomethaniminium species, revealing a previouslyunrecognized reactivity pathway. In addition to oxime ether formation,these intermediates undergo a base-promoted rearrangement to esters,enabling a base-gated tandem transformation directly from vinyl triflates.A broad substrate scope (64 examples) demonstrates the robustnessof this vinyl cation platform and provides unified access to definedoxime ethers and esters.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"6 9","pages":"4968–4979"},"PeriodicalIF":8.5,"publicationDate":"2026-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149071108","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
Channel-Anchored Relaxation Maps for Electrochemical Impedance Spectroscopy: A Complementary Perspective to DRT 电化学阻抗谱的通道锚定松弛图:对DRT的补充观点
IF 8.5
JACS Au Pub Date : 2026-09-28 Epub Date: 2026-08-14 DOI: 10.1021/jacsau.6c00849
Kaicong Yang, Lin Zhuang
{"title":"Channel-Anchored Relaxation Maps for Electrochemical Impedance Spectroscopy: A Complementary Perspective to DRT","authors":"Kaicong Yang,&nbsp;Lin Zhuang","doi":"10.1021/jacsau.6c00849","DOIUrl":"https://doi.org/10.1021/jacsau.6c00849","url":null,"abstract":"<p>Electrochemical impedance spectroscopy (EIS) probes chargetransfer,interfacial charging, transport, adsorption, and feedback dynamicsin a single small-signal experiment. The distribution of relaxationtimes (DRT) has become a widely used bridge between raw Nyquist plotsand fully specified physical models. However, the conventional DRTkernel is an <em>RC</em>-Debye response basis. A DRT peakis therefore first a Debye response mode; assignment to a physicalprocess requires additional assumptions about separability, coupling,and the admissible basis. This Perspective develops channel-anchoreddistribution of relaxation times (CA-DRT), an inherently DRT-formrepresentation in which peaks are anchored to model-defined physicalchannels rather than obtained by a second inversion of a DRT spectrum.Four analytically controlled examples define the interpretation boundary:coupled ideal <em>RC</em> circuits redistribute modal timesand resistances; constant phase element (CPE)/Zarc responses broadenDRT peaks at fixed resistance; finite-length Warburg diffusion generatesmultiple Debye eigenmodes from one diffusion channel; and inductiverelaxation requires a negatively signed <em>RC</em>-basiscoefficient. CA-DRT complements response-basis DRT rather than servingas a DRT-based deconvolution algorithm. Its physically meaningfulanchors include channel resistance, characteristic time, state susceptibility,and, for a Zarc channel, the CPE exponent. Once these descriptorsare established by a physically admissible model, the CA-DRT constructionis independent of the electrochemical origin of the EIS data. Experimentaldemonstrations of the complete workflow, particularly model assessment,parameter identifiability, and uncertainty propagation, remain animportant next step.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"6 9","pages":"4819–4828"},"PeriodicalIF":8.5,"publicationDate":"2026-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149067507","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
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