Journal of the American Chemical Society最新文献_第2页

Hydration-Dependent Working-Surface Chemistry in Photocatalytic Methane Coupling 光催化甲烷偶联中水合作用的工作表面化学

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2026-11-10 DOI: 10.1021/jacs.6c18674

Feiyan Xu,Weiyuan Luo,Wantian Mei,Jianjun Zhang,Chuanbiao Bie,Hermenegildo García,Xusheng Zheng,Jiaguo Yu

{"title":"Hydration-Dependent Working-Surface Chemistry in Photocatalytic Methane Coupling","authors":"Feiyan Xu,Weiyuan Luo,Wantian Mei,Jianjun Zhang,Chuanbiao Bie,Hermenegildo García,Xusheng Zheng,Jiaguo Yu","doi":"10.1021/jacs.6c18674","DOIUrl":"https://doi.org/10.1021/jacs.6c18674","url":null,"abstract":"Selective photocatalytic methane coupling requires directing methane-derived intermediates toward C–C bond formation while limiting their oxidation to CO2, yet how the reaction environment controls this competition through surface chemistry remains unclear. Water is ubiquitous in photocatalytic methane conversion, but its influence is commonly interpreted through specific chemical functions rather than through its broader effects on working-surface chemistry. Here, Au/ZnO is used as a compositionally defined, coupling-competent model catalyst to reveal how hydration regulates carbon transformation pathways by reshaping the working-surface chemistry. Systematic variation of water availability reveals three hydration-dependent catalytic regimes with markedly different product distributions. Moderate hydration increases the ethane production rate from 1590 to 8407 μmol g–1 h–1 and enables ethylene formation, whereas excessive hydration increases CO2 production and lowers C2 selectivity. In situ spectroscopies show that these catalytic regimes are accompanied by hydration-dependent changes in methane adsorption, methane-derived and coupling-related surface intermediates, and oxygen-deficient surface states within a reaction network involving both carbon- and oxygen-centered radical chemistry. Moderate hydration establishes surface conditions that favor C–C coupling and C2 hydrocarbon accumulation, whereas excessive hydration favors oxidized surface species and carbonate formation. These results identify hydration as a key determinant of the steady-state surface chemistry governing carbon partitioning between C–C coupling and oxidation during photocatalytic methane conversion.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"10 3 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374783","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

Photoresponsive Mechanically Interlocked [an]Daisy Chain Network 光响应机械互锁[a]菊花链网络

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2026-11-10 DOI: 10.1021/jacs.6c14090

Guoquan Liu,Jingxi Deng,Jun Zhao,Ruixue Bai,Yongming Wang,Shaolei Qu,Yuanhao Wang,Zhiwei Fan,Yuan Liu,Lin Cheng,Jianzhen Wu,Yuhang Liu,Tao Wen,Li Yang,Yang Wang,Panchao Yin,Wei Yu,Zhaoming Zhang,Xuzhou Yan

{"title":"Photoresponsive Mechanically Interlocked [an]Daisy Chain Network","authors":"Guoquan Liu,Jingxi Deng,Jun Zhao,Ruixue Bai,Yongming Wang,Shaolei Qu,Yuanhao Wang,Zhiwei Fan,Yuan Liu,Lin Cheng,Jianzhen Wu,Yuhang Liu,Tao Wen,Li Yang,Yang Wang,Panchao Yin,Wei Yu,Zhaoming Zhang,Xuzhou Yan","doi":"10.1021/jacs.6c14090","DOIUrl":"https://doi.org/10.1021/jacs.6c14090","url":null,"abstract":"Muscle integrates molecular-machine motion with hierarchical structural organization, enabling it to sustain large deformations under physiological loads. Mechanically interlocked molecules offer a versatile platform to mimic such molecular-level motion, but efficiently translating it into macroscopic material performance, akin to muscle, remains challenging. Herein, we report a mechanically interlocked network (MIN) with [an]daisy chain backbone which can efficiently scale up the photoresponsive behavior of mechanical bonds, exhibiting intelligently tunable mechanical properties. In specific, photoresponsive unit of arylazopyrazole (AAP) is embedded onto the axis of each mechanical bond in the [an]daisy chain backbone. Ultraviolet light triggers the trans-to-cis (E/Z) isomerization of the AAP moieties, and when amplified through the [an]daisy chain backbone, it brings about significant changes in the material’s properties. On one hand, the E/Z isomerization significantly shortens the dimension of the [an]daisy chain framework, resulting in a notable increase in the material modulus (from 1.6 to 4.0 MPa). On the other hand, the cis configuration of AAP formed after the isomerization restricts the mobility of the mechanical bonds, resulting in a shorter elongation at break (from 343% to 272%). Our work presents an efficient method for amplifying mechanical bond responsiveness, providing a fresh perspective for the development of intelligent materials.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"37 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374780","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

Design and Evolution of an Orthogonal HaloTag for Multiplexed Labeling in Cells 用于细胞多路标记的正交卤化标签的设计与发展

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2026-11-10 DOI: 10.1021/jacs.6c20679

Benjamin J. Goldberg,Bryan J. Lampkin,Alexander T. Stead,Siena L. Stanten,Patrick Rabe,Joshua A. Kritzer

{"title":"Design and Evolution of an Orthogonal HaloTag for Multiplexed Labeling in Cells","authors":"Benjamin J. Goldberg,Bryan J. Lampkin,Alexander T. Stead,Siena L. Stanten,Patrick Rabe,Joshua A. Kritzer","doi":"10.1021/jacs.6c20679","DOIUrl":"https://doi.org/10.1021/jacs.6c20679","url":null,"abstract":"The self-labeling protein HaloTag is used to install a wide variety of functional small molecules in cells and living organisms with exquisite specificity with respect to cell type and subcellular localization. HaloTag is a core part of many biotechnology-based tools for sensing, tracking, and manipulating biological systems with a high degree of spatial and temporal control. Due to the limitations of fluorescent proteins and other self-labeling proteins, most of these tools have historically been restricted to a single channel. In this work, we used structure-guided rational design and directed evolution to produce an orthogonal HaloTag protein called OrthoTag which reacts selectively with a modified chloroalkane substrate. OrthoTag retains many of HaloTag’s superior properties, and reaction rate measurements with purified proteins show OrthoTag and its substrate have 109-fold mutual orthogonality to HaloTag with respect to substrate concentration. We demonstrate the application of OrthoTag for multiplexed labeling experiments in mammalian cells with minimal optimization. Going forward, OrthoTag should be straightforward to incorporate into HaloTag-based systems to allow simultaneous measurement or manipulation of two biological targets or processes. The availability of multiple high-performance self-labeling proteins will enable the continued development of new multiplexed biotechnology methods.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"18 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374785","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

Unlocking Intrinsic Chirality in Luminescent Copper Clusters via Intramolecular Spatial Confinement 通过分子内空间约束解锁发光铜团簇的本征手性

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2026-11-10 DOI: 10.1021/jacs.6c17674

Ying Xu,Hao Tian,YuLin Chen,Hao Li,Zhijia Hu,Xi Kang,Manzhou Zhu

{"title":"Unlocking Intrinsic Chirality in Luminescent Copper Clusters via Intramolecular Spatial Confinement","authors":"Ying Xu,Hao Tian,YuLin Chen,Hao Li,Zhijia Hu,Xi Kang,Manzhou Zhu","doi":"10.1021/jacs.6c17674","DOIUrl":"https://doi.org/10.1021/jacs.6c17674","url":null,"abstract":"Most luminescent clusters that exhibit pronounced chiral signals typically rely on predesigned chiral ligands; however, stimulating the intrinsic chirality of clusters in the absence of exogenous asymmetric ligands remains a significant challenge. In this study, based on a series of structure-correlated Cu2 clusters, we demonstrate that intramolecular spatial confinement effectively induces distortions in flexible ligands, thereby imparting asymmetry to the cluster framework. This molecular asymmetry further determines the orientation of cluster entities during supramolecular assembly, thus enabling the modulation of chirality across this cluster series between inactive (“off”) and active (“on”) states. In addition, these structure-correlated Cu2 clusters display bright and tunable luminescence, allowing for the fabrication of uniform thin films that function as practical scintillation materials for high-resolution X-ray imaging. Collectively, this work provides a novel perspective for regulating the chiroptical properties of metal clusters through the activation of intramolecular spatial confinement and offers valuable insights into the fabrication of cluster-based nanomaterials with tailored photophysical performances.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"44 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374774","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

Synthesis and Crystal Structure of Bulk Methanetetrol C(OH)4 大块甲烷乙醇C(OH)4的合成与晶体结构

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2026-11-10 DOI: 10.1021/jacs.6c12079

Dominik Spahr,Lkhamsuren Bayarjargal,Lukas Brüning,Valentin Kovalev,Pascal L. Jurzick,Maxim Bykov,Victor Milman,Björn Winkler,Elena Bykova

{"title":"Synthesis and Crystal Structure of Bulk Methanetetrol C(OH)4","authors":"Dominik Spahr,Lkhamsuren Bayarjargal,Lukas Brüning,Valentin Kovalev,Pascal L. Jurzick,Maxim Bykov,Victor Milman,Björn Winkler,Elena Bykova","doi":"10.1021/jacs.6c12079","DOIUrl":"https://doi.org/10.1021/jacs.6c12079","url":null,"abstract":"Methanetetrol, C(OH)4 (orthocarbonic acid), is an elusive tethrahydroxymethane that, due to its rapid dissociation under ambient conditions, has never been synthesized in bulk. A recent study detected the formation of C(OH)4 molecules in the gas phase. Here, we show that C(OH)4 can be synthesized in a diamond anvil cell through the reaction between H2O and CO2 at 45(3) GPa and 50(3) GPa and temperatures <1200(200) K. The crystal structure of C(OH)4 was determined by single-crystal X-ray diffraction and corroborated by density-functional theory calculations together with Raman spectroscopy. It is composed of isolated [C(OH)4]-molecules linked by strong hydrogen bonds. Under high-pressure conditions, orthocarbonic and carbonic acids are denser than coexisting water ice phases, allowing them to segregate gravitationally and form stable reservoirs of oxidized carbon. These phases incorporate large amounts of carbon into their crystal structures as part of [CO4]4–- or [CO3]2–-building blocks. Because the amount of carbon that can be stored as CO2 in clathrates or filled-ices is significantly smaller, orthocarbonic and carbonic acids may provide a host mechanism for sequestering large carbon inventories in the icy mantles of water-rich exoplanets.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"64 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374777","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

Catalytic Interphases Enable Sulfur Redox Catalysis in All-Solid-State Lithium–Sulfur Batteries 全固态锂硫电池中催化界面实现硫氧化还原催化

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2026-11-09 DOI: 10.1021/jacs.6c13825

Mingyang Jiang,Jiwei Shi,Zhonghao Hu,Tianyu Yin,Bohan Zhang,Yun Cao,Yufei Zhao,Junjie Wang,Chuannan Geng,Wei Lv

{"title":"Catalytic Interphases Enable Sulfur Redox Catalysis in All-Solid-State Lithium–Sulfur Batteries","authors":"Mingyang Jiang,Jiwei Shi,Zhonghao Hu,Tianyu Yin,Bohan Zhang,Yun Cao,Yufei Zhao,Junjie Wang,Chuannan Geng,Wei Lv","doi":"10.1021/jacs.6c13825","DOIUrl":"https://doi.org/10.1021/jacs.6c13825","url":null,"abstract":"Weak solid–solid contact with limited chemical and transport continuity is a common bottleneck in solid-state batteries, particularly in all-solid-state lithium–sulfur batteries (ASSLSBs), where Li2S/S8 conversion requires catalytic acceleration but lacks a continuous solid-state catalytic pathway. Here, we propose an interphase catalysis strategy for solid–solid sulfur conversion by transforming discrete catalyst/reactant interfaces into a chemically integrated reaction interphase. WO3 is identified as a suitable oxide to construct such a metastable mixed-anion S–W–O catalytic interphase on Li2S based on the work-function difference between the metal oxide catalyst and Li2S/S8, which serves as a practical screening rationale for evaluating the relative tendency toward sulfur–oxygen coordination exchange. The interphase contains unsaturated W centers and a polarized electronic environment, enabling coupled electron/Li+ transport and dynamically regulating sulfur redox through coupled sulfur-species exchange. This integrated interphase further stabilizes cathode interfaces during repeated Li2S/S8 conversion. As a result, the optimized cathode sustains stable cycling over 15000 cycles at 10 C and a temperature of 60 °C. A record-high Li2S loading of 30 mg cm–2 with an areal capacity of 21.2 mAh cm–2 is also achieved, demonstrating interphase catalysis as an effective route to overcome solid-state sulfur-conversion limitations in practical ASSLSBs.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"9 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368296","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

A Mixed Conducting Polymer with pH-Dependent Selectivity for the Oxygen Reduction Reaction 氧还原反应中ph依赖选择性的混合导电聚合物

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2026-11-09 DOI: 10.1021/jacs.6c17241

Ana de la Fuente Durán,Emily Penn,Adam Marks,Nicholas Siemons,Jeremy Treiber,Beatrice Tremblay,William C. Chueh,Alberto Salleo,Alexander Giovannitti,J. Tyler Mefford

{"title":"A Mixed Conducting Polymer with pH-Dependent Selectivity for the Oxygen Reduction Reaction","authors":"Ana de la Fuente Durán,Emily Penn,Adam Marks,Nicholas Siemons,Jeremy Treiber,Beatrice Tremblay,William C. Chueh,Alberto Salleo,Alexander Giovannitti,J. Tyler Mefford","doi":"10.1021/jacs.6c17241","DOIUrl":"https://doi.org/10.1021/jacs.6c17241","url":null,"abstract":"Achieving 4-electron oxygen reduction with metal-free electrodes has remained a longstanding challenge. Here, we show that poly(benzimidazobenzophenanthroline) (BBL), an n-type ladder polymer, breaks this barrier through an electrocatalytic inner-sphere 2 + 2 series mechanism─a mode of reactivity unprecedented among organic mixed ionic-electronic conductors (OMIECs). Using pH-dependent rotating ring-disk voltammetry, we find that this series mechanism occurs over separate potential windows on BBL. At more positive potentials, an initial reduction wave correlated with electron polaron formation in BBL produces exclusively hydro(gen) peroxide across all pH values, followed by a second, pH-dependent wave for hydro(gen) peroxide reduction at more negative potentials. At pH 14.0, this second wave enables complete four-electron reduction of O2 (n ≈ 4) to OH–, driven by formation of a bipolaronic state in BBL. Decreasing the pH instead stabilizes a hydrogenated state in BBL incapable of O–O bond cleavage, reverting selectivity to n ≈ 2. These insights reveal that the coupling between ion selectivity during electrochemical ion-insertion and product selectivity during ORR catalysis shapes active-site structure and poisoning, establishing a new design principle in the emerging field of OMIEC electrocatalysis.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"64 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368302","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

The Catalytic Stereocontrolled Tetrahydropyranyl Protection 催化立体控制四氢吡喃保护剂

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2026-11-09 DOI: 10.1021/jacs.6c19341

Jan Samsonowicz-Górski,Sunggi Lee,Sebastian Brunen,Markus Leutzsch,Oleg Grossmann,Nobuya Tsuji,Benjamin List

引用次数: 0

Cationic Ionomer Coatings Promote Anion Electroreduction: Nitrate Reduction as a Model Reaction 阳离子离子涂层促进阴离子电还原：硝酸还原为模型反应

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2026-11-09 DOI: 10.1021/jacs.6c12410

Zikai Xu,Madeline H. Hicks,Matthew Salazar,Jonas C. Peters,Theodor Agapie

{"title":"Cationic Ionomer Coatings Promote Anion Electroreduction: Nitrate Reduction as a Model Reaction","authors":"Zikai Xu,Madeline H. Hicks,Matthew Salazar,Jonas C. Peters,Theodor Agapie","doi":"10.1021/jacs.6c12410","DOIUrl":"https://doi.org/10.1021/jacs.6c12410","url":null,"abstract":"Electrolysis technologies represent a promising pathway to valorize abundant feedstocks using renewable electricity. While ionomers serve critical roles as ion conductors and catalyst binders in electrolyzers, their impact on electrochemical transformations of ionic species remains poorly understood compared to extensively studied neutral-molecule conversions like water splitting and CO2 reduction. Herein, we use the electrochemical nitrate reduction reaction as a model transformation to investigate the influence of ionomer coatings in anion electroreduction reactions, which face fundamental challenges from electrostatic anion depletion near negatively polarized cathodes and premature desorption of anionic intermediates. We demonstrate that cationic ionomer coatings increase local nitrate concentration up to 10-fold compared to bulk electrolyte due to the interfacial Donnan potential. While prior studies have shown that ionomers can influence the local reaction microenvironment, this work provides, to the best of our knowledge, the first quantitative measurement of nitrate concentration within ionomer coatings as a function of charge density and its impact on catalysis. A 5-fold enhancement in ammonium partial current density was achieved with the ionomer bearing the highest charge density. Using in situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS), we quantified enhanced local nitrate concentration (up to 1.1 M versus 0.1 M in bulk electrolyte), conversion, and supply with increasing charge density. This study establishes guiding principles for tuning ionomer charge identity and density to control interfacial ion concentrations in electrochemical transformations of dilute charged substrates.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"6 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368295","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

Tunable Aza-BODIPY Photocatalysts for Near-Infrared Metallaphotoredox Atom Transfer Radical Polymerization 用于近红外金属氧化还原原子转移自由基聚合的可调Aza-BODIPY光催化剂

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2026-11-09 DOI: 10.1021/jacs.6c14724

Jakub Piątkowski,Paulina H. Marek-Urban,Martyna Cybularczyk-Cecotka,Magdalena Z. Wiloch-Szyborska,Joanna Jankowska,Yoichi Kobayashi,Grzegorz Szczepaniak

{"title":"Tunable Aza-BODIPY Photocatalysts for Near-Infrared Metallaphotoredox Atom Transfer Radical Polymerization","authors":"Jakub Piątkowski,Paulina H. Marek-Urban,Martyna Cybularczyk-Cecotka,Magdalena Z. Wiloch-Szyborska,Joanna Jankowska,Yoichi Kobayashi,Grzegorz Szczepaniak","doi":"10.1021/jacs.6c14724","DOIUrl":"https://doi.org/10.1021/jacs.6c14724","url":null,"abstract":"The merger of photoredox and transition-metal catalysis has significantly advanced radical and redox transformations, yet its reliance on UV or visible light continues to limit applications in optically complex and spatially confined environments. Herein, we introduce a modular family of tetraaryl aza-boron-dipyrromethene (aza-BODIPY) organic photocatalysts (PCs) for near-infrared (NIR) metallaphotoredox atom transfer radical polymerization (ATRP). We systematically modulated peripheral electronics and core bromination, evaluating the dyes through quantum-chemical, electrochemical, and spectroscopic methods. This approach identified the key parameters governing catalytic performance: a delicate interplay between triplet-state accessibility, redox properties, and photostability. The optimized aza-BODIPY dye enables well-controlled ATRP of diverse acrylates and methacrylates at ultralow catalyst loadings, down to 5 ppm PC and 50 ppm copper complex. The system is further translated to open-air aqueous conditions, enabling rapid, high-throughput synthesis of water-soluble polymers in a 96-well plate format. Taking advantage of the enhanced penetration of NIR light, we demonstrate controlled polymerization through challenging physical barriers, including ex vivo tissue. Overall, this work defines design principles for far-red/NIR-absorbing aza-BODIPY PCs and expands the scope of NIR-mediated polymer synthesis to optically turbid, spatially restricted, and aqueous environments.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"65 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368414","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