IF 8.5

JACS Au Pub Date : 2025-06-03 DOI: 10.1021/jacsau.5c0037110.1021/jacsau.5c00371

Sung Gyu Kim, Jinrok Oh, Dongyoung Kim, Dae Eui Choi and Seung Jun Hwang*,

{"title":"Direct O2 Activation by Ligand-Constrained Pnictogen Complexes: Contrasting Mechanisms and OAT Reactivity across the P, Sb, and Bi Triad","authors":"Sung Gyu Kim, Jinrok Oh, Dongyoung Kim, Dae Eui Choi and Seung Jun Hwang*, ","doi":"10.1021/jacsau.5c0037110.1021/jacsau.5c00371","DOIUrl":"https://doi.org/10.1021/jacsau.5c00371https://doi.org/10.1021/jacsau.5c00371","url":null,"abstract":"Electronic structure–reactivity relationships are fundamental to advancing the redox chemistry of main-group elements. Herein, we investigate a series of planarized C2v pnictogen complexes (Pn = P, Sb, Bi) to correlate their electronic structures with reactivity trends across the pnictogen group. Through single-crystal X-ray diffraction, UV–vis spectroscopy, electrochemical measurements, and density functional theory (DFT) calculations, we demonstrate a systematic reduction in HOMO–LUMO gap progressing from phosphorus to bismuth, accompanied by enhanced stabilization of the nucleophilic lone pair. Oxygen atom transfer (OAT) reactivity, probed using triphenylpnictines (PnPh3, Pn = P, Sb, Bi) as mechanistic and thermodynamic reporters, reveals distinctive oxidation pathways. The phosphorus complex (1) undergoes a four-electron oxidation to yield a dioxophosphorane species, whereas the heavier congeners (2 and 3) generate monooxygenated Pn=O products exclusively. This mechanistic divergence is attributed to pronounced orbital contraction in heavier pnictogens, which stabilizes the lone pair and attenuates its participation in multielectron redox processes. Computational and experimental analyses corroborate these trends, with Hammett studies and pKa calculations of peroxo intermediates revealing enhanced nucleophilicity of the oxygen center with increasing pnictogen atomic weight, thereby influencing the OAT mechanism. These findings provide fundamental insights into periodic trends governing oxidation chemistry and demonstrate how strategic ligand design can modulate pnictogen-based multielectron reactivity. The broader implications extend to small-molecule activation and catalysis, offering a predictive framework for designing advanced redox-active main-group systems.","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 6","pages":"2779–2791 2779–2791"},"PeriodicalIF":8.5,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.5c00371","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144338068","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Accelerating Oxygen Evolution Activity via Premagnetization-Induced Active Sites in Ferromagnetic Nickel-Iron Hydroxide Catalysts. 通过预磁化诱导的活性位点加速铁磁性氢氧化镍-铁催化剂的析氧活性。

IF 8.5

JACS Au Pub Date : 2025-06-02 eCollection Date: 2025-06-23 DOI: 10.1021/jacsau.5c00118

Xiangbowen Du, Mingwu Tan, Jichao Shi, Lili Zhang, Xiaojun Qin, Yu Duan, Shanjun Mao, Selvi Mushina, Wen Liu, Yong Wang, Renhong Li

{"title":"Accelerating Oxygen Evolution Activity via Premagnetization-Induced Active Sites in Ferromagnetic Nickel-Iron Hydroxide Catalysts.","authors":"Xiangbowen Du, Mingwu Tan, Jichao Shi, Lili Zhang, Xiaojun Qin, Yu Duan, Shanjun Mao, Selvi Mushina, Wen Liu, Yong Wang, Renhong Li","doi":"10.1021/jacsau.5c00118","DOIUrl":"10.1021/jacsau.5c00118","url":null,"abstract":"Magnetization induced by an external magnetic field has emerged as a potential strategy to enhance the catalytic performance of the oxygen evolution reaction (OER). However, the underlying mechanism, particularly its impact on surface adsorbates, reaction intermediates, and surface reconfiguration, remains unclear. Here we delve into the adsorbate evolution mechanism during the OER catalyzed by ferromagnetic NiFe-hydroxide (LDH-FeOOH) after temporary exposure to a magnetic field (premagnetization, PM). The heterojunction induces crucial interfacial electronic modulation, specifically altering the electronic structure and Ni-O bonding configuration of interfacial Ni sites in the LDH phase, which potentially enhances the magnetic field sensitivity of Ni sites during the premagnetization processes. Following PM treatment, the Tafel slope of LDH-FeOOH significantly decreases from 111.7 to 44.6 mV/dec, indicating the enhancement of catalytic activity. Our investigation reveals that PM improved deprotonation ability induces surface reconstruction, forming highly active high-valenced nickle (oxy)-hydroxide that serves as more possible active sites. Additionally, the PM process promotes to establish a spin conduction channel that optimizes the adsorption energy of key intermediates and enhances spin-oriented electron transfer processes. Furthermore, enhancement of OER kinetics via PM treatment has been validated with both laboratory-scale anion-exchange membrane (AME) eletrcolyzer and industrial-scale commercial alkaline water electrolyzer. This study not only offers new insights into the role of PM in catalyst performance but also highlights its substantial potential for industrial hydrogen production applications.","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 6","pages":"2500-2512"},"PeriodicalIF":8.5,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12188396/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144510104","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Advancements and Prospects in DNA-Based Bioanalytical Technology for Environmental Toxicant Detection. 基于dna的环境毒物检测生物分析技术的进展与展望。

IF 8.5

JACS Au Pub Date : 2025-06-02 eCollection Date: 2025-06-23 DOI: 10.1021/jacsau.5c00398

Siqian Liu, Benfeng Xu, Chongyang Li, Yanlin Ren, Hao Gan, Shi Kuang, Chunyang Lei, Zhou Nie

{"title":"Advancements and Prospects in DNA-Based Bioanalytical Technology for Environmental Toxicant Detection.","authors":"Siqian Liu, Benfeng Xu, Chongyang Li, Yanlin Ren, Hao Gan, Shi Kuang, Chunyang Lei, Zhou Nie","doi":"10.1021/jacsau.5c00398","DOIUrl":"10.1021/jacsau.5c00398","url":null,"abstract":"The mounting global crisis of environmental pollution necessitates transformative advances in analytical technologies that combine speed, precision, and field applicability. To meet this demand, next-generation analytical platforms must achieve seamless integration of two critical features: molecular-level recognition fidelity and reliable signal transduction. DNA nanotechnology leverages sequence-specific molecular recognition and programmable self-assembly to enable both natural (e.g., riboswitches) and synthetic (e.g., aptamers, DNAzymes) biosensing modalities. The structural programmability and predictable Watson-Crick base pairing of DNA provide a modular framework for designing next-generation biosensors with tunable specificity and sensitivity. When integrated with portable point-of-care (POC) platforms, these biosensing systems enable field-deployable, rapid, and operator-agnostic detection of toxicants across diverse matrixes, making them highly suitable for complex environmental monitoring tasks. This perspective highlights the potential and strategic approaches for constructing biosensors utilizing DNA-based recognition elements and structural materials. It explores the progress in field-deployable DNA-based biosensors, which are revolutionizing the on-site detection of environmental toxicants. We also discuss the current challenges and future perspectives for DNA-based biosensing systems in environmental pollution monitoring, offering insights into their broader applications.","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 6","pages":"2443-2462"},"PeriodicalIF":8.5,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12188486/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144510105","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Advancements and Prospects in DNA-Based Bioanalytical Technology for Environmental Toxicant Detection 基于dna的环境毒物检测生物分析技术的进展与展望

IF 8.5

JACS Au Pub Date : 2025-06-02 DOI: 10.1021/jacsau.5c0039810.1021/jacsau.5c00398

Siqian Liu, Benfeng Xu, Chongyang Li, Yanlin Ren, Hao Gan, Shi Kuang*, Chunyang Lei and Zhou Nie*,

{"title":"Advancements and Prospects in DNA-Based Bioanalytical Technology for Environmental Toxicant Detection","authors":"Siqian Liu, Benfeng Xu, Chongyang Li, Yanlin Ren, Hao Gan, Shi Kuang*, Chunyang Lei and Zhou Nie*, ","doi":"10.1021/jacsau.5c0039810.1021/jacsau.5c00398","DOIUrl":"https://doi.org/10.1021/jacsau.5c00398https://doi.org/10.1021/jacsau.5c00398","url":null,"abstract":"The mounting global crisis of environmental pollution necessitates transformative advances in analytical technologies that combine speed, precision, and field applicability. To meet this demand, next-generation analytical platforms must achieve seamless integration of two critical features: molecular-level recognition fidelity and reliable signal transduction. DNA nanotechnology leverages sequence-specific molecular recognition and programmable self-assembly to enable both natural (e.g., riboswitches) and synthetic (e.g., aptamers, DNAzymes) biosensing modalities. The structural programmability and predictable Watson–Crick base pairing of DNA provide a modular framework for designing next-generation biosensors with tunable specificity and sensitivity. When integrated with portable point-of-care (POC) platforms, these biosensing systems enable field-deployable, rapid, and operator-agnostic detection of toxicants across diverse matrixes, making them highly suitable for complex environmental monitoring tasks. This perspective highlights the potential and strategic approaches for constructing biosensors utilizing DNA-based recognition elements and structural materials. It explores the progress in field-deployable DNA-based biosensors, which are revolutionizing the on-site detection of environmental toxicants. We also discuss the current challenges and future perspectives for DNA-based biosensing systems in environmental pollution monitoring, offering insights into their broader applications.","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 6","pages":"2443–2462 2443–2462"},"PeriodicalIF":8.5,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.5c00398","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144338009","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A Sinking Approach to Explore Arbitrary Areas in Free Energy Landscapes. 探索自由能景观中任意区域的下沉方法。

IF 8.5

JACS Au Pub Date : 2025-06-02 eCollection Date: 2025-06-23 DOI: 10.1021/jacsau.5c00460

Zhijun Pan, Maodong Li, Dechin Chen, Yi Isaac Yang

{"title":"A Sinking Approach to Explore Arbitrary Areas in Free Energy Landscapes.","authors":"Zhijun Pan, Maodong Li, Dechin Chen, Yi Isaac Yang","doi":"10.1021/jacsau.5c00460","DOIUrl":"10.1021/jacsau.5c00460","url":null,"abstract":"To address the time-scale limitations in molecular dynamics (MD) simulations, numerous enhanced sampling methods have been developed to expedite the exploration of complex free energy landscapes. A commonly employed approach accelerates the sampling of degrees of freedom associated with predefined collective variables (CVs), which typically tend to traverse the entire CV range. However, in many scenarios, the focus of interest is on specific regions within the CV space. In this paper, we introduce a novel \"sinking\" approach that enables enhanced sampling of arbitrary areas within the CV space. This method, referred to as SinkMeta, \"sinks\" the interior bias potential to create a restraining potential \"cliff\" at the grid edges, thus confining the exploration of CVs in MD simulations to a predefined area. SinkMeta requires minimal sampling steps to estimate the free energy landscape for CV subspaces of various shapes and dimensions, offering an efficient and flexible solution for sampling minimum free energy paths in high-dimensional spaces. We believe that SinkMeta will pioneer a new paradigm for sampling partial phase spaces and provide an efficient and straightforward way to study the interaction of drugs with biomolecules such as proteins and DNA in MD simulations.","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 6","pages":"2898-2908"},"PeriodicalIF":8.5,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12188410/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144510103","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Accelerating Oxygen Evolution Activity via Premagnetization-Induced Active Sites in Ferromagnetic Nickel–Iron Hydroxide Catalysts 通过预磁化诱导的活性位点加速铁磁性氢氧化镍-铁催化剂的析氧活性

IF 8.5

JACS Au Pub Date : 2025-06-02 DOI: 10.1021/jacsau.5c0011810.1021/jacsau.5c00118

Xiangbowen Du, Mingwu Tan*, Jichao Shi, Lili Zhang, Xiaojun Qin, Yu Duan, Shanjun Mao, Selvi Mushina, Wen Liu, Yong Wang* and Renhong Li*,

{"title":"Accelerating Oxygen Evolution Activity via Premagnetization-Induced Active Sites in Ferromagnetic Nickel–Iron Hydroxide Catalysts","authors":"Xiangbowen Du, Mingwu Tan*, Jichao Shi, Lili Zhang, Xiaojun Qin, Yu Duan, Shanjun Mao, Selvi Mushina, Wen Liu, Yong Wang* and Renhong Li*, ","doi":"10.1021/jacsau.5c0011810.1021/jacsau.5c00118","DOIUrl":"https://doi.org/10.1021/jacsau.5c00118https://doi.org/10.1021/jacsau.5c00118","url":null,"abstract":"Magnetization induced by an external magnetic field has emerged as a potential strategy to enhance the catalytic performance of the oxygen evolution reaction (OER). However, the underlying mechanism, particularly its impact on surface adsorbates, reaction intermediates, and surface reconfiguration, remains unclear. Here we delve into the adsorbate evolution mechanism during the OER catalyzed by ferromagnetic NiFe-hydroxide (LDH-FeOOH) after temporary exposure to a magnetic field (premagnetization, PM). The heterojunction induces crucial interfacial electronic modulation, specifically altering the electronic structure and Ni–O bonding configuration of interfacial Ni sites in the LDH phase, which potentially enhances the magnetic field sensitivity of Ni sites during the premagnetization processes. Following PM treatment, the Tafel slope of LDH-FeOOH significantly decreases from 111.7 to 44.6 mV/dec, indicating the enhancement of catalytic activity. Our investigation reveals that PM improved deprotonation ability induces surface reconstruction, forming highly active high-valenced nickle (oxy)hydroxide that serves as more possible active sites. Additionally, the PM process promotes to establish a spin conduction channel that optimizes the adsorption energy of key intermediates and enhances spin-oriented electron transfer processes. Furthermore, enhancement of OER kinetics via PM treatment has been validated with both laboratory-scale anion-exchange membrane (AME) eletrcolyzer and industrial-scale commercial alkaline water electrolyzer. This study not only offers new insights into the role of PM in catalyst performance but also highlights its substantial potential for industrial hydrogen production applications.","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 6","pages":"2500–2512 2500–2512"},"PeriodicalIF":8.5,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.5c00118","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144338051","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A Sinking Approach to Explore Arbitrary Areas in Free Energy Landscapes 探索自由能景观中任意区域的下沉方法

IF 8.5

JACS Au Pub Date : 2025-06-02 DOI: 10.1021/jacsau.5c0046010.1021/jacsau.5c00460

Zhijun Pan, Maodong Li, Dechin Chen and Yi Isaac Yang*,

{"title":"A Sinking Approach to Explore Arbitrary Areas in Free Energy Landscapes","authors":"Zhijun Pan, Maodong Li, Dechin Chen and Yi Isaac Yang*, ","doi":"10.1021/jacsau.5c0046010.1021/jacsau.5c00460","DOIUrl":"https://doi.org/10.1021/jacsau.5c00460https://doi.org/10.1021/jacsau.5c00460","url":null,"abstract":"To address the time-scale limitations in molecular dynamics (MD) simulations, numerous enhanced sampling methods have been developed to expedite the exploration of complex free energy landscapes. A commonly employed approach accelerates the sampling of degrees of freedom associated with predefined collective variables (CVs), which typically tend to traverse the entire CV range. However, in many scenarios, the focus of interest is on specific regions within the CV space. In this paper, we introduce a novel “sinking” approach that enables enhanced sampling of arbitrary areas within the CV space. This method, referred to as SinkMeta, “sinks” the interior bias potential to create a restraining potential “cliff” at the grid edges, thus confining the exploration of CVs in MD simulations to a predefined area. SinkMeta requires minimal sampling steps to estimate the free energy landscape for CV subspaces of various shapes and dimensions, offering an efficient and flexible solution for sampling minimum free energy paths in high-dimensional spaces. We believe that SinkMeta will pioneer a new paradigm for sampling partial phase spaces and provide an efficient and straightforward way to study the interaction of drugs with biomolecules such as proteins and DNA in MD simulations.","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 6","pages":"2898–2908 2898–2908"},"PeriodicalIF":8.5,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.5c00460","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144338048","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Broad PFAS Binding with Fatty Acid Binding Protein 4 Is Enabled by Variable Binding Modes. 可变结合模式使PFAS与脂肪酸结合蛋白4的广泛结合成为可能。

IF 8.5

JACS Au Pub Date : 2025-06-02 eCollection Date: 2025-06-23 DOI: 10.1021/jacsau.5c00504

Aaron S Birchfield, Faik N Musayev, Abdul J Castillo, George Zorn, Brian Fuglestad

{"title":"Broad PFAS Binding with Fatty Acid Binding Protein 4 Is Enabled by Variable Binding Modes.","authors":"Aaron S Birchfield, Faik N Musayev, Abdul J Castillo, George Zorn, Brian Fuglestad","doi":"10.1021/jacsau.5c00504","DOIUrl":"10.1021/jacsau.5c00504","url":null,"abstract":"Per- and polyfluoroalkyl substances (PFAS) are ubiquitous pollutants that bioaccumulate in wildlife and humans, yet the molecular basis of their protein interactions remains poorly understood. Here, we show that human adipocyte fatty acid-binding protein 4 (FABP4) can bind a diverse array of PFAS, including next-generation replacements for legacy chemicals and longer-chain perfluorocarboxylic acids. Shorter-chain PFAS, although weaker binders, still displayed measurable affinities, surpassing those of their nonfluorinated analogs. We determined crystal structures of FABP4 bound to perfluorooctanoic acid (PFOA), perfluorodecanoic acid (PFDA), and perfluorohexadecanoic acid (PFHxDA), revealing three distinct binding modes. Notably, PFOA binds in two separate sites, and two distinct conformations define single-ligand binding of PFDA and PFHxDA. These arrangements enhance hydrophobic interactions within the binding cavity and likely explain the low micromolar dissociation constants observed in fluorescence competition assays. Our findings underscore the critical roles of chain length, headgroup functionality, and protein conformation in PFAS-FABP4 interactions. Given the emerging implications of the role of FABP4 in endocrine function, even subtle PFAS-induced perturbations could affect metabolic regulation and disease risk. Overall, this work highlights the value of direct structural and biochemical insights into PFAS-FABP4 interactions and paves the way for future research on PFAS transport and toxicological outcomes.","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 6","pages":"2469-2474"},"PeriodicalIF":8.5,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12188406/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144510110","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Broad PFAS Binding with Fatty Acid Binding Protein 4 Is Enabled by Variable Binding Modes 可变结合模式使PFAS与脂肪酸结合蛋白4的广泛结合成为可能

IF 8.5

JACS Au Pub Date : 2025-06-02 DOI: 10.1021/jacsau.5c0050410.1021/jacsau.5c00504

Aaron S. Birchfield, Faik N. Musayev, Abdul J. Castillo, George Zorn and Brian Fuglestad*,

{"title":"Broad PFAS Binding with Fatty Acid Binding Protein 4 Is Enabled by Variable Binding Modes","authors":"Aaron S. Birchfield, Faik N. Musayev, Abdul J. Castillo, George Zorn and Brian Fuglestad*, ","doi":"10.1021/jacsau.5c0050410.1021/jacsau.5c00504","DOIUrl":"https://doi.org/10.1021/jacsau.5c00504https://doi.org/10.1021/jacsau.5c00504","url":null,"abstract":"Per- and polyfluoroalkyl substances (PFAS) are ubiquitous pollutants that bioaccumulate in wildlife and humans, yet the molecular basis of their protein interactions remains poorly understood. Here, we show that human adipocyte fatty acid-binding protein 4 (FABP4) can bind a diverse array of PFAS, including next-generation replacements for legacy chemicals and longer-chain perfluorocarboxylic acids. Shorter-chain PFAS, although weaker binders, still displayed measurable affinities, surpassing those of their nonfluorinated analogs. We determined crystal structures of FABP4 bound to perfluorooctanoic acid (PFOA), perfluorodecanoic acid (PFDA), and perfluorohexadecanoic acid (PFHxDA), revealing three distinct binding modes. Notably, PFOA binds in two separate sites, and two distinct conformations define single-ligand binding of PFDA and PFHxDA. These arrangements enhance hydrophobic interactions within the binding cavity and likely explain the low micromolar dissociation constants observed in fluorescence competition assays. Our findings underscore the critical roles of chain length, headgroup functionality, and protein conformation in PFAS–FABP4 interactions. Given the emerging implications of the role of FABP4 in endocrine function, even subtle PFAS-induced perturbations could affect metabolic regulation and disease risk. Overall, this work highlights the value of direct structural and biochemical insights into PFAS–FABP4 interactions and paves the way for future research on PFAS transport and toxicological outcomes.","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 6","pages":"2469–2474 2469–2474"},"PeriodicalIF":8.5,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.5c00504","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144338010","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

De Novo Synthesis of Single-Crystalline Multi-Module Chromium(III) Metal–Organic Frameworks for Water Adsorption 单晶多模组铬（III）金属-有机水吸附框架的从头合成

IF 8.5

JACS Au Pub Date : 2025-05-30 DOI: 10.1021/jacsau.5c0014810.1021/jacsau.5c00148

Yexin Huang, Zhenghan Zhang, Yongcheng Tao, Kai Zhu, Xinyi Huang, Yijun Yang, Hongliang Huang, Jian Li* and Huajun Yang*,

{"title":"De Novo Synthesis of Single-Crystalline Multi-Module Chromium(III) Metal–Organic Frameworks for Water Adsorption","authors":"Yexin Huang, Zhenghan Zhang, Yongcheng Tao, Kai Zhu, Xinyi Huang, Yijun Yang, Hongliang Huang, Jian Li* and Huajun Yang*, ","doi":"10.1021/jacsau.5c0014810.1021/jacsau.5c00148","DOIUrl":"https://doi.org/10.1021/jacsau.5c00148https://doi.org/10.1021/jacsau.5c00148","url":null,"abstract":"The robust Cr(III) metal–organic frameworks (MOFs) have attracted considerable interest in water adsorptions. However, the synthesis of highly crystalline Cr-MOFs is complicated by the kinetically inert nature of Cr(III). The main method for the preparation of Cr-MOFs now is postsynthetic metathesis, which is all consuming. Here, we report the de novo synthesis of a series of multi-module, single-crystalline Cr-MOFs at the micro scale (up to 6 μm). A dual-modulator (HF-pyridine) strategy is developed to modulate the multiple competitive coordination bonding in dual-ligand-based Cr-MOFs, with the secondary modulator of pyridine having the functional group of the secondary module of tripyridyl ligands, which thus acts as an additional inhibitor to nucleation. The high crystallinity has enabled the structure determination of a novel Cr-MOF (Cr-bpdc-tph) at atomic resolution by the continuous rotation electron diffraction (cRED) technique. Cr-bpdc-tph integrates both high porosity with a BET surface area up to 3191 m2/g and exceptional chemical resistance in extreme acidic and basic solutions (pH < 0 and pH > 14). The water adsorption results show that Cr-bpdc-tph has achieved an effective working efficiency of 76% within the relative humidity range of 45–65%.","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 6","pages":"2533–2541 2533–2541"},"PeriodicalIF":8.5,"publicationDate":"2025-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.5c00148","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144338136","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

JACS Au最新文献