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

Nickel-Mediated Radical Capture: Evidence for a Concerted Inner-Sphere Mechanism 镍介导的自由基捕获：协调内球机制的证据

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-29 DOI: 10.1021/jacs.5c01554

Ethan H. Spielvogel, Jonathan Yuan, Norah M. Hoffmann, Tianning Diao

{"title":"Nickel-Mediated Radical Capture: Evidence for a Concerted Inner-Sphere Mechanism","authors":"Ethan H. Spielvogel, Jonathan Yuan, Norah M. Hoffmann, Tianning Diao","doi":"10.1021/jacs.5c01554","DOIUrl":"https://doi.org/10.1021/jacs.5c01554","url":null,"abstract":"Nickel catalysis enables cross-coupling of a broad scope of C(sp3) moieties by mediating carbon–carbon bond formation from carbon-centered radicals. A widely proposed mechanism involves stepwise radical capture by a nickel(II) complex that forms a nickel(III) intermediate. The alternative pathway, a concerted radical capture and carbon–carbon bond formation, has been largely overlooked. This study investigates the ligand effect and kinetics of nickel-mediated radical capture and reductive elimination, which provide evidence to distinguish between stepwise and concerted pathways. Through radical clock experiments, spectroscopic investigation, electrochemical studies, and multivariate linear regression analysis of a series of [(pybox)Ni(Ar)]BArF4 complexes, we established a strong correlation between the rate of radical capture and HOMO and LUMO energies, along with positive charge stabilization at nickel and the aryl actor ligand. These data rule out the stepwise formation of a nickel(III) intermediate and support a concerted pathway. Redox-active nitrogen ligands and nonredox-active phosphine ligands exhibit contrasting reactivity, with only redox-active ligands facilitating radical capture and carbon–carbon bond formation. This critical role of ligand redox activity can be attributed to the participation of the LUMO in bond cleavage and formation. Among redox-active ligands, bidentate and tridentate ligands exhibit similar rates, suggesting a consistent mechanism with relatively minimal ancillary ligand effect. Our results highlight the critical interplay between ligand electronics, sterics, and orbital contributions, offering valuable design principles for nickel-catalyzed cross-coupling reactions involving radical intermediates.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"36 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144176839","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

Sterically Induced Acceleration of Aryl Halide Activation by Pd(0): A Radical Alternative to 2-Electron Oxidative Addition Pd(0)立体诱导加速芳基卤化物活化：取代2电子氧化加成的自由基

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-29 DOI: 10.1021/jacs.5c04407

Daniel Hupperich, Jaime Ponce-de-León, Ignacio Funes-Ardoiz, Theresa Sperger, Franziska Schoenebeck

引用次数: 0

Developing Pharmaceutically Relevant Pd-Catalyzed C–N Coupling Reactivity Models Leveraging High-Throughput Experimentation 利用高通量实验开发与制药相关的pd催化C-N偶联反应性模型

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-29 DOI: 10.1021/jacs.5c00933

Seung Kyun Ha, Dipannita Kalyani, Michael S. West, Jessica Xu, Yu-hong Lam, Thomas Struble, Spencer Dreher, Shane W. Krska, Stephen L. Buchwald, Klavs F. Jensen

{"title":"Developing Pharmaceutically Relevant Pd-Catalyzed C–N Coupling Reactivity Models Leveraging High-Throughput Experimentation","authors":"Seung Kyun Ha, Dipannita Kalyani, Michael S. West, Jessica Xu, Yu-hong Lam, Thomas Struble, Spencer Dreher, Shane W. Krska, Stephen L. Buchwald, Klavs F. Jensen","doi":"10.1021/jacs.5c00933","DOIUrl":"https://doi.org/10.1021/jacs.5c00933","url":null,"abstract":"This manuscript presents machine learning models for Pd-catalyzed C–N couplings constructed using a large, pharmaceutically relevant, structurally diverse dataset (4204 unique products) generated de novo using high-throughput experimentation. The dataset generation was enabled by the discovery of novel nanomole scale compatible automation friendly C–N coupling reaction conditions using LiOTMS as the base. The large dataset enabled the systematic evaluation of model performance using five different data-splitting strategies that were carefully designed to assess the models’ ability to both interpolate and extrapolate. The models exhibit high predictive performance across all splits as gauged by standard metrics. In addition, the models predicted with high accuracy the outcome of validation libraries that were outside the scope of the training set. Employing these models in the context of medicinal chemistry campaigns should result in significant enrichment of successful C–N couplings.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"134 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165294","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

Accessing a Hidden Pathway to Supramolecular Toroid through Vibrational Strong Coupling 通过振动强耦合获取通往超分子环面的隐藏途径

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-29 DOI: 10.1021/jacs.5c02960

Shunsuke Imai, Takumi Hamada, Misa Nozaki, Takatoshi Fujita, Mariko Takahashi, Yasuhiko Fujita, Koji Harano, Hiroshi Uji-i, Atsuro Takai, Kenji Hirai

{"title":"Accessing a Hidden Pathway to Supramolecular Toroid through Vibrational Strong Coupling","authors":"Shunsuke Imai, Takumi Hamada, Misa Nozaki, Takatoshi Fujita, Mariko Takahashi, Yasuhiko Fujita, Koji Harano, Hiroshi Uji-i, Atsuro Takai, Kenji Hirai","doi":"10.1021/jacs.5c02960","DOIUrl":"https://doi.org/10.1021/jacs.5c02960","url":null,"abstract":"Control over specific intermolecular interactions is crucial to the formation of unique supramolecular assemblies. Recently, vibrational strong coupling (VSC) has emerged as a new tool for manipulating these interactions. Although VSC shows promise for controlling molecular assembly, it has not yet demonstrated the capability to open a pathway for creating structures that are inaccessible by conventional assembly methods. Here, we used VSC to control the transformation process of a naphthalenediimide supramolecular polymer induced by a click reaction. The supramolecular polymers with reactive ethynyl groups undergo a transformation from long fibers to thick fibers upon induction by an amino-yne click reaction in the absence of VSC. Under VSC of the C–H stretch, the click reaction within supramolecular polymers is accelerated; no such acceleration occurs in the reaction of individual monomers, suggesting that the acceleration is due to changes in the assembled structures. Indeed, applying the VSC to the C–H stretch uniquely altered the morphological transformation process, leading to the formation of metastable toroids instead of thick fibers. Notably, the molecular assembly cannot be directed toward a toroidal structure without a VSC. Theoretical simulations suggested that slipped packing configurations in the supramolecular polymers form the curvature necessary for toroidal structures. The experimental results, supported by theoretical simulations, suggest that intermolecular interactions among naphthalenediimide molecules are modified under VSC, leading to a slipped packing configuration of the toroidal assembly. These findings link the VSC-induced modulation of intermolecular interactions to structural outcomes, establishing VSC as a tool for manipulating molecular assembly beyond traditional assembly methods.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"57 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144176840","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

Shifting Gears: Photochromic Metal–Organic Frameworks with Stimulus-Adaptable Performance 变速齿轮：具有刺激适应性能的光致变色金属-有机框架

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-29 DOI: 10.1021/jacs.5c04466

Johanna Haimerl, Grace C. Thaggard, Buddhima K. P. Maldeni Kankanamalage, Raphael Bühler, Jaewoong Lim, Kyoung Chul Park, Julien Warnan, Roland A. Fischer, Natalia B. Shustova

{"title":"Shifting Gears: Photochromic Metal–Organic Frameworks with Stimulus-Adaptable Performance","authors":"Johanna Haimerl, Grace C. Thaggard, Buddhima K. P. Maldeni Kankanamalage, Raphael Bühler, Jaewoong Lim, Kyoung Chul Park, Julien Warnan, Roland A. Fischer, Natalia B. Shustova","doi":"10.1021/jacs.5c04466","DOIUrl":"https://doi.org/10.1021/jacs.5c04466","url":null,"abstract":"The tunability of the reaction parameter space is probed in the presented work through photoswitch-directed energy and charge transfer pathways induced by organic chromophores, hierarchically organized within a well-defined, light-harvesting metal–organic framework. Unique matrix-imposed changes in photoswitch photophysical properties, including the first report of visible light-induced photoisomerization of a spiropyran derivative, illustrate the critical synergy between the selected matrix and the photoresponsive compound. Moreover, the confined space of the utilized porous matrix allowed for mimicking isomerization kinetics of integrated sterically demanding photochromic moieties in solution. More importantly, such photoisomerization suppresses the charge transfer processes in favor of resonance energy transfer pathways instead. The demonstrated ability to shift between multiple relaxation pathways (e.g., charge transfer, energy transfer, or photoluminescence) as a function of the excitation wavelength resulted in photoswitch-directed tailoring of model phosphinylation reaction outcomes. Thus, incorporating spiropyran moieties within the framework allows for visible light to be harvested and funneled toward either a ligand-based reactive center or an acceptor molecule such as a photochromic unit. Moreover, the framework’s chemical activity was promoted exclusively by organic linkers without the participation of metal nodes, the addition of (co)catalysts, or the use of harsh conditions at room temperature. Overall, this work paves the way for the development of stimulus-responsive platforms, for which chemical activity could be controlled through a photochromic moiety.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"43 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144176848","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

Stereoselectivity of Aminoacyl-RNA Loop-Closing Ligation 氨基酰基- rna闭合环连接的立体选择性

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-29 DOI: 10.1021/jacs.4c16905

Shannon Kim, Marco Todisco, Aleksandar Radakovic, Jack W. Szostak

{"title":"Stereoselectivity of Aminoacyl-RNA Loop-Closing Ligation","authors":"Shannon Kim, Marco Todisco, Aleksandar Radakovic, Jack W. Szostak","doi":"10.1021/jacs.4c16905","DOIUrl":"https://doi.org/10.1021/jacs.4c16905","url":null,"abstract":"The origin of amino acid homochirality remains an unresolved question in the origin of life. The requirement of enantiopure nucleotides for nonenzymatic RNA copying strongly suggests that the homochirality of nucleotides and RNA arose early. However, this leaves open the question of whether and how homochiral RNA subsequently imposes biological homochirality on other metabolites, including amino acids. Previous studies have reported moderate stereoselectivity for various aminoacyl-RNA transfer reactions. Here, we examine aminoacyl-RNA loop-closing ligation, a reaction that “captures” aminoacylated RNA in a stable phosphoramidate product, such that the amino acid bridges two nucleotides in the RNA backbone. We find that the rate of this reaction is much higher for RNA aminoacylated with L-amino acids than for RNA aminoacylated with D-amino acids. We present an RNA sequence that nearly exclusively captures L-amino acids in loop-closing ligation. Finally, we demonstrate that ligation of aminoacyl-L-RNA results in an inverse stereoselectivity for D-amino acids. The observed stereochemical link between D-RNA and L-amino acids in the synthesis of RNA stem-loops containing bridging amino acids constitutes a stereoselective structure-building process. We suggest that this process led to a selection for the evolution of aminoacyl-RNA synthetase ribozymes that were selective for L-amino acids, thereby setting the stage for the subsequent evolution of homochiral peptides and, ultimately, protein synthesis.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"11 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165445","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

Visualization and Quantification of Base-Level SO2 in Live Cells without Intracellular Background Interference Using Sensitive 19F-NMR 使用敏感19F-NMR可视化和定量无细胞内背景干扰的活细胞中基础水平SO2

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-29 DOI: 10.1021/jacs.5c04351

Chao-Yu Cui, Bin Li, Xing Zhang, Shu-Li Guo, Bin-Bin Pan, Xun-Cheng Su

{"title":"Visualization and Quantification of Base-Level SO2 in Live Cells without Intracellular Background Interference Using Sensitive 19F-NMR","authors":"Chao-Yu Cui, Bin Li, Xing Zhang, Shu-Li Guo, Bin-Bin Pan, Xun-Cheng Su","doi":"10.1021/jacs.5c04351","DOIUrl":"https://doi.org/10.1021/jacs.5c04351","url":null,"abstract":"Sulfur dioxide (SO2), as an endogenous gasotransmitter, is involved in a variety of physiological processes in living systems, however, distinction and quantification of base-level SO2 in live cells pose great challenges for the current analytical techniques. We report an efficient way to visualize and quantify base-level SO2 in different live mammalian cells by 19F-NMR. This method relies on a high-performance 19F-probe (P1-CF3) that reacts with the reactive sulfur species (RSS) in the generation of distinct chemical shift profiles, which are well-resolved in the NMR spectrum. The quantitative reaction of the 19F-probe with SO2 is fast and produces a stable addition product that is well distinguishable between the intra- and extracellular environment. The high performance of this method discloses that the base-level SO2 in live cells varies greatly in different cell lines. The high accuracy and precision of RSS measurement by the reactive 19F NMR probe allow simultaneous quantification of base-level SO2 in living cells and culture medium in real time without interference from other RSS and potential competitors and also without background signals.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"98 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165450","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

Polarization-Induced Breaching of the Liquid/Liquid Interface Formed with Water-in-Salt Electrolytes 由盐水电解质形成的液/液界面的极化诱导破坏

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-29 DOI: 10.1021/jacs.5c04832

Lihao Feng, Michael Goldstein, Yang Wang, Udayan Mohanty, Alexis Grimaud

{"title":"Polarization-Induced Breaching of the Liquid/Liquid Interface Formed with Water-in-Salt Electrolytes","authors":"Lihao Feng, Michael Goldstein, Yang Wang, Udayan Mohanty, Alexis Grimaud","doi":"10.1021/jacs.5c04832","DOIUrl":"https://doi.org/10.1021/jacs.5c04832","url":null,"abstract":"The solvation properties of water-in-salt electrolytes (WiSEs) have been extensively studied by spectroscopic and computational means and were shown to impart them with unique chemical and physical properties when compared to more classical superconcentrated aqueous solutions. More specifically, the formation of ionic aggregates in solutions containing a large concentration of TFSI anions was shown to alter the water and anion reactivity at electrochemical interfaces, often improving the performance of aqueous rechargeable batteries. However, insights into the role of the WiSE solvation structure on ion transfer at electrochemical interfaces are scarce. Herein, interfaces between two immiscible electrolytes (ITIESs) are used to study the energetics for ion transfer between aqueous LiCl and LiTFSI solutions and dichloroethane. Combining electrochemical measurements at microinterfaces with metadynamics molecular dynamics (MD) simulations, the effect of solvation properties on the energy for transferring Li+ and Cl–/TFSI– ions across the liquid/liquid interface was studied. While increasing the LiCl concentration increases the amount of ion pairs, it only marginally impacts the ion transfer energy. Instead, using large LiTFSI concentrations at which ionic aggregates are formed, ion transfer across the liquid/liquid interface shows a unique behavior that departs from that observed for polarizable or nonpolarizable interfaces. Ions do not freely cross the interface, with a transfer energy found to be ≈8–10 kcal/mol. However, upon polarization, ionic aggregates are found to breach the liquid/liquid interface, locally mixing both solutions. We believe that such a finding calls for reevaluating our current understanding of ion transfer across chemical interfaces in superconcentrated electrolytes, including liquid/liquid interfaces used in membrane-less electrochemical systems.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"223 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165528","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

Domino Effect of Catalysis: Coherence between Reaction Network and Catalyst Restructuring Accelerating Surface Carburization for CO2 Hydrogenation 催化的多米诺效应：反应网络和催化剂重组之间的一致性加速了CO2加氢的表面渗碳

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-29 DOI: 10.1021/jacs.5c01435

Pengfei Du, Yafeng Zhang, Rui Qi, Qingqing Gu, Xiaoyan Xu, Aiqin Wang, Beien Zhu, Bing Yang, Tao Zhang

{"title":"Domino Effect of Catalysis: Coherence between Reaction Network and Catalyst Restructuring Accelerating Surface Carburization for CO2 Hydrogenation","authors":"Pengfei Du, Yafeng Zhang, Rui Qi, Qingqing Gu, Xiaoyan Xu, Aiqin Wang, Beien Zhu, Bing Yang, Tao Zhang","doi":"10.1021/jacs.5c01435","DOIUrl":"https://doi.org/10.1021/jacs.5c01435","url":null,"abstract":"Dynamic carburization is a common and important phenomenon in many industrial reactions. Finding the critical factor governing this process is significant for catalyst optimization, which is complicated due to the coherence between catalyst dynamics and reaction dynamics. In this work, we manipulate the in situ formation of fast carburization on the Pd-FeOx surface by revealing a domino effect between the reaction network and catalyst restructuring during long-term CO2 hydrogenation reaction. We prepared catalysts of three sizes (5Pd-FeOx, 0.5Pd-FeOx, 0.05Pd-FeOx) and found that the large size of Pd NP (5Pd-FeOx) induces the reactive metal–support interaction, following the in situ Pd3Fe formation, the reaction route change, the fast surface carburization (Fe5C2), and finally the superior catalytic performance. Among these changes, we identify that in situ alloying instead of the apparent size difference is crucial for the formation of the active Fe5C2 phase. As a proof of concept, we further design a presynthesized Pd3Fe alloy on FeOx and find an enhanced activity with reduced Pd loading by controlled fast carburization. This work not only demonstrates the controllability of dynamic carburization but also presents a benchmark of optimizing catalysts through the comprehensive understanding of in situ catalyst changes.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"64 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165447","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

Open the Pores: Particles with Fully Accessible Hierarchical Pore Networks by Controlling Phase Separation in Confinement 打开孔隙：在限制条件下控制相分离的具有完全可访问的分层孔隙网络的颗粒

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-29 DOI: 10.1021/jacs.5c03923

Umair Sultan, Alexander Götz, Nicolas Salcedo, Lukas Sandner, Johannes Martinus Peter Beunen, Alexander Kichigin, Carola Vorndran, Paolo Malgaretti, Benjamin Apeleo Zubiri, Matthias Thommes, Jens Harting, Erdmann Spiecker, Nicolas Vogel

{"title":"Open the Pores: Particles with Fully Accessible Hierarchical Pore Networks by Controlling Phase Separation in Confinement","authors":"Umair Sultan, Alexander Götz, Nicolas Salcedo, Lukas Sandner, Johannes Martinus Peter Beunen, Alexander Kichigin, Carola Vorndran, Paolo Malgaretti, Benjamin Apeleo Zubiri, Matthias Thommes, Jens Harting, Erdmann Spiecker, Nicolas Vogel","doi":"10.1021/jacs.5c03923","DOIUrl":"https://doi.org/10.1021/jacs.5c03923","url":null,"abstract":"Hierarchical porous materials combine large surface area with efficient mass transport, in particular when macropores directly connect mesopores. Polymerization-induced spinodal decomposition of poly(ethylene glycol) and tetraethyl orthosilicate can produce such macro-mesoporous material in bulk. However, the confinement of this spinodal decomposition process to emulsion droplets typically produces porous particles with a dense silica shell that blocks pore accessibility. Here, we address this issue by controlling the interfacial energies of the two phases undergoing spinodal decomposition within the emulsion droplet. We use surfactant mixtures to induce neutral wetting to prevent shell formation and generate particles with fully open, accessible and interconnected pore systems. Lattice Boltzmann simulations corroborate the experimental findings and underline that neutral wetting conditions with a contact angle to the continuous phase of ∼90° for both phases are essential to form open surface pores. Our work provides a simple strategy for producing hierarchical porous particles with controlled surface and bulk porosity between ∼200 and ∼6000 nm, expanding their potential for applications in catalysis, separation technologies, and adsorption.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"148 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165449","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