Pub Date : 2026-02-11DOI: 10.1021/acssuschemeng.5c12134
Francisco Velasco,Rocio Villa,Rebeca Salas,Francisco J. Ruiz,Susana Nieto,Jairton Dupont,Eduardo Garcia-Verdugo,Pedro Lozano
The increasing production of polyurethane foams (PUFs) and their inherently cross-linked, recalcitrant structure pose major challenges for waste management and circular economy implementation. While mechanical recycling remains the preferred option for thermoplastics, its applicability to thermoset materials such as PUFs is severely limited. Chemical depolymerization has therefore emerged as a key strategy for closing the loop on PUF waste (PUFW). This review provides a critical overview of the chemistry, mechanisms, and technological readiness of the main chemical recycling pathways─particularly glycolysis and acidolysis─highlighting their reaction dynamics, process parameters, and environmental implications. Glycolysis stands out as a mature and versatile technology capable of recovering high-purity polyols under optimized catalytic conditions, whereas acidolysis using (di)carboxylic acids offers milder operation, faster kinetics, and reduced release of toxic aromatic amines. Hybrid processes that combine both approaches are now entering industrial deployment, as demonstrated by large-scale consortia, such as Renuva, Circufoam, and Recpur, which collectively illustrate the progression from laboratory research to pilot-scale or commercial implementation. Additionally, emerging biotechnological routes─encompassing enzymatic depolymerization and nonisocyanate polyurethane synthesis─and Dynamic Covalent Polymer Networks (DCPNs) approaches are discussed as complementary long-term solutions, though they remain at low technology readiness levels (TRL < 4). Overall, this review identifies the current advances, limitations, and prospects of PUF chemical recycling technologies and provides a roadmap for integrating these strategies into sustainable polymer value chains within a truly circular economy framework.
{"title":"Closing the Loop on Polyurethane Foam Waste: Challenges, Emerging Technologies, and the Road to Sustainable Circularity","authors":"Francisco Velasco,Rocio Villa,Rebeca Salas,Francisco J. Ruiz,Susana Nieto,Jairton Dupont,Eduardo Garcia-Verdugo,Pedro Lozano","doi":"10.1021/acssuschemeng.5c12134","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12134","url":null,"abstract":"The increasing production of polyurethane foams (PUFs) and their inherently cross-linked, recalcitrant structure pose major challenges for waste management and circular economy implementation. While mechanical recycling remains the preferred option for thermoplastics, its applicability to thermoset materials such as PUFs is severely limited. Chemical depolymerization has therefore emerged as a key strategy for closing the loop on PUF waste (PUFW). This review provides a critical overview of the chemistry, mechanisms, and technological readiness of the main chemical recycling pathways─particularly glycolysis and acidolysis─highlighting their reaction dynamics, process parameters, and environmental implications. Glycolysis stands out as a mature and versatile technology capable of recovering high-purity polyols under optimized catalytic conditions, whereas acidolysis using (di)carboxylic acids offers milder operation, faster kinetics, and reduced release of toxic aromatic amines. Hybrid processes that combine both approaches are now entering industrial deployment, as demonstrated by large-scale consortia, such as Renuva, Circufoam, and Recpur, which collectively illustrate the progression from laboratory research to pilot-scale or commercial implementation. Additionally, emerging biotechnological routes─encompassing enzymatic depolymerization and nonisocyanate polyurethane synthesis─and Dynamic Covalent Polymer Networks (DCPNs) approaches are discussed as complementary long-term solutions, though they remain at low technology readiness levels (TRL < 4). Overall, this review identifies the current advances, limitations, and prospects of PUF chemical recycling technologies and provides a roadmap for integrating these strategies into sustainable polymer value chains within a truly circular economy framework.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"91 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152384","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}
Pub Date : 2026-02-11DOI: 10.1021/acscatal.5c08338
Salai Cheettu Ammal,Andreas Heyden
Earth-abundant ZrO2-based catalysts exhibit high performance for light alkane dehydrogenation; however, the reaction mechanism and the nature of the active sites responsible for this high activity remain under debate. Microkinetic reactor simulations based on density functional theory identify low-coordinated Zr–O Lewis acid–base pairs─modeled as Zr(O)2 adatom species on the m-ZrO2(1̅11) surface─as highly active and selective sites for C2–C4 alkane dehydrogenation at low conversions (<20%). The mechanism involves kinetically favored terminal C–H activation followed by a rate-determining β-hydride elimination to yield olefins. Dehydrogenation rates increase, and apparent activation barriers decrease, with increasing carbon chain length. At higher conversions, the thermodynamically favorable β-alkyl elimination pathway becomes dominant, producing C–C cleavage products. The low-coordinated Zr–O sites can, however, deactivate in the presence of H2O; chemical or thermal treatments are required to remove strongly bound hydroxyl species and restore high catalytic activity.
{"title":"Mechanistic Insights into Light Alkane Dehydrogenation over Coordinatively Unsaturated Zr Sites on Zirconia","authors":"Salai Cheettu Ammal,Andreas Heyden","doi":"10.1021/acscatal.5c08338","DOIUrl":"https://doi.org/10.1021/acscatal.5c08338","url":null,"abstract":"Earth-abundant ZrO2-based catalysts exhibit high performance for light alkane dehydrogenation; however, the reaction mechanism and the nature of the active sites responsible for this high activity remain under debate. Microkinetic reactor simulations based on density functional theory identify low-coordinated Zr–O Lewis acid–base pairs─modeled as Zr(O)2 adatom species on the m-ZrO2(1̅11) surface─as highly active and selective sites for C2–C4 alkane dehydrogenation at low conversions (<20%). The mechanism involves kinetically favored terminal C–H activation followed by a rate-determining β-hydride elimination to yield olefins. Dehydrogenation rates increase, and apparent activation barriers decrease, with increasing carbon chain length. At higher conversions, the thermodynamically favorable β-alkyl elimination pathway becomes dominant, producing C–C cleavage products. The low-coordinated Zr–O sites can, however, deactivate in the presence of H2O; chemical or thermal treatments are required to remove strongly bound hydroxyl species and restore high catalytic activity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"29 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152439","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}
Pub Date : 2026-02-11DOI: 10.1021/acscatal.5c07014
Matteo Monai,Wiebke Albrecht,Achim Alkemper,Nongnuch Artrith,Andrea Baldi,Arik Beck,Ryan T. Berry,Ettore Bianco,Floor A. Brzesowsky,Qi Dong,Jimmy A. Faria Albanese,Renee R. Frontiera,Elaina Galvin,Erik C. Garnett,Nick Gerrits,Marek Grzelczak,Marc Herzog,Franziska Hess,Alexander A. Kolganov,Wouter Koopman,Nikolay Kosinov,Sarah Lander,Enrico Lepre,D. Nicolette Maaskant,Guobin Miao,Aadesh Mohan Naik,Tzia Ming Onn,Andrew A. Peterson,Diana Piankova,Evgeny A. Pidko,Korawich Trangwachirachai,Floris van den Bosch,Di Xu,Begum Yilmaz,Johannes Zeininger,Esther Alarcón Lladó,Jörg Meyer,Paul J. Dauenhauer,Sven H. C. Askes
Traditional heterogeneous catalysis is constrained by kinetic and thermodynamic limits, such as the Sabatier principle and reaction equilibrium. Dynamic and resonant catalysts hold promise to overcome these limitations by actively oscillating a catalyst’s physical or electronic structure at the time scale of the catalytic cycle, allowing programmable control over reaction pathways, and leading to improved rate and selectivity. External stimuli such as temperature swing, mechanical strain, electric charge, and light can perturb catalyst surfaces in different ways, altering adsorbate coverage, binding energies, and transition states beyond what steady-state catalysis allows. This work surveys the current state of dynamic catalysis, introduces the concept of “stimulando” characterization for observing transient dynamics, and outlines key modeling, mechanistic, and benchmarking strategies to advance the field toward improved chemical transformation.
{"title":"Grand Challenges and Opportunities in Stimulated Dynamic and Resonant Catalysis","authors":"Matteo Monai,Wiebke Albrecht,Achim Alkemper,Nongnuch Artrith,Andrea Baldi,Arik Beck,Ryan T. Berry,Ettore Bianco,Floor A. Brzesowsky,Qi Dong,Jimmy A. Faria Albanese,Renee R. Frontiera,Elaina Galvin,Erik C. Garnett,Nick Gerrits,Marek Grzelczak,Marc Herzog,Franziska Hess,Alexander A. Kolganov,Wouter Koopman,Nikolay Kosinov,Sarah Lander,Enrico Lepre,D. Nicolette Maaskant,Guobin Miao,Aadesh Mohan Naik,Tzia Ming Onn,Andrew A. Peterson,Diana Piankova,Evgeny A. Pidko,Korawich Trangwachirachai,Floris van den Bosch,Di Xu,Begum Yilmaz,Johannes Zeininger,Esther Alarcón Lladó,Jörg Meyer,Paul J. Dauenhauer,Sven H. C. Askes","doi":"10.1021/acscatal.5c07014","DOIUrl":"https://doi.org/10.1021/acscatal.5c07014","url":null,"abstract":"Traditional heterogeneous catalysis is constrained by kinetic and thermodynamic limits, such as the Sabatier principle and reaction equilibrium. Dynamic and resonant catalysts hold promise to overcome these limitations by actively oscillating a catalyst’s physical or electronic structure at the time scale of the catalytic cycle, allowing programmable control over reaction pathways, and leading to improved rate and selectivity. External stimuli such as temperature swing, mechanical strain, electric charge, and light can perturb catalyst surfaces in different ways, altering adsorbate coverage, binding energies, and transition states beyond what steady-state catalysis allows. This work surveys the current state of dynamic catalysis, introduces the concept of “stimulando” characterization for observing transient dynamics, and outlines key modeling, mechanistic, and benchmarking strategies to advance the field toward improved chemical transformation.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"46 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152444","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}
The study of rare events is one of the major challenges in atomistic simulations, and several enhanced sampling methods toward its solution have been proposed. Recently, it has been suggested that the use of the committor, which provides a precise formal description of rare events, could be of use in this context. We have recently followed up on this suggestion and proposed a committor-based method that promotes frequent transitions between the metastable states of the system and allows extensive sampling of the process transition state ensemble. One of the strengths of our approach is being self-consistent and semiautomatic, exploiting a variational criterion to iteratively optimize a neural-network-based parametrization of the committor, which uses a set of physical descriptors as input. Here, we further automate this procedure by combining our previous method with the expressive power of graph neural networks, which can directly process atomic coordinates rather than descriptors. Besides applications on benchmark systems, we highlight the advantages of a graph-based approach in describing the role of solvent molecules in systems, such as ion pair dissociation or ligand binding.
{"title":"Committors without Descriptors","authors":"Peilin Kang,Jintu Zhang,Enrico Trizio,TingJun Hou,Michele Parrinello","doi":"10.1021/acs.jctc.5c01848","DOIUrl":"https://doi.org/10.1021/acs.jctc.5c01848","url":null,"abstract":"The study of rare events is one of the major challenges in atomistic simulations, and several enhanced sampling methods toward its solution have been proposed. Recently, it has been suggested that the use of the committor, which provides a precise formal description of rare events, could be of use in this context. We have recently followed up on this suggestion and proposed a committor-based method that promotes frequent transitions between the metastable states of the system and allows extensive sampling of the process transition state ensemble. One of the strengths of our approach is being self-consistent and semiautomatic, exploiting a variational criterion to iteratively optimize a neural-network-based parametrization of the committor, which uses a set of physical descriptors as input. Here, we further automate this procedure by combining our previous method with the expressive power of graph neural networks, which can directly process atomic coordinates rather than descriptors. Besides applications on benchmark systems, we highlight the advantages of a graph-based approach in describing the role of solvent molecules in systems, such as ion pair dissociation or ligand binding.","PeriodicalId":45,"journal":{"name":"Journal of Chemical Theory and Computation","volume":"29 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152520","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}
Pub Date : 2026-02-11DOI: 10.1021/acs.langmuir.5c06220
Arka Biswas,Suresh K. Jewrajka
We report the development of a membrane surface featuring both fouling release and antimicrobial properties, incorporating biocidal and fouling release structural motifs. The ultrafiltration membrane surface is modified by the PEGylated cross-linked micelles of partially alkylated poly(vinyl imidazole) followed by brief solvent evaporation to obtain an interconnected micelles network via intra- and intermicellar cross-linking and alkyl chain entanglement. The resulting PEGylated micellar coating endows the membrane surface with strong antimicrobial and biofilm inhibition activity. The modified membrane (MUF-PEG2k) displays good antifouling/antibiofouling performance during the separation of emulsified oil, protein, and bacteria with flux recovery ratios of 86.6%, 86%, and 93%, respectively, after total 40 h of test. The combined effects of low-surface-energy alkyl and polar hydrophilic PEG chains promote fouling release activity, while quaternized amine groups and lipophilic alkyl segments provide antimicrobial and biofilm inhibition properties. Glass and 96-cell well surfaces are also modified by this process. This strategy offers a platform for engineering robust, multifunctional membrane surfaces toward sustainable separation and biofouling mitigation.
{"title":"PEGylated Cross-Linked Amphiphilic Micellar Network for Fouling Release and Antibiofouling Ultrafiltration Membranes","authors":"Arka Biswas,Suresh K. Jewrajka","doi":"10.1021/acs.langmuir.5c06220","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c06220","url":null,"abstract":"We report the development of a membrane surface featuring both fouling release and antimicrobial properties, incorporating biocidal and fouling release structural motifs. The ultrafiltration membrane surface is modified by the PEGylated cross-linked micelles of partially alkylated poly(vinyl imidazole) followed by brief solvent evaporation to obtain an interconnected micelles network via intra- and intermicellar cross-linking and alkyl chain entanglement. The resulting PEGylated micellar coating endows the membrane surface with strong antimicrobial and biofilm inhibition activity. The modified membrane (MUF-PEG2k) displays good antifouling/antibiofouling performance during the separation of emulsified oil, protein, and bacteria with flux recovery ratios of 86.6%, 86%, and 93%, respectively, after total 40 h of test. The combined effects of low-surface-energy alkyl and polar hydrophilic PEG chains promote fouling release activity, while quaternized amine groups and lipophilic alkyl segments provide antimicrobial and biofilm inhibition properties. Glass and 96-cell well surfaces are also modified by this process. This strategy offers a platform for engineering robust, multifunctional membrane surfaces toward sustainable separation and biofouling mitigation.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"60 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152536","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-11DOI: 10.1021/acs.orglett.6c00403
Jiong Xu Ng,Gang Liao,Yu Zhao
Chiral sulfoxides are highly important structural motifs that find wide application in asymmetric synthesis and the pharmaceutical industry. While traditional access to chiral sulfoxides mainly relies on asymmetric oxidation of the sulfide center, innovation in catalytic strategy can lead to new and valuable analogs. Herein, we present an unprecedented enantioselective imine condensation approach, resulting in efficient kinetic resolution of sulfoxide molecules bearing an aldehyde functionality with selectivity factor up to >100. Using this chiral acid-catalyzed process with an operationally simple procedure, chiral sulfoxides could be accessed in good yields and excellent enantioselectivities. The resultant chiral sulfoxides could be further transformed via a one-step derivatization to previously inaccessible bifunctional molecules with great potential in asymmetric synthesis.
{"title":"Access to Chiral Sulfoxides by Enantioselective Imine Condensation","authors":"Jiong Xu Ng,Gang Liao,Yu Zhao","doi":"10.1021/acs.orglett.6c00403","DOIUrl":"https://doi.org/10.1021/acs.orglett.6c00403","url":null,"abstract":"Chiral sulfoxides are highly important structural motifs that find wide application in asymmetric synthesis and the pharmaceutical industry. While traditional access to chiral sulfoxides mainly relies on asymmetric oxidation of the sulfide center, innovation in catalytic strategy can lead to new and valuable analogs. Herein, we present an unprecedented enantioselective imine condensation approach, resulting in efficient kinetic resolution of sulfoxide molecules bearing an aldehyde functionality with selectivity factor up to >100. Using this chiral acid-catalyzed process with an operationally simple procedure, chiral sulfoxides could be accessed in good yields and excellent enantioselectivities. The resultant chiral sulfoxides could be further transformed via a one-step derivatization to previously inaccessible bifunctional molecules with great potential in asymmetric synthesis.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"307 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152556","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}
Fine-tuning the solid–electrolyte interface (SEI) on the Li anode has been widely developed to break through the cyclability bottleneck of Li metal batteries (LMBs). Meanwhile, the cycling behavior of LMBs is also dependent on cathode stability, and hence, it is promising to develop strategies that simultaneously constrain Li dendrite growth and cathode particle distortion. Herein, through copolymerization of maleic anhydride (MA) and hexafluorobutyl acrylate (HFA) monomers, an artificial interface (noted as MAF) is constructed on the Li anode. Such an MAF layer establishes hybrid SEI components consisting of an inorganic-rich interior and a polymer exterior. Its bifunctional contributions on the Li anode and the LiFePO4 (LFP) or LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode are validated by virtue of its dynamic polymer evolution upon LMB cycling. Besides providing lithophilic sites for even Li+ plating, the fluorinated oligomers within the MAF exterior further evolve under an ethylene carbonate (EC)-based electrolyte, inducing dynamic maturation of the LiF-rich cathode–electrolyte interface (CEI). As a result, Li||Li symmetric cells perform for over 900 h of cycling at 1 mA cm–2, while Li||LFP and Li||NCM811 cells maintain capacity retentions of 90.2% after 1500 cycles and 80.6% after 350 cycles at their respective 1 C rate.
为了突破锂金属电池的可循环瓶颈，锂阳极固液界面（SEI）的微调得到了广泛的发展。同时，lmb的循环行为也依赖于阴极稳定性，因此，开发同时抑制Li枝晶生长和阴极颗粒畸变的策略是有希望的。本文通过马来酸酐（MA）和六氟丙烯酸丁酯（HFA）单体的共聚，在锂阳极上构建了一个人工界面（MAF）。这样的MAF层建立了由富无机内部和聚合物外部组成的杂化SEI组分。其在锂阳极和LiFePO4 （LFP）或LiNi0.8Co0.1Mn0.1O2 （NCM811）阴极上的双功能贡献通过其在LMB循环过程中的动态聚合物演化得到验证。除了为均匀的Li+电镀提供亲石位点外，MAF外部的氟化低聚物在基于碳酸乙烯（EC）的电解质下进一步演化，诱导富锂阴极-电解质界面（CEI）的动态成熟。结果表明，Li||Li对称电池在1 mA cm-2下的循环时间超过900小时，而Li||LFP和Li||NCM811电池在各自的1℃速率下，在1500次循环后和350次循环后的容量保持率分别为90.2%和80.6%。
{"title":"Dynamic Anode/Cathode–Electrolyte Interface Induced through Polymer Evolution for Durable Lithium Metal Batteries","authors":"Wanru Lin,Kang Zhou,Chao Yang,Huayu Huang,Jian Lan,Hao Peng,Songzhi Zheng,Tianpeng Jiao,Shiwen Wang,Jianming Zheng,Wanwisa Limphirat,Ling Huang,Shi-Gang Sun,Ya-Ping Deng","doi":"10.1021/jacs.5c18082","DOIUrl":"https://doi.org/10.1021/jacs.5c18082","url":null,"abstract":"Fine-tuning the solid–electrolyte interface (SEI) on the Li anode has been widely developed to break through the cyclability bottleneck of Li metal batteries (LMBs). Meanwhile, the cycling behavior of LMBs is also dependent on cathode stability, and hence, it is promising to develop strategies that simultaneously constrain Li dendrite growth and cathode particle distortion. Herein, through copolymerization of maleic anhydride (MA) and hexafluorobutyl acrylate (HFA) monomers, an artificial interface (noted as MAF) is constructed on the Li anode. Such an MAF layer establishes hybrid SEI components consisting of an inorganic-rich interior and a polymer exterior. Its bifunctional contributions on the Li anode and the LiFePO4 (LFP) or LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode are validated by virtue of its dynamic polymer evolution upon LMB cycling. Besides providing lithophilic sites for even Li+ plating, the fluorinated oligomers within the MAF exterior further evolve under an ethylene carbonate (EC)-based electrolyte, inducing dynamic maturation of the LiF-rich cathode–electrolyte interface (CEI). As a result, Li||Li symmetric cells perform for over 900 h of cycling at 1 mA cm–2, while Li||LFP and Li||NCM811 cells maintain capacity retentions of 90.2% after 1500 cycles and 80.6% after 350 cycles at their respective 1 C rate.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"89 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152572","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}
Two-electron oxygen reduction reaction (2e–ORR) in neutral media offers an eco-friendly and practical strategy for efficient synthesis of hydrogen peroxide (H2O2), yet limited understanding of electrocatalytic mechanisms and poor catalyst activity hinder its development. We propose a strategic design principle for high-performance four-coordinated Co single-atom catalysts based on atomic entropy fluctuation by both geometric and electronic modifications, quantitatively described by the descriptor φ, which is able to capture the impact of local entropy fluctuations on catalytic performance. φ serves as an effective metric for elucidating the relationship between ORR activity and the coordination environment in Co single-atom catalyst systems, thereby elucidating the origin of the high activity of CoN3S, which lies close to the apex of the volcano peak. Based on the prediction, the as-synthesized Co–N3SC catalyst achieved a 97% selectivity for H2O2 electrosynthesis at low overpotentials in neutral electrolytes. Impressively, Co–N3SC exhibited remarkable stability and delivered a cumulative yield of 10.58 g of H2O2 in flow cell devices (110 h @0.18A). In a solid-state electrolyte electrolyzer, it achieved a production rate of 10.25 mol gcat–1 h–1, enabling the direct synthesis of high-purity urea peroxide. This work offers not only strategies for designing highly active and selective 2e–ORR catalysts but deep insights into coordination environment–activity regulation and validation of practical catalyst applications.
中性介质中的双电子氧还原反应（2e-ORR）为高效合成过氧化氢（H2O2）提供了一种环保实用的策略，但对电催化机理的了解有限，催化剂活性差，阻碍了其发展。我们提出了一种基于原子熵波动的高性能四配位Co单原子催化剂的策略设计原则，通过几何和电子修饰，用描述符φ定量描述，能够捕捉局部熵波动对催化性能的影响。φ可以作为解释Co单原子催化剂体系中ORR活性与配位环境之间关系的有效度量，从而解释了CoN3S高活性的来源，它位于靠近火山顶点的位置。基于预测，合成的Co-N3SC催化剂在中性电解质中低过电位下电合成H2O2的选择性达到97%。令人印象深刻的是，Co-N3SC表现出了显著的稳定性，在流动电池装置中（110 h @0.18A）累计产H2O2量为10.58 g。在固态电解质电解槽中，其产率达到10.25 mol gcat-1 h-1，可直接合成高纯度过氧化脲。这项工作不仅为设计高活性和选择性的2 - orr催化剂提供了策略，而且为协调环境-活性调节和实际催化剂应用的验证提供了深刻的见解。
{"title":"Chaos of Active Site Structure as a Ladder to Climbing the Apex of the 2e–ORR Volcano Plot","authors":"Jiannan Du,Guokang Han,Xin Zhang,Dongyue Xin,Yuqi Yan,Xiaodan Wen,Hua Huo,Geping Yin,Yong Shuai,Chunyu Du","doi":"10.1021/jacs.5c15908","DOIUrl":"https://doi.org/10.1021/jacs.5c15908","url":null,"abstract":"Two-electron oxygen reduction reaction (2e–ORR) in neutral media offers an eco-friendly and practical strategy for efficient synthesis of hydrogen peroxide (H2O2), yet limited understanding of electrocatalytic mechanisms and poor catalyst activity hinder its development. We propose a strategic design principle for high-performance four-coordinated Co single-atom catalysts based on atomic entropy fluctuation by both geometric and electronic modifications, quantitatively described by the descriptor φ, which is able to capture the impact of local entropy fluctuations on catalytic performance. φ serves as an effective metric for elucidating the relationship between ORR activity and the coordination environment in Co single-atom catalyst systems, thereby elucidating the origin of the high activity of CoN3S, which lies close to the apex of the volcano peak. Based on the prediction, the as-synthesized Co–N3SC catalyst achieved a 97% selectivity for H2O2 electrosynthesis at low overpotentials in neutral electrolytes. Impressively, Co–N3SC exhibited remarkable stability and delivered a cumulative yield of 10.58 g of H2O2 in flow cell devices (110 h @0.18A). In a solid-state electrolyte electrolyzer, it achieved a production rate of 10.25 mol gcat–1 h–1, enabling the direct synthesis of high-purity urea peroxide. This work offers not only strategies for designing highly active and selective 2e–ORR catalysts but deep insights into coordination environment–activity regulation and validation of practical catalyst applications.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"7 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152574","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}
Deqin Cai,Xuankun Chen,Yaxian Zhou,Malick Bio Idrissou,Reinier Hernandez,Weiping Tang
Targeted protein degradation (TPD) technologies have emerged as transformative therapeutic modality for treating cancers and other diseases. While significant progress has been achieved in intracellular protein degradation, degradation of membrane proteins and extracellular targets remains in an early stage. In this study, we developed a prostate-specific lysosome-targeting degradation strategy using a prostate-specific membrane antigen (PSMA) as a lysosome-targeting receptor (LTR). We demonstrated that both extracellular and membrane proteins can be selectively degraded in prostate cancer cells via the lysosome pathway. These PSMA TArgeting Chimeras (PTACs) were shown to facilitate lysosomal degradation in a selective, potent, rapid, and sustained manner. Notably, Ctx-L3 and Atz-L5 exhibited exceptional degradation potencies in LNCaP cells, with DC50 values of 4.3 pM for EGFR and 2 pM for PD-L1, respectively─among the most potent degraders reported to date. Furthermore, the application of PTACs to degrade PD-L1, using both antibody- and small-molecule-based formats, highlights the versatility of this platform. Collectively, this work advances the application of TPD technology and offers promising avenues for precision medicine in prostate-related diseases.
{"title":"Development of Prostate-Specific Lysosome-Targeting Degraders","authors":"Deqin Cai,Xuankun Chen,Yaxian Zhou,Malick Bio Idrissou,Reinier Hernandez,Weiping Tang","doi":"10.1021/jacs.5c18594","DOIUrl":"https://doi.org/10.1021/jacs.5c18594","url":null,"abstract":"Targeted protein degradation (TPD) technologies have emerged as transformative therapeutic modality for treating cancers and other diseases. While significant progress has been achieved in intracellular protein degradation, degradation of membrane proteins and extracellular targets remains in an early stage. In this study, we developed a prostate-specific lysosome-targeting degradation strategy using a prostate-specific membrane antigen (PSMA) as a lysosome-targeting receptor (LTR). We demonstrated that both extracellular and membrane proteins can be selectively degraded in prostate cancer cells via the lysosome pathway. These PSMA TArgeting Chimeras (PTACs) were shown to facilitate lysosomal degradation in a selective, potent, rapid, and sustained manner. Notably, Ctx-L3 and Atz-L5 exhibited exceptional degradation potencies in LNCaP cells, with DC50 values of 4.3 pM for EGFR and 2 pM for PD-L1, respectively─among the most potent degraders reported to date. Furthermore, the application of PTACs to degrade PD-L1, using both antibody- and small-molecule-based formats, highlights the versatility of this platform. Collectively, this work advances the application of TPD technology and offers promising avenues for precision medicine in prostate-related diseases.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"99 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152594","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}
Pub Date : 2026-02-11DOI: 10.1038/s41557-026-02073-1
Xiaodong Ye, Bo Sun, Shi-Liang Shi
Grignard reagents—cornerstones of synthetic chemistry—are hindered by enduring limitations in accessing complex architectures, which poses a persistent synthetic bottleneck. Meanwhile, quaternary carbon (stereo)centres, ubiquitous in bioactive molecules and natural products, remain formidable synthetic targets despite decades of research. Here we introduce a nickel-catalysed carbomagnesiation strategy that simultaneously overcomes these challenges through a rare contra-electronegativity transmetallation (Ni to Mg). This approach enables the efficient and modular synthesis of β-quaternary Grignard reagents via carbomagnesiation of 1,1-disubstituted alkenes and 1,3-dienes, employing aryl triflate and PhMgBr as carbon and magnesium sources, respectively. The resulting organomagnesium reagents undergo one-pot reactions with diverse electrophiles, delivering stereochemically complex quaternary centres with high precision. Mechanistically, bulky N-heterocyclic carbene (NHC)-based catalysts divert classical cross-coupling pathways, enforcing a counterintuitive Ni-to-Mg transmetallation that defies conventional electronegativity trends while achieving exceptional regio- and enantiocontrol. This contra-electronegativity transmetallation demonstrates substantial potential to advance carbometallation reactions and open new avenues for cross-coupling chemistry.
{"title":"Contra-electronegativity transmetallation unlocks alkene carbomagnesiation to access quaternary stereocentres","authors":"Xiaodong Ye, Bo Sun, Shi-Liang Shi","doi":"10.1038/s41557-026-02073-1","DOIUrl":"https://doi.org/10.1038/s41557-026-02073-1","url":null,"abstract":"Grignard reagents—cornerstones of synthetic chemistry—are hindered by enduring limitations in accessing complex architectures, which poses a persistent synthetic bottleneck. Meanwhile, quaternary carbon (stereo)centres, ubiquitous in bioactive molecules and natural products, remain formidable synthetic targets despite decades of research. Here we introduce a nickel-catalysed carbomagnesiation strategy that simultaneously overcomes these challenges through a rare contra-electronegativity transmetallation (Ni to Mg). This approach enables the efficient and modular synthesis of β-quaternary Grignard reagents via carbomagnesiation of 1,1-disubstituted alkenes and 1,3-dienes, employing aryl triflate and PhMgBr as carbon and magnesium sources, respectively. The resulting organomagnesium reagents undergo one-pot reactions with diverse electrophiles, delivering stereochemically complex quaternary centres with high precision. Mechanistically, bulky N-heterocyclic carbene (NHC)-based catalysts divert classical cross-coupling pathways, enforcing a counterintuitive Ni-to-Mg transmetallation that defies conventional electronegativity trends while achieving exceptional regio- and enantiocontrol. This contra-electronegativity transmetallation demonstrates substantial potential to advance carbometallation reactions and open new avenues for cross-coupling chemistry.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"7 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152238","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：