Chi Duan, Jiaqi Zhao, Run Shi, Jinjia Liu, Li-Ping Zhang, Li-Zhu Wu, Zhenhua Li, Tierui Zhang
Photocatalytic propane dehydrogenation (PDH) offers a promising route for propylene production under mild conditions despite the unsatisfactory propylene yield at present. Herein, we have introduced several second metals into Pt/ZnO catalyst to modulate the electronic structure of Pt by forming PtM alloys. Among all these catalysts, PtPb alloys/ZnO catalyst (PtPb/ZnO) exhibits the optimum photocatalytic PDH activity. Both experiments and density functional theory calculations reveals that PtPb alloys significantly increases the electron density of Pt, weakening the interaction between Pt and propylene. This facilitates the desorption of the produced propylene during photocatalytic PDH, thus helping to release Pt active sites for reactant conversion. A 3.6-fold increase on propylene yield of photocatalytic PDH has been achieved over PtPb/ZnO with a propylene production rate of 5.4 mmol g−1 h−1. Our findings highlight the critical relationship between the electronic structure of Pt active sites and performance, marking product desorption modulation an effective strategy to boost photocatalytic PDH.
{"title":"Enhancing Photocatalytic Propane Dehydrogenation via Electronic Structure Modulation of Platinum Sites Over Platinum-Based Alloys","authors":"Chi Duan, Jiaqi Zhao, Run Shi, Jinjia Liu, Li-Ping Zhang, Li-Zhu Wu, Zhenhua Li, Tierui Zhang","doi":"10.1002/anie.202524711","DOIUrl":"https://doi.org/10.1002/anie.202524711","url":null,"abstract":"Photocatalytic propane dehydrogenation (PDH) offers a promising route for propylene production under mild conditions despite the unsatisfactory propylene yield at present. Herein, we have introduced several second metals into Pt/ZnO catalyst to modulate the electronic structure of Pt by forming PtM alloys. Among all these catalysts, PtPb alloys/ZnO catalyst (PtPb/ZnO) exhibits the optimum photocatalytic PDH activity. Both experiments and density functional theory calculations reveals that PtPb alloys significantly increases the electron density of Pt, weakening the interaction between Pt and propylene. This facilitates the desorption of the produced propylene during photocatalytic PDH, thus helping to release Pt active sites for reactant conversion. A 3.6-fold increase on propylene yield of photocatalytic PDH has been achieved over PtPb/ZnO with a propylene production rate of 5.4 mmol g<sup>−1</sup> h<sup>−1</sup>. Our findings highlight the critical relationship between the electronic structure of Pt active sites and performance, marking product desorption modulation an effective strategy to boost photocatalytic PDH.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"46 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146153717","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/acssuschemeng.5c11739
Patrick A. Bailie,Pamela J. Walsh,Andrew C. Marr,Patricia C. Marr
A class of NaturIL gels was prepared from alginate and ionic liquids containing ions that can be derived from nature. Aqueous Cholinium Amino Acid Ionic Liquids (ChAAILs) solutions with sodium alginate derived from Laminaria digitata were cross-linked by calcium ions and the variation of rheological properties investigated relative to the parent hydrogel. Viscoelastic gels were formed for the four amino acid anions [Pro], [Gly], [Lys] and [Val] and their rheological properties were compared to those of an analogous hydrogel. All four were found to be stiffer and more viscoelastic than the hydrogel and have properties that varied as the amino acid anion was changed.
{"title":"NaturIL Gels: Gels Formed from the Synergy of Alginates and Bioderived Ions. Tunable Gels from Seaweed","authors":"Patrick A. Bailie,Pamela J. Walsh,Andrew C. Marr,Patricia C. Marr","doi":"10.1021/acssuschemeng.5c11739","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11739","url":null,"abstract":"A class of NaturIL gels was prepared from alginate and ionic liquids containing ions that can be derived from nature. Aqueous Cholinium Amino Acid Ionic Liquids (ChAAILs) solutions with sodium alginate derived from Laminaria digitata were cross-linked by calcium ions and the variation of rheological properties investigated relative to the parent hydrogel. Viscoelastic gels were formed for the four amino acid anions [Pro], [Gly], [Lys] and [Val] and their rheological properties were compared to those of an analogous hydrogel. All four were found to be stiffer and more viscoelastic than the hydrogel and have properties that varied as the amino acid anion was changed.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"59 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152382","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}
Monoclonal antibodies are widely used biotherapeutics, whose efficacy and pharmacokinetics critically depend on their structural integrity. Among chemical degradation pathways, methionine oxidation is a particularly important post-translational modification that compromises antibody stability, Fc receptor binding, and thereby FcRn-mediated recycling and FcγR-mediated effector functions. However, the structural consequences of oxidation remain poorly understood, largely due to the subtle and localized nature of the modification. Here, we present an integrated analytical framework combining methyl-based NMR spectroscopy, selective enzymatic reduction, and peptide mapping to resolve methionine oxidation in the Fc region of human IgG1 antibodies at residue- and stereochemical-level resolution. By selectively labeling methionine methyl groups, we monitored oxidation-induced spectral changes in conserved Fc residues Met252 and Met428. Site-directed mutagenesis revealed a mutual influence between these residues, consistent with their spatial proximity at the CH2–CH3 domain interface. Stereospecific reduction with methionine sulfoxide reductase A enabled the assignment of R- and S-isomers, while peptide mapping by liquid chromatography–mass spectrometry corroborated the NMR findings. This combined approach demonstrated that Met252, which is solvent-exposed, is more susceptible to oxidation than buried Met428 and that both residues display stereochemical heterogeneity that modulates local structure. By bridging chemical modifications and higher-order structural perturbations, this integrated framework provides mechanistic insights into how methionine oxidation impairs antibody function. More broadly, it establishes a basis for quality assurance and rational design of therapeutic antibodies with improved stability.
{"title":"Stereochemical and Structural Characterization of Methionine Oxidation in the IgG1 Fc Region by Integrated NMR and LC-MS Analysis","authors":"Maho Yagi-Utsumi,Saeko Yanaka,Noritaka Hashii,Kohei Tomita,Takashi Misawa,Yosuke Demizu,Akiko Ishii-Watabe,Koichi Kato","doi":"10.1021/acs.analchem.5c06092","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c06092","url":null,"abstract":"Monoclonal antibodies are widely used biotherapeutics, whose efficacy and pharmacokinetics critically depend on their structural integrity. Among chemical degradation pathways, methionine oxidation is a particularly important post-translational modification that compromises antibody stability, Fc receptor binding, and thereby FcRn-mediated recycling and FcγR-mediated effector functions. However, the structural consequences of oxidation remain poorly understood, largely due to the subtle and localized nature of the modification. Here, we present an integrated analytical framework combining methyl-based NMR spectroscopy, selective enzymatic reduction, and peptide mapping to resolve methionine oxidation in the Fc region of human IgG1 antibodies at residue- and stereochemical-level resolution. By selectively labeling methionine methyl groups, we monitored oxidation-induced spectral changes in conserved Fc residues Met252 and Met428. Site-directed mutagenesis revealed a mutual influence between these residues, consistent with their spatial proximity at the CH2–CH3 domain interface. Stereospecific reduction with methionine sulfoxide reductase A enabled the assignment of R- and S-isomers, while peptide mapping by liquid chromatography–mass spectrometry corroborated the NMR findings. This combined approach demonstrated that Met252, which is solvent-exposed, is more susceptible to oxidation than buried Met428 and that both residues display stereochemical heterogeneity that modulates local structure. By bridging chemical modifications and higher-order structural perturbations, this integrated framework provides mechanistic insights into how methionine oxidation impairs antibody function. More broadly, it establishes a basis for quality assurance and rational design of therapeutic antibodies with improved stability.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"29 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152386","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}
Alkenylboronates represent a cornerstone functional group in modern organic synthesis owing to their versatile reactivity in Suzuki–Miyaura cross-coupling reactions and other key transformations. However, catalytic asymmetric methods for producing stereodefined tetrasubstituted axially chiral alkenylboronates remain underdeveloped. Here, we report a copper-catalyzed atroposelective protoboration of allenes, providing a facile strategy to access tetrasubstituted axially chiral Z-alkenylboronates with excellent regio- and atroposelectivities. The enantiomerically enriched axially chiral alkenylboronates could be further transformed into diverse stereodefined tetrasubstituted axially chiral olefins via the cross-coupling reaction of the C–B bond. This methodology also provides a new avenue to construct C–C or C–N axially chiral alkene–phosphine frameworks.
{"title":"Cu-Catalyzed Atroposelective Protoboration of Allenes to Access Stereodefined Tetrasubstituted Axially Chiral Alkenylboronates","authors":"Baoli Li,Zhan Huang,Shichao Hong,Liangzhi Pang,Yan Wu,Xuechen Li,Hao Li,Hua-Jie Jiang,Jie Yu,Xue Zhang,Qiankun Li","doi":"10.1021/acs.orglett.6c00026","DOIUrl":"https://doi.org/10.1021/acs.orglett.6c00026","url":null,"abstract":"Alkenylboronates represent a cornerstone functional group in modern organic synthesis owing to their versatile reactivity in Suzuki–Miyaura cross-coupling reactions and other key transformations. However, catalytic asymmetric methods for producing stereodefined tetrasubstituted axially chiral alkenylboronates remain underdeveloped. Here, we report a copper-catalyzed atroposelective protoboration of allenes, providing a facile strategy to access tetrasubstituted axially chiral Z-alkenylboronates with excellent regio- and atroposelectivities. The enantiomerically enriched axially chiral alkenylboronates could be further transformed into diverse stereodefined tetrasubstituted axially chiral olefins via the cross-coupling reaction of the C–B bond. This methodology also provides a new avenue to construct C–C or C–N axially chiral alkene–phosphine frameworks.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"7 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152557","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}
Traditional triethylamine (TEA) gas sensors suffer from the drawback of high detection limits due to the low charge-transfer ability of materials. Herein, the Pr3+-doped WO3 one-dimensional (1D) yoga-pillar-shaped nanorods have been successfully synthesized via electrostatic spinning and oxidative calcination. The gas sensor based on WO3:1%Pr3+ 1D yoga-pillar-shaped nanorods exhibits excellent performance in terms of rapid response (3-fold), higher response (3.75-fold), and lower detection limits compared with the WO3 gas sensor. Furthermore, the sensor features excellent repeatability and long-term stability, indicating the potential commercial value. The findings reveal that doping Pr3+ is one of the effective strategies to improve the gas-sensing performance of WO3. Based on the above analysis, as well as literature reports, the gas-sensing mechanism is explored systematically. The enhancement can be attributed to the formation of impurity energy levels, which can effectively optimize the band structure and facilitate electron transfer. The recombination between electrons in the conduction band and holes in the valence band is partly suppressed, providing more opportunities for electron exchange between WO3 and oxygen molecules. The content of chemically adsorbed oxygen on the WO3 surface has significantly increased, which is one of the fundamental reasons for the improvement in gas sensitivity. In addition, the practical value of the WO3:1%Pr3+ 1D yoga-pillar-shaped nanorod gas sensor is demonstrated by testing the freshness of fish stored under various conditions. This work presents a high-performance ppb-level TEA detection method and broadens the application scope of WO3 gas sensors.
{"title":"Pr3+-Doped WO3 1D Yoga-Pillar-Shaped Nanorod Gas Sensor: A High-Performance Ppb-Level Triethylamine Gas Sensor for Fish Freshness Monitoring","authors":"Jiale Wang,Xiang Zhao,Xiang Li,Rundong Xue,Dan Li,Feng Li,Ying Yang,Tianqi Wang,Duanduan Yin,Xiangting Dong","doi":"10.1021/acssensors.5c03942","DOIUrl":"https://doi.org/10.1021/acssensors.5c03942","url":null,"abstract":"Traditional triethylamine (TEA) gas sensors suffer from the drawback of high detection limits due to the low charge-transfer ability of materials. Herein, the Pr3+-doped WO3 one-dimensional (1D) yoga-pillar-shaped nanorods have been successfully synthesized via electrostatic spinning and oxidative calcination. The gas sensor based on WO3:1%Pr3+ 1D yoga-pillar-shaped nanorods exhibits excellent performance in terms of rapid response (3-fold), higher response (3.75-fold), and lower detection limits compared with the WO3 gas sensor. Furthermore, the sensor features excellent repeatability and long-term stability, indicating the potential commercial value. The findings reveal that doping Pr3+ is one of the effective strategies to improve the gas-sensing performance of WO3. Based on the above analysis, as well as literature reports, the gas-sensing mechanism is explored systematically. The enhancement can be attributed to the formation of impurity energy levels, which can effectively optimize the band structure and facilitate electron transfer. The recombination between electrons in the conduction band and holes in the valence band is partly suppressed, providing more opportunities for electron exchange between WO3 and oxygen molecules. The content of chemically adsorbed oxygen on the WO3 surface has significantly increased, which is one of the fundamental reasons for the improvement in gas sensitivity. In addition, the practical value of the WO3:1%Pr3+ 1D yoga-pillar-shaped nanorod gas sensor is demonstrated by testing the freshness of fish stored under various conditions. This work presents a high-performance ppb-level TEA detection method and broadens the application scope of WO3 gas sensors.","PeriodicalId":24,"journal":{"name":"ACS Sensors","volume":"156 1","pages":""},"PeriodicalIF":8.9,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152355","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}
Our previous study demonstrated that apurinic/apyrimidinic endonuclease 1 (APE1) and miR-514a are significantly overexpressed in the cytoplasm of drug-resistant neuroblastoma (NB) cells. Furthermore, we have developed a novel strategy for monitoring drug resistance in NB by targeting cytoplasmic APE1 and miR-514a. The overexpression of key enzymes in the mitochondrial base excision repair pathway, along with dysregulated miRNAs, is closely associated with chemotherapy resistance in tumors. Therefore, this study leverages cytochrome c (cyt c), located in the inner mitochondrial membrane as a targeting agent and the mitochondria-specific expression of 16S rRNA as a response switch to develop a spatially resolved, sequential activation system for an allosteric DNA nanomachine (AP-miR-tFNA), enabling in vivo detection of APE1 and miR-514a within mitochondria and facilitating molecular imaging of NB. AP-miR-tFNA sequentially responds to cyt c, 16S rRNA, miR-514a, and APE1, thereby undergoing a conformational change that efficiently achieves progressive dissociation of the fluorophore from the quencher through a sequential mechanism, ultimately generating a detectable fluorescence signal. Experimental results demonstrate that AP-miR-tFNA enables in vivo monitoring of drug resistance in NB, providing an innovative and dependable approach for monitoring therapeutic resistance in NB. In particular, AP-miR-tFNA enables in situ detection of APE1 and miR-514a within NB plasma exosomes, thereby allowing non-invasive differentiation between high-risk and low-to-intermediate-risk NB, as well as between drug-resistant NB and non-drug-resistant NB.
{"title":"Spatially Resolved Sequential Activation of Allosteric DNA for In Vivo Dual-Target Detection within Mitochondria: A Strategy to Visualize of Drug-Resistant Neuroblastoma","authors":"Jingzhe Zang,Yingyu Zhang,Kangbo Liu,Yuyin Xu,Liang Zhao,Wentao Wang,Mengxin Zhang,Xueyi Qin,Qionglin Wang,Xianwei Zhang,Wancun Zhang","doi":"10.1021/acssensors.5c04083","DOIUrl":"https://doi.org/10.1021/acssensors.5c04083","url":null,"abstract":"Our previous study demonstrated that apurinic/apyrimidinic endonuclease 1 (APE1) and miR-514a are significantly overexpressed in the cytoplasm of drug-resistant neuroblastoma (NB) cells. Furthermore, we have developed a novel strategy for monitoring drug resistance in NB by targeting cytoplasmic APE1 and miR-514a. The overexpression of key enzymes in the mitochondrial base excision repair pathway, along with dysregulated miRNAs, is closely associated with chemotherapy resistance in tumors. Therefore, this study leverages cytochrome c (cyt c), located in the inner mitochondrial membrane as a targeting agent and the mitochondria-specific expression of 16S rRNA as a response switch to develop a spatially resolved, sequential activation system for an allosteric DNA nanomachine (AP-miR-tFNA), enabling in vivo detection of APE1 and miR-514a within mitochondria and facilitating molecular imaging of NB. AP-miR-tFNA sequentially responds to cyt c, 16S rRNA, miR-514a, and APE1, thereby undergoing a conformational change that efficiently achieves progressive dissociation of the fluorophore from the quencher through a sequential mechanism, ultimately generating a detectable fluorescence signal. Experimental results demonstrate that AP-miR-tFNA enables in vivo monitoring of drug resistance in NB, providing an innovative and dependable approach for monitoring therapeutic resistance in NB. In particular, AP-miR-tFNA enables in situ detection of APE1 and miR-514a within NB plasma exosomes, thereby allowing non-invasive differentiation between high-risk and low-to-intermediate-risk NB, as well as between drug-resistant NB and non-drug-resistant NB.","PeriodicalId":24,"journal":{"name":"ACS Sensors","volume":"92 1","pages":""},"PeriodicalIF":8.9,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152360","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.analchem.5c06894
Yameng Wang,Guantong Shen,Daniel Shiu-Hin Chan,Lei Wu,Chun-Yuen Wong,Jing Wang,Chung-Hang Leung,Wanhe Wang
Sulfur dioxide (SO2), a gaseous signaling molecule that can be produced endogenously in mitochondria, is an important antioxidant for maintaining redox homeostasis. Abnormal levels of mitochondrial SO2 are associated with the pathogenesis and progression of rheumatoid arthritis (RA). Therefore, it is crucial to develop a luminescence probe that can detect subcellular SO2 levels for unmasking the pathological changes and diagnosis of RA. However, current luminescence probes for SO2 in RA suffer from low photostability, weak response, short emission wavelengths below 650 nm, and/or poor mitochondria targetability. In this work, we developed a near-infrared (NIR) iridium(III) complex-based probe based on the Michael addition mechanism for rapid, real-time, and accurate detection of mitochondrial SO2. The probe not only achieved sensitive detection of SO2 in aqueous solution with a detection limit of 2.12 μM but also imaged endogenous mitochondrial SO2 levels in a cellular RA model. Furthermore, it visualized aspartate aminotransferase 1 (AAT1)-mediated SO2 generation, offering insight into the mechanism of SO2 generation in RA. Finally, it also exhibits an excellent penetration capability within 3D tumor spheroids (approximately 103 μm). Overall, this probe offers a powerful tool for effectively imaging subcellular SO2 in RA, thereby enhancing our understanding of the pathological mechanisms of RA and accelerating the development of diagnostic tools for RA.
{"title":"Dissecting Mitochondrial Sulfur Dioxide Generation Mechanism in Rheumatoid Arthritis with a NIR Luminogenic Iridium(III)-Based Probe","authors":"Yameng Wang,Guantong Shen,Daniel Shiu-Hin Chan,Lei Wu,Chun-Yuen Wong,Jing Wang,Chung-Hang Leung,Wanhe Wang","doi":"10.1021/acs.analchem.5c06894","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c06894","url":null,"abstract":"Sulfur dioxide (SO2), a gaseous signaling molecule that can be produced endogenously in mitochondria, is an important antioxidant for maintaining redox homeostasis. Abnormal levels of mitochondrial SO2 are associated with the pathogenesis and progression of rheumatoid arthritis (RA). Therefore, it is crucial to develop a luminescence probe that can detect subcellular SO2 levels for unmasking the pathological changes and diagnosis of RA. However, current luminescence probes for SO2 in RA suffer from low photostability, weak response, short emission wavelengths below 650 nm, and/or poor mitochondria targetability. In this work, we developed a near-infrared (NIR) iridium(III) complex-based probe based on the Michael addition mechanism for rapid, real-time, and accurate detection of mitochondrial SO2. The probe not only achieved sensitive detection of SO2 in aqueous solution with a detection limit of 2.12 μM but also imaged endogenous mitochondrial SO2 levels in a cellular RA model. Furthermore, it visualized aspartate aminotransferase 1 (AAT1)-mediated SO2 generation, offering insight into the mechanism of SO2 generation in RA. Finally, it also exhibits an excellent penetration capability within 3D tumor spheroids (approximately 103 μm). Overall, this probe offers a powerful tool for effectively imaging subcellular SO2 in RA, thereby enhancing our understanding of the pathological mechanisms of RA and accelerating the development of diagnostic tools for RA.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"46 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152366","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/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.
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