Degradation of mass-manufactured acrylate/methyl acrylate polymers is considered to be a promising path to alleviate the growing and alarming plastic waste issue. However, deconstruction of such stable polymers remains a daunting challenge due to the stable saturated backbone, with previous strategies primarily relying on harsh reaction conditions or cumbersome synthetic polymers that are not suitable for practical implementation and industrialization. Herein, we report a main chaininitiated, visible light-induced degradation methodology under mild conditions, which is applicable to various categories of acrylate or methacrylate copolymers. These acrylate or methacrylate copolymers could be readily prepared by copolymerizing diverse acrylate/methacrylate monomers with low mol % acrylic acid/methacrylic acid (AA/MAA), which could serve as degradable triggers. These triggers consisting of COOH groups could generate -COOCe Ⅳ species by coordinating with a cerium catalyst followed by oxidation in the presence of O 2 , thereby initiating the ligand-to-metal charge transfer process and decarboxylation under visible light irradiation to produce alkyl radicals to trigger degradation via backbone scission. More importantly, this efficient degradation could be accomplished regardless of the synthetic routes, pendant groups, chain-end functionalities, molecular weights, topological architectures and concentrations of polymers, rendering this strategy a robust route to degrade diverse acrylate/methacrylate polymers.
{"title":"Visible Light-induced Degradation of Acrylate/Methacrylate Copolymers with Comonomer Triggers","authors":"Xuzheng Guo, Wenhua Peng, Wenjie Zhang, Chengli Wang, Xiaomeng Zhang, Zhe Cui, Peng Fu, Minying Liu, Ge Shi, Shuang Liang, Yanjie He, Xinchang Pang","doi":"10.1039/d5py01063b","DOIUrl":"https://doi.org/10.1039/d5py01063b","url":null,"abstract":"Degradation of mass-manufactured acrylate/methyl acrylate polymers is considered to be a promising path to alleviate the growing and alarming plastic waste issue. However, deconstruction of such stable polymers remains a daunting challenge due to the stable saturated backbone, with previous strategies primarily relying on harsh reaction conditions or cumbersome synthetic polymers that are not suitable for practical implementation and industrialization. Herein, we report a main chaininitiated, visible light-induced degradation methodology under mild conditions, which is applicable to various categories of acrylate or methacrylate copolymers. These acrylate or methacrylate copolymers could be readily prepared by copolymerizing diverse acrylate/methacrylate monomers with low mol % acrylic acid/methacrylic acid (AA/MAA), which could serve as degradable triggers. These triggers consisting of COOH groups could generate -COOCe Ⅳ species by coordinating with a cerium catalyst followed by oxidation in the presence of O 2 , thereby initiating the ligand-to-metal charge transfer process and decarboxylation under visible light irradiation to produce alkyl radicals to trigger degradation via backbone scission. More importantly, this efficient degradation could be accomplished regardless of the synthetic routes, pendant groups, chain-end functionalities, molecular weights, topological architectures and concentrations of polymers, rendering this strategy a robust route to degrade diverse acrylate/methacrylate polymers.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"26 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145665225","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}
Guonan Ji, Shan An, Gianluca Torres, Fergal J. O'Brien, Ziyuan Song, Bo Li, Andreas Heise
Hydrogels are widely employed in biomedical applications such as drug delivery, tissue engineering, and wound healing due to their ability to mimic the properties of biological tissues. Here, the development of novel simultaneous interpenetrating network (SIN) hydrogels composed of polysarcosine (PSar) and polyethylene glycol (PEG), crosslinked through orthogonal photochemical reactions is reported. The PSar single network was formed by free-radical polymerization of methacrylate-functionalized PSar, while the second network was generated simultaneously from cinnamic acid-modified PEG via [2+2] cycloaddition. Comprehensive characterization revealed that the SIN hydrogels exhibit enhanced mechanical performance, including higher elongation at break, ultimate tensile strength, compressive strength, fracture strain, and Young’s modulus, compared to the individual networks. Furthermore, rat mesenchymal stem cell assays confirmed superior cytocompatibility, with robust metabolic activity and proliferation on SIN hydrogels. Collectively, these findings demonstrate that PSar-based SIN hydrogels combine mechanical robustness with biocompatibility, highlighting their strong potential as functional materials for artificial tissue applications.
{"title":"Simultaneous Interpenetrating Network (SIN) Hydrogels from Poly(sarcosine) and Poly(ethylene glycol) (PEG)","authors":"Guonan Ji, Shan An, Gianluca Torres, Fergal J. O'Brien, Ziyuan Song, Bo Li, Andreas Heise","doi":"10.1039/d5py01018g","DOIUrl":"https://doi.org/10.1039/d5py01018g","url":null,"abstract":"Hydrogels are widely employed in biomedical applications such as drug delivery, tissue engineering, and wound healing due to their ability to mimic the properties of biological tissues. Here, the development of novel simultaneous interpenetrating network (SIN) hydrogels composed of polysarcosine (PSar) and polyethylene glycol (PEG), crosslinked through orthogonal photochemical reactions is reported. The PSar single network was formed by free-radical polymerization of methacrylate-functionalized PSar, while the second network was generated simultaneously from cinnamic acid-modified PEG via [2+2] cycloaddition. Comprehensive characterization revealed that the SIN hydrogels exhibit enhanced mechanical performance, including higher elongation at break, ultimate tensile strength, compressive strength, fracture strain, and Young’s modulus, compared to the individual networks. Furthermore, rat mesenchymal stem cell assays confirmed superior cytocompatibility, with robust metabolic activity and proliferation on SIN hydrogels. Collectively, these findings demonstrate that PSar-based SIN hydrogels combine mechanical robustness with biocompatibility, highlighting their strong potential as functional materials for artificial tissue applications.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145658329","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}
Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) has been extensively employed as a flexible conductive coating in diverse application fields. However, the existence of numerous weak electrostatic interactions within the PEDOT:PSS matrix presents a significant challenge to material’s stability. Herein, we demonstrate that a slight reduction in the charge density of the outer-shell polyanion can effectively inhibit the penetration of degradation-inducing molecules, preserving the structural integrity and electrostatic stability of the entire matrix. Specifically, reducing the polyanion’s charge density lowers the electrostatic repulsion encountered by oxidant ions during the oxidative polymerization process, thereby accelerating the reaction kinetics and facilitating the formation of enlarged PEDOT:polyanion matrix. The increased matrix size leads to a significant decrease in its specific surface area, thus effectively reducing the number of surface charges available for interaction with degradation-inducing agents such as 1,8-diiodooctane, chloroform, and water. Simultaneously, enhanced Coulombic trapping of polarons was observed, providing a complementary mechanism that contributes to improved overall stability. Impressively, the PEDOT film demonstrates remarkable resistance to water immersion, maintaining structural integrity for over 40 days without evidence of exfoliation, swelling, or dissolution. This study offers a meaningful reference for improving the stability of PEDOT coatings via polyanion engineering.
{"title":"Highly stable PEDOT coatings realized via a simple yet robust charge regulation strategy","authors":"Xiaojing Xu, Yuting Diao, Yanzhuo Zhu, Jingyi Xiong, Qi Guo, Xiangyu Li, Yuda Li","doi":"10.1039/d5py00750j","DOIUrl":"https://doi.org/10.1039/d5py00750j","url":null,"abstract":"Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) has been extensively employed as a flexible conductive coating in diverse application fields. However, the existence of numerous weak electrostatic interactions within the PEDOT:PSS matrix presents a significant challenge to material’s stability. Herein, we demonstrate that a slight reduction in the charge density of the outer-shell polyanion can effectively inhibit the penetration of degradation-inducing molecules, preserving the structural integrity and electrostatic stability of the entire matrix. Specifically, reducing the polyanion’s charge density lowers the electrostatic repulsion encountered by oxidant ions during the oxidative polymerization process, thereby accelerating the reaction kinetics and facilitating the formation of enlarged PEDOT:polyanion matrix. The increased matrix size leads to a significant decrease in its specific surface area, thus effectively reducing the number of surface charges available for interaction with degradation-inducing agents such as 1,8-diiodooctane, chloroform, and water. Simultaneously, enhanced Coulombic trapping of polarons was observed, providing a complementary mechanism that contributes to improved overall stability. Impressively, the PEDOT film demonstrates remarkable resistance to water immersion, maintaining structural integrity for over 40 days without evidence of exfoliation, swelling, or dissolution. This study offers a meaningful reference for improving the stability of PEDOT coatings via polyanion engineering.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"127 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145658327","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}
Muhammad Zeeshan Shah, Evelyn A Okorafor, Nancy C Rotich, Quinton Henoch, Ranjita Thapa Acharya, Richard C. Page, Gary A Lorigan, Dominik Konkolewicz
Vinyl ether-maleic anhydride (VEMAn) copolymers were chain extended with n-butyl acrylate (nBA) and tert-butyl acrylate (tBA) blocks using reversible addition-fragmentation chain transfer (RAFT) copolymerization. Subsequently, the copolymers underwent hydrolysis to synthesize vinyl ether-maleic acid (VEMA) copolymers with different tail structures. The nBA block yielded VEMA extended with an acrylic acid (AA) block after hydrolysis. The tBA block gave VEMA extended with a mixture of tBA and AA blocks. This study investigates the effect of VEMA hydrophilicity/ hydrophobicity and monomer structure in the second block on the formation and properties of self-assembled lipid nanodiscs. In particular, the size of the polymer-lipid discs and their interaction with a model membrane protein, KCNE1.The findings indicate that both AA and tBA/AA VEMA blocks yield lipid discs, however copolymers with tBA/AA blocks tend to form relatively larger lipid nanodiscs potentially due to steric differences in the copolymer tail. The change in hydrophobicity of VEMA block copolymers affects the resulting dimensions of lipid nanodiscs; similarly, the type of lipid also influences the size of lipid discs. Electron Paramagnetic Resonance (EPR) studies revealed that these block copolymers do not affect the structural dynamics of the KCNE1 protein, confirming their suitability for membrane protein studies in native-like environments. This study demonstrates the compatibility of VEMA-block copolymers with membrane protein systems by enabling control over the size of lipid discs. Furthermore, it provides insight into the self-assembly understanding of these lipid nanodiscs and their interactions with membrane proteins.
{"title":"Vinyl Ether Maleic Acid Block Copolymers: A Versatile Platform for Tunable Self-Assembled Lipid Nanodiscs and Membrane Protein Characterization","authors":"Muhammad Zeeshan Shah, Evelyn A Okorafor, Nancy C Rotich, Quinton Henoch, Ranjita Thapa Acharya, Richard C. Page, Gary A Lorigan, Dominik Konkolewicz","doi":"10.1039/d5py00767d","DOIUrl":"https://doi.org/10.1039/d5py00767d","url":null,"abstract":"Vinyl ether-maleic anhydride (VEMAn) copolymers were chain extended with n-butyl acrylate (nBA) and tert-butyl acrylate (tBA) blocks using reversible addition-fragmentation chain transfer (RAFT) copolymerization. Subsequently, the copolymers underwent hydrolysis to synthesize vinyl ether-maleic acid (VEMA) copolymers with different tail structures. The nBA block yielded VEMA extended with an acrylic acid (AA) block after hydrolysis. The tBA block gave VEMA extended with a mixture of tBA and AA blocks. This study investigates the effect of VEMA hydrophilicity/ hydrophobicity and monomer structure in the second block on the formation and properties of self-assembled lipid nanodiscs. In particular, the size of the polymer-lipid discs and their interaction with a model membrane protein, KCNE1.The findings indicate that both AA and tBA/AA VEMA blocks yield lipid discs, however copolymers with tBA/AA blocks tend to form relatively larger lipid nanodiscs potentially due to steric differences in the copolymer tail. The change in hydrophobicity of VEMA block copolymers affects the resulting dimensions of lipid nanodiscs; similarly, the type of lipid also influences the size of lipid discs. Electron Paramagnetic Resonance (EPR) studies revealed that these block copolymers do not affect the structural dynamics of the KCNE1 protein, confirming their suitability for membrane protein studies in native-like environments. This study demonstrates the compatibility of VEMA-block copolymers with membrane protein systems by enabling control over the size of lipid discs. Furthermore, it provides insight into the self-assembly understanding of these lipid nanodiscs and their interactions with membrane proteins.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"14 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145658328","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}
Saurabh S. Chitnis, Rebekka S. Klausen and Erin M. Leitao
A graphical abstract is available for this content
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{"title":"Introduction to hybrid inorganic–organic polymers","authors":"Saurabh S. Chitnis, Rebekka S. Klausen and Erin M. Leitao","doi":"10.1039/D5PY90139A","DOIUrl":"10.1039/D5PY90139A","url":null,"abstract":"<p >A graphical abstract is available for this content</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 48","pages":" 5125-5126"},"PeriodicalIF":3.9,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145612008","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}
Yuhka Uda, Eddie Wai Chi Chan, Timothy Lambden, Scott T. Keene, Xin Sun, Zoran Dusan Zujovic, David Barker, Paul Midgley, Jadranka Travas-Sejdic
Compositional modifications of conducting polymer-based graft copolymers enable precise tuning of their properties, including conductivity, degradation and opto-electrochemical properties. This work investigates how the composition of poly(caprolactone)-graft-oligo(3-hexylthiophene)s, (P(CL-co-AVL)-g-O3HT), previously shown to be degradable, effects the morphological and opto-electrochemical properties of the copolymers. Effect of different grafting density and the length of the O3HT grafts on the material's properties were investigated using a range of advanced techniques, such as, spectroelectrochemistry, cyclic voltammetry, 2D-GIXRD and 4D-STEM. Short O3HT grafts (n = 15) yielded amorphous copolymers, whereas longer grafts (n = 30, 40) produced semi-crystalline material with distinct crystalline and amorphous redox signatures. High grafting density promoted formation of interconnected nanoscale O3HT crystallites. Thermal annealing (40–60 °C) or trace acetonitrile (1 vol.%) in casting solutions enhanced intrachain order and crystallization, and, in turn, enhanced optoelectronic properties of the high-density, long grafts copolymers. These findings establish structure - property relationship in conducting polymer-based graft copolymers, guiding their macromolecular design, including for transient electronics.
{"title":"Graft Length and Density Govern Morphology and Optoelectronic Properties of Poly(caprolactone)-graft-oligo(3-hexylthiophene)s","authors":"Yuhka Uda, Eddie Wai Chi Chan, Timothy Lambden, Scott T. Keene, Xin Sun, Zoran Dusan Zujovic, David Barker, Paul Midgley, Jadranka Travas-Sejdic","doi":"10.1039/d5py00815h","DOIUrl":"https://doi.org/10.1039/d5py00815h","url":null,"abstract":"Compositional modifications of conducting polymer-based graft copolymers enable precise tuning of their properties, including conductivity, degradation and opto-electrochemical properties. This work investigates how the composition of poly(caprolactone)-graft-oligo(3-hexylthiophene)s, (P(CL-co-AVL)-g-O3HT), previously shown to be degradable, effects the morphological and opto-electrochemical properties of the copolymers. Effect of different grafting density and the length of the O3HT grafts on the material's properties were investigated using a range of advanced techniques, such as, spectroelectrochemistry, cyclic voltammetry, 2D-GIXRD and 4D-STEM. Short O3HT grafts (n = 15) yielded amorphous copolymers, whereas longer grafts (n = 30, 40) produced semi-crystalline material with distinct crystalline and amorphous redox signatures. High grafting density promoted formation of interconnected nanoscale O3HT crystallites. Thermal annealing (40–60 °C) or trace acetonitrile (1 vol.%) in casting solutions enhanced intrachain order and crystallization, and, in turn, enhanced optoelectronic properties of the high-density, long grafts copolymers. These findings establish structure - property relationship in conducting polymer-based graft copolymers, guiding their macromolecular design, including for transient electronics.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145612009","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}
Te Yang, Zhenjie Yang, Yulu Zhang, Chenyang Hu, Zhenbiao Xie, Zhiqiang Sun, Xuan Pang, Xuesi Chen
Polyethylene terephthalate (PET), a dominant polymer in global plastic production, faces critical recycling challenges due to its persistence in ecosystems and limitations of conventional mechanical/thermal recycling. Upcycling PET waste into valueadded polymers represents a transformative approach toward a circular plastics economy. This review systematically examines innovative strategies for chemically converting post-consumer PET into novel polymeric materials, thereby bypassing the performance degradation typically associated with traditional recycling. Key pathways include (1) depolymerization into monomers (terephthalic acid, ethylene glycol) for repolymerization into high-purity PET or advanced polyesters (e.g., biodegradable or bio-based variants), (2) transformation into functional polymers such as polyurethanes, epoxy resins, and ion-exchange membranes via tailored catalytic processes, and (3) copolymerization/blending with biopolymers to enhance material properties. Breakthroughs in catalysts (enzymes, ionic liquids), solvent-free systems, and energy-efficient reactors are highlighted for improving reaction selectivity and scalability. Despite progress, challenges persist in managing mixed plastic wastes, removing contaminants, and achieving cost parity with virgin polymers. Emerging trends, including enzymatic engineering and AI-guided monomer-to-polymer design, are proposed to address these barriers.By bridging molecular innovation with industrial feasibility, PET upcycling offers a dual environmental and economic incentive to close the plastic lifecycle loop.
{"title":"Upcycling of PET Waste: From One Polymer to Another Polymer","authors":"Te Yang, Zhenjie Yang, Yulu Zhang, Chenyang Hu, Zhenbiao Xie, Zhiqiang Sun, Xuan Pang, Xuesi Chen","doi":"10.1039/d5py00861a","DOIUrl":"https://doi.org/10.1039/d5py00861a","url":null,"abstract":"Polyethylene terephthalate (PET), a dominant polymer in global plastic production, faces critical recycling challenges due to its persistence in ecosystems and limitations of conventional mechanical/thermal recycling. Upcycling PET waste into valueadded polymers represents a transformative approach toward a circular plastics economy. This review systematically examines innovative strategies for chemically converting post-consumer PET into novel polymeric materials, thereby bypassing the performance degradation typically associated with traditional recycling. Key pathways include (1) depolymerization into monomers (terephthalic acid, ethylene glycol) for repolymerization into high-purity PET or advanced polyesters (e.g., biodegradable or bio-based variants), (2) transformation into functional polymers such as polyurethanes, epoxy resins, and ion-exchange membranes via tailored catalytic processes, and (3) copolymerization/blending with biopolymers to enhance material properties. Breakthroughs in catalysts (enzymes, ionic liquids), solvent-free systems, and energy-efficient reactors are highlighted for improving reaction selectivity and scalability. Despite progress, challenges persist in managing mixed plastic wastes, removing contaminants, and achieving cost parity with virgin polymers. Emerging trends, including enzymatic engineering and AI-guided monomer-to-polymer design, are proposed to address these barriers.By bridging molecular innovation with industrial feasibility, PET upcycling offers a dual environmental and economic incentive to close the plastic lifecycle loop.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"29 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145600252","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}
Simon Joyson Galbao, Sherlin Samantha Menezes, Syeda Reha Khadri, Dharmapura H. K. Murthy
Due to its metal-free polymeric nature, ease of synthesis using low-cost earth abundant precursors and tunable optoelectronic properties, graphitic carbon nitride (GCN) is extensively used for solar fuel production. Despite two decades of extensive research, the fundamental understanding of the thermal polymerization process leading to the formation of GCN is inadequately understood. In this work, we employ cyanamide (CYN) and dicyandiamide (DCDA) precursors and systematically reveal polymerization mechanism. Though CYN has half the number of C and N content than DCDA, it yielded virtually similar structural properties, degree of conjugation that determines the energetic difference between π to π* fundamental (optical) transition and photoexcited lifetimes. Detailed complementary analysis using thermal methods along with quantifying the amount of NH3 released using temperature programmed desorption technique offered unique insights into the polymerization process. Unlike previous notion, results unambiguously demonstrate that GCN formation need not always release NH3 as a result of thermal condensation reaction. Rather, it is amenable that molecular rearrangement (dimerization and/or cyclization) of the intermediate condensates would also play a major role in the formation of melamine, which is found to be an important intermediate. Obtained mechanistic insights into thermodynamics of polymerization process and its impact on optoelectronic properties and photoelectrochemical performance will aid in rational design of GCN to enhance the efficiency of solar energy conversion.
{"title":"Precursor-dependent distinctive polymerization process controls optoelectronic properties in graphitic carbon nitride photocatalyst","authors":"Simon Joyson Galbao, Sherlin Samantha Menezes, Syeda Reha Khadri, Dharmapura H. K. Murthy","doi":"10.1039/d5py01003a","DOIUrl":"https://doi.org/10.1039/d5py01003a","url":null,"abstract":"Due to its metal-free polymeric nature, ease of synthesis using low-cost earth abundant precursors and tunable optoelectronic properties, graphitic carbon nitride (GCN) is extensively used for solar fuel production. Despite two decades of extensive research, the fundamental understanding of the thermal polymerization process leading to the formation of GCN is inadequately understood. In this work, we employ cyanamide (CYN) and dicyandiamide (DCDA) precursors and systematically reveal polymerization mechanism. Though CYN has half the number of C and N content than DCDA, it yielded virtually similar structural properties, degree of conjugation that determines the energetic difference between π to π* fundamental (optical) transition and photoexcited lifetimes. Detailed complementary analysis using thermal methods along with quantifying the amount of NH<small><sub>3</sub></small> released using temperature programmed desorption technique offered unique insights into the polymerization process. Unlike previous notion, results unambiguously demonstrate that GCN formation need not always release NH<small><sub>3</sub></small> as a result of thermal condensation reaction. Rather, it is amenable that molecular rearrangement (dimerization and/or cyclization) of the intermediate condensates would also play a major role in the formation of melamine, which is found to be an important intermediate. Obtained mechanistic insights into thermodynamics of polymerization process and its impact on optoelectronic properties and photoelectrochemical performance will aid in rational design of GCN to enhance the efficiency of solar energy conversion.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145600253","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}
Timo Sehn, Mickaël Du Fraysseix, Cédric Le Coz, Emmanuel Ibarboure, Michael A. R. Meier, Audrey Llevot
Herein, we introduce the synthesis of fully renewable and extrudable high oleic sunflower oil-based acetal containing covalent adaptable networks (CANs) via a catalyst and solvent-free click-like reaction between a bio-based polyol and divinyl ether, i.e. 1,4-cyclohexanedimethanol divinyl ether. High oleic sunflower oil was therefore first converted into the respective polyol via a simple H2SO4 catalyzed Friedel-Crafts alkylation using catechol within 30 minutes at 120 °C. After subsequent structural characterization of the polyol, acetal containing CANs showing high cross-linking densities, fast stress relaxation, and excellent malleability were synthesized without releasing any small-molecule byproducts. The introduction of the catechol moiety is particularly interesting, as the presence of an adjacent phenolic group induces neighboring group participation effects and accelerates exchange reaction rates. The dynamic behavior of the new cross-linked materials was confirmed by stress relaxation measurements at different temperatures as well as by their reprocessability via compression molding and extrusion. Additionally, the materials were degraded under weak acidic conditions, and the starting biobased polyol was recovered in a yield of 72 %, thus enabling a closed-loop chemical recycling of this monomer.
{"title":"Efficient catechol functionalization of High Oleic Sunflower Oil for the preparation of fully biobased and extrudable acetal CANs","authors":"Timo Sehn, Mickaël Du Fraysseix, Cédric Le Coz, Emmanuel Ibarboure, Michael A. R. Meier, Audrey Llevot","doi":"10.1039/d5py00927h","DOIUrl":"https://doi.org/10.1039/d5py00927h","url":null,"abstract":"Herein, we introduce the synthesis of fully renewable and extrudable high oleic sunflower oil-based acetal containing covalent adaptable networks (CANs) via a catalyst and solvent-free click-like reaction between a bio-based polyol and divinyl ether, i.e. 1,4-cyclohexanedimethanol divinyl ether. High oleic sunflower oil was therefore first converted into the respective polyol via a simple H2SO4 catalyzed Friedel-Crafts alkylation using catechol within 30 minutes at 120 °C. After subsequent structural characterization of the polyol, acetal containing CANs showing high cross-linking densities, fast stress relaxation, and excellent malleability were synthesized without releasing any small-molecule byproducts. The introduction of the catechol moiety is particularly interesting, as the presence of an adjacent phenolic group induces neighboring group participation effects and accelerates exchange reaction rates. The dynamic behavior of the new cross-linked materials was confirmed by stress relaxation measurements at different temperatures as well as by their reprocessability via compression molding and extrusion. Additionally, the materials were degraded under weak acidic conditions, and the starting biobased polyol was recovered in a yield of 72 %, thus enabling a closed-loop chemical recycling of this monomer.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"29 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145600228","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}
Catherine Mollart, Ellena Sherrett, Patrick Heasman, Michael Joseph George Peach, Adam Rowling, Lewis J. Beck, Ellie Varley, David Seed, Abbie Trewin
An alternative route to synthesise TCNQ-CTF by using trifluoromethanesulfonic (TFMS) acid catalysis is presented, in comparison to a previously reported ZnCl2-catalysed synthesis. The new synthetic route yields a polymer with additional structural diversity compared to the previously reported material. The composition of the framework is rationalised by 'artificial' acid-catalysed synthesis of TCNQ-CTF, together with a novel approach to structural feature identification, with a range of alternative structural features appearing that were not present in the previously reported polymer formed by ZnCl2 catalysis. These results will inform the design of new CTF materials with additional functionality and broader applications.
{"title":"Diversity-oriented route to functional covalent triazine frameworks","authors":"Catherine Mollart, Ellena Sherrett, Patrick Heasman, Michael Joseph George Peach, Adam Rowling, Lewis J. Beck, Ellie Varley, David Seed, Abbie Trewin","doi":"10.1039/d5py00872g","DOIUrl":"https://doi.org/10.1039/d5py00872g","url":null,"abstract":"An alternative route to synthesise TCNQ-CTF by using trifluoromethanesulfonic (TFMS) acid catalysis is presented, in comparison to a previously reported ZnCl2-catalysed synthesis. The new synthetic route yields a polymer with additional structural diversity compared to the previously reported material. The composition of the framework is rationalised by 'artificial' acid-catalysed synthesis of TCNQ-CTF, together with a novel approach to structural feature identification, with a range of alternative structural features appearing that were not present in the previously reported polymer formed by ZnCl2 catalysis. These results will inform the design of new CTF materials with additional functionality and broader applications.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145583650","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}
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