Chemoenzymatic methods are essential tools for synthesising a wide range of saccharides and their derivatives, including oligosaccharides, polysaccharides, and glycoconjugates, in the fields of glycotechnology and polymer chemistry. This review summarises recent progress and provides an overview of research on chemoenzymatic synthesis of oligosaccharides and polysaccharides through the combined use of chemical and enzymatic reactions. The methodologies are discussed separately for each class of enzyme: glycosyltransferases, glycan phosphorylases, and glycosyl hydrolases.
{"title":"Recent advances in chemoenzymatic synthesis of oligosaccharides and polysaccharides","authors":"Tomonari Tanaka","doi":"10.1039/D5PY00938C","DOIUrl":"10.1039/D5PY00938C","url":null,"abstract":"<p >Chemoenzymatic methods are essential tools for synthesising a wide range of saccharides and their derivatives, including oligosaccharides, polysaccharides, and glycoconjugates, in the fields of glycotechnology and polymer chemistry. This review summarises recent progress and provides an overview of research on chemoenzymatic synthesis of oligosaccharides and polysaccharides through the combined use of chemical and enzymatic reactions. The methodologies are discussed separately for each class of enzyme: glycosyltransferases, glycan phosphorylases, and glycosyl hydrolases.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 2","pages":" 125-147"},"PeriodicalIF":3.9,"publicationDate":"2025-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145508970","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}
Ayomi Vidana Pathiranage, Mark-Jefferson Buer Boyetey, Oluwatoosin B. A. Agbaje and Nathan R. B. Boase
Polymer nanomedicines are a transformative class of therapeutics, offering tunable architectures for targeted delivery, controlled release, and improved pharmacokinetics. However, limited understanding of how these systems interact with cellular membranes, undergo internalization, and release their cargo continues to hinder their clinical translation. Membrane interactions are a key determinant of these processes yet remain underexplored in nanomedicine research. This review provides an overview of analytical techniques used to study the interaction of polymers with lipid membranes, drawing on methods from biophysics, physical chemistry, and colloid science. We introduce common model membrane systems and explain how they can complement in vitro studies. A wide range of characterization approaches are discussed, from microscopy and spectroscopy to more advanced scattering and nanomechanical techniques. By illustrating how these methods can be integrated to build a complete mechanistic understanding of dynamic interfacial behaviour, this review aims to bridge disciplinary gaps and support the development of more effective nanomedicines.
{"title":"Unravelling the mechanisms of nanomedicines: analytical tools to characterise the interaction between synthetic macromolecules and lipid membranes","authors":"Ayomi Vidana Pathiranage, Mark-Jefferson Buer Boyetey, Oluwatoosin B. A. Agbaje and Nathan R. B. Boase","doi":"10.1039/D5PY00850F","DOIUrl":"10.1039/D5PY00850F","url":null,"abstract":"<p >Polymer nanomedicines are a transformative class of therapeutics, offering tunable architectures for targeted delivery, controlled release, and improved pharmacokinetics. However, limited understanding of how these systems interact with cellular membranes, undergo internalization, and release their cargo continues to hinder their clinical translation. Membrane interactions are a key determinant of these processes yet remain underexplored in nanomedicine research. This review provides an overview of analytical techniques used to study the interaction of polymers with lipid membranes, drawing on methods from biophysics, physical chemistry, and colloid science. We introduce common model membrane systems and explain how they can complement <em>in vitro</em> studies. A wide range of characterization approaches are discussed, from microscopy and spectroscopy to more advanced scattering and nanomechanical techniques. By illustrating how these methods can be integrated to build a complete mechanistic understanding of dynamic interfacial behaviour, this review aims to bridge disciplinary gaps and support the development of more effective nanomedicines.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 3","pages":" 261-290"},"PeriodicalIF":3.9,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145509155","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}
Lenka Kotrchová , Martina Nevoralová , Michaela Hrochová , Zdeněk Starý , Tomáš Etrych , Libor Kostka
Water-soluble polymers are extensively studied materials in the field of biomedical chemistry research. This study investigates the behavior of methacrylamide-based homopolymers and copolymers with linear, two-arm, and star-like structures in aqueous solutions. The research focuses on how the polymer structure affects its solution behavior. The study uses intrinsic and shear viscosity measurements to examine the influence of these structures on solution behavior at both molecular and macroscopic levels.
{"title":"Structural dependence of the solution behavior of HPMA-based polymers","authors":"Lenka Kotrchová , Martina Nevoralová , Michaela Hrochová , Zdeněk Starý , Tomáš Etrych , Libor Kostka","doi":"10.1039/d5py01007a","DOIUrl":"10.1039/d5py01007a","url":null,"abstract":"<div><div>Water-soluble polymers are extensively studied materials in the field of biomedical chemistry research. This study investigates the behavior of methacrylamide-based homopolymers and copolymers with linear, two-arm, and star-like structures in aqueous solutions. The research focuses on how the polymer structure affects its solution behavior. The study uses intrinsic and shear viscosity measurements to examine the influence of these structures on solution behavior at both molecular and macroscopic levels.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 48","pages":"Pages 5127-5131"},"PeriodicalIF":3.9,"publicationDate":"2025-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145560540","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}
Mary Hnatyshyn , Matthew Halloran , Maxwell Laykish , Jim A. Nicell , Richard L. Leask , Milan Maric
Itaconic acid (IA) is a bio-renewable molecule with increasing industrial availability. However, IA-based polymers have been limited by low molecular weights and conversions. In this work, we report the synthesis of two novel methacrylate-functionalized IA monomers. Using various reversible-deactivation radical polymerization methods, we achieved well-defined polymers with high conversions (≥98%) and moderate reaction times (e.g., 70 minutes by atom transfer radical polymerization at 80 °C). Homopolymers of these two monomers exhibited a range of properties, with glass transition temperatures (Tg) ranging from −40 °C for heptyl-functionalized moieties to 14 °C for benzyl-functionalized moieties. Controllable reaction kinetics enabled the synthesis of pre-designed AB-type diblock copolymers, demonstrating the potential of the heptyl-functionalized moiety as a soft block in phase-separated materials. The favorable reaction kinetics of these methacrylate-functionalized IA monomers make this approach one of the most promising pathways for incorporating renewably sourced IA into polymeric materials.
{"title":"Expanding the polymerization potential of itaconic acid through methacrylate functionalization","authors":"Mary Hnatyshyn , Matthew Halloran , Maxwell Laykish , Jim A. Nicell , Richard L. Leask , Milan Maric","doi":"10.1039/d5py00911a","DOIUrl":"10.1039/d5py00911a","url":null,"abstract":"<div><div>Itaconic acid (IA) is a bio-renewable molecule with increasing industrial availability. However, IA-based polymers have been limited by low molecular weights and conversions. In this work, we report the synthesis of two novel methacrylate-functionalized IA monomers. Using various reversible-deactivation radical polymerization methods, we achieved well-defined polymers with high conversions (≥98%) and moderate reaction times (<em>e.g.</em>, 70 minutes by atom transfer radical polymerization at 80 °C). Homopolymers of these two monomers exhibited a range of properties, with glass transition temperatures (<em>T</em><sub>g</sub>) ranging from −40 °C for heptyl-functionalized moieties to 14 °C for benzyl-functionalized moieties. Controllable reaction kinetics enabled the synthesis of pre-designed AB-type diblock copolymers, demonstrating the potential of the heptyl-functionalized moiety as a soft block in phase-separated materials. The favorable reaction kinetics of these methacrylate-functionalized IA monomers make this approach one of the most promising pathways for incorporating renewably sourced IA into polymeric materials.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 48","pages":"Pages 5155-5165"},"PeriodicalIF":3.9,"publicationDate":"2025-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145499302","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}
Christine W. Barker , Bailey Eberle , Mark D. Dadmun , Brian K. Long
There is growing interest in the management of end-of-life plastic waste due to the lack of recycling of these materials into valuable products. This is due, in part, to the challenge of waste plastics collection, sorting, and limitations arising from the immiscibility of reprocessed plastic blends. Mixtures of these immiscible polymer components have poor properties due to weak interfaces, driven by phase separation. To address this, compatibilizers are often used to strengthen the interface between phases and stabilize the blend morphology. Previous research by our group has examined the ability of chlorinated polyethylene (c-PE) to compatibilize polyvinyl chloride (PVC) and polyolefin elastomers (POE). However, the specific molecular level processes that improve the interface of these amorphous–semicrystalline materials are not fully understood. To address this knowledge gap, a series of gradient c-PE copolymers were synthesized via ring-opening metathesis polymerization (ROMP) with varying ratios of dichlorinated cyclooctene and cyclooctene monomers. The ability of these polymers, with molar masses ranging from ∼25–150 kg mol−1, to strengthen the PVC/POE interface were compared to that of commercial blocky c-PEs. The results of this study elucidate the role of crystallinity and molecular sequence distribution of the compatibilizer on its efficacy as a compatibilizer. Herein, we show that the blockiest and most crystalline commercial samples exhibit the greatest improvement in interfacial adhesion whereas the synthesized gradient copolymer compatibilizers increase interfacial adhesion as a function of increasing PE-like segment block length. This indicates that while co-crystallization between semicrystalline components is important in compatibilization, entanglement between polymer phases is also necessary and may be notably impacted by the comonomer sequence distribution along the compatibilizer backbone. These studies provide insight into the molecular design and crucial molecular-level processes that drive the development of morphology and properties of compatibilized phase-separated amorphous–semicrystalline polymer blends, including those that are most relevant for mixed waste streams in polymer recycling.
{"title":"Correlating chlorinated polyethylene molecular structure to compatibilization efficiency for mixed polymer waste","authors":"Christine W. Barker , Bailey Eberle , Mark D. Dadmun , Brian K. Long","doi":"10.1039/d5py00719d","DOIUrl":"10.1039/d5py00719d","url":null,"abstract":"<div><div>There is growing interest in the management of end-of-life plastic waste due to the lack of recycling of these materials into valuable products. This is due, in part, to the challenge of waste plastics collection, sorting, and limitations arising from the immiscibility of reprocessed plastic blends. Mixtures of these immiscible polymer components have poor properties due to weak interfaces, driven by phase separation. To address this, compatibilizers are often used to strengthen the interface between phases and stabilize the blend morphology. Previous research by our group has examined the ability of chlorinated polyethylene (c-PE) to compatibilize polyvinyl chloride (PVC) and polyolefin elastomers (POE). However, the specific molecular level processes that improve the interface of these amorphous–semicrystalline materials are not fully understood. To address this knowledge gap, a series of gradient c-PE copolymers were synthesized <em>via</em> ring-opening metathesis polymerization (ROMP) with varying ratios of dichlorinated cyclooctene and cyclooctene monomers. The ability of these polymers, with molar masses ranging from ∼25–150 kg mol<sup>−1</sup>, to strengthen the PVC/POE interface were compared to that of commercial blocky c-PEs. The results of this study elucidate the role of crystallinity and molecular sequence distribution of the compatibilizer on its efficacy as a compatibilizer. Herein, we show that the blockiest and most crystalline commercial samples exhibit the greatest improvement in interfacial adhesion whereas the synthesized gradient copolymer compatibilizers increase interfacial adhesion as a function of increasing PE-like segment block length. This indicates that while co-crystallization between semicrystalline components is important in compatibilization, entanglement between polymer phases is also necessary and may be notably impacted by the comonomer sequence distribution along the compatibilizer backbone. These studies provide insight into the molecular design and crucial molecular-level processes that drive the development of morphology and properties of compatibilized phase-separated amorphous–semicrystalline polymer blends, including those that are most relevant for mixed waste streams in polymer recycling.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 48","pages":"Pages 5143-5154"},"PeriodicalIF":3.9,"publicationDate":"2025-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145508968","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}
Xiang Wu , Xin-Hui Wang , Chen-Xi Chen , Yu-Jiao Chen , Song-Wei Yang , Hai Nan , Xiao-Li Sun , Li-Ren Xiao , Wen-Ming Wan
Thermoplastics are an important class of polymer materials and dominantly used in industries because of their versatility, remoldability, cost performance, etc.; however, they are mainly used as matrices and lack functionalities, e.g., luminescence. Herein, a ketyl-mediated polymerization-induced emission (KMPIE) strategy is demonstrated to achieve emission-tunable aggregation-induced emission (AIE) thermoplastics, including a general thermoplastic (polystyrene as an example) and a degradable thermoplastic (polycaprolactone as an example). Through KMPIE of styrene and caprolactone in the presence of different enone initiators, polystyrene and polycaprolactone with different end groups were prepared with emission-tunable AIE properties from blue to green. Investigations revealed that a single-fluorophore end group can trigger different nontraditional intrinsic luminescence (NTIL) in AIE polystyrene and polycaprolactone with quantum yields of up to >20%. Investigations into further applications in explosive detection at ppm levels in solution and ng levels on test paper and in enhancement of luminescence in films were carried out. Chemical degradation of the prepared thermoplastics was investigated as well. This work therefore expands the functionality library of general and degradable thermoplastics with AIE-type NTIL properties and may inspire developments in luminescent materials, polymer chemistry, NTIL, AIE and PIE.
{"title":"Emission-tunable aggregation-induced emission thermoplastics via ketyl-mediated polymerization-induced emission","authors":"Xiang Wu , Xin-Hui Wang , Chen-Xi Chen , Yu-Jiao Chen , Song-Wei Yang , Hai Nan , Xiao-Li Sun , Li-Ren Xiao , Wen-Ming Wan","doi":"10.1039/d5py00814j","DOIUrl":"10.1039/d5py00814j","url":null,"abstract":"<div><div>Thermoplastics are an important class of polymer materials and dominantly used in industries because of their versatility, remoldability, cost performance, <em>etc.</em>; however, they are mainly used as matrices and lack functionalities, <em>e.g.</em>, luminescence. Herein, a ketyl-mediated polymerization-induced emission (KMPIE) strategy is demonstrated to achieve emission-tunable aggregation-induced emission (AIE) thermoplastics, including a general thermoplastic (polystyrene as an example) and a degradable thermoplastic (polycaprolactone as an example). Through KMPIE of styrene and caprolactone in the presence of different enone initiators, polystyrene and polycaprolactone with different end groups were prepared with emission-tunable AIE properties from blue to green. Investigations revealed that a single-fluorophore end group can trigger different nontraditional intrinsic luminescence (NTIL) in AIE polystyrene and polycaprolactone with quantum yields of up to >20%. Investigations into further applications in explosive detection at ppm levels in solution and ng levels on test paper and in enhancement of luminescence in films were carried out. Chemical degradation of the prepared thermoplastics was investigated as well. This work therefore expands the functionality library of general and degradable thermoplastics with AIE-type NTIL properties and may inspire developments in luminescent materials, polymer chemistry, NTIL, AIE and PIE.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 48","pages":"Pages 5182-5191"},"PeriodicalIF":3.9,"publicationDate":"2025-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145536196","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}
Zehui Wei , Shuangxian Yan , Jilei Yin , Yu Cheng , Shuxian Ge , Yukai He , Weiling Wang , Mei Tian
Docosahexaenoic acid (DHA), widely found in marine organisms, is subject to continuously growing demand in the fields of pharmaceuticals, infant nutrition, and biomaterials. However, due to the low content of DHA in biological samples and the complexity of the matrices, a complicated extraction process is required to obtain a high-purity product. In this experiment, an imprinted polymer microsphere with specific selectivity for DHA was successfully synthesized using a rare earth metal ion-mediated strategy with europium(iii) acetate hydrate (Eu(CH3COO)3·4H2O) as the mediator, DHA as the template molecule, and methacrylic acid (MAA) as the functional monomer. The imprinted polymer microsphere was used for the enrichment and purification of DHA from Antarctic krill meal (AKM). Through systematic optimization of key synthesis parameters, including mediating ion species and concentration, functional monomer content, etc., the adsorption capacity of the developed molecular-imprinted polymers (MIPs) has been enhanced to 0.054 g g−1, with an imprinting factor reaching 4.203. Physical characterization methods, such as scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy, were used to confirm the successful preparation of the porous imprinted microspheres. The solid phase extraction of AKM under the optimal adsorption conditions yielded DHA with 62.18% purity, while the total purity of DHA + EPA could reach 95.98%, which was a 2.4-fold increase in purity, and the recoveries of MIPs ranged from 86.58% to 93.35% (RSD = 3.19%). The linear range of the method was 58.77–100 000 μg mL−1, the limit of detection was 19.40 μg mL−1, and the limit of quantification was 58.77 μg mL−1. In summary, the imprinted microspheres prepared in this experiment demonstrate the selective enrichment and purification of DHA from AKM, offering a novel extraction method for isolating DHA.
{"title":"Preparation and performance evaluation of rare earth metal Eu(iii)-mediated docosahexaenoic acid-imprinted microspheres","authors":"Zehui Wei , Shuangxian Yan , Jilei Yin , Yu Cheng , Shuxian Ge , Yukai He , Weiling Wang , Mei Tian","doi":"10.1039/d5py00738k","DOIUrl":"10.1039/d5py00738k","url":null,"abstract":"<div><div>Docosahexaenoic acid (DHA), widely found in marine organisms, is subject to continuously growing demand in the fields of pharmaceuticals, infant nutrition, and biomaterials. However, due to the low content of DHA in biological samples and the complexity of the matrices, a complicated extraction process is required to obtain a high-purity product. In this experiment, an imprinted polymer microsphere with specific selectivity for DHA was successfully synthesized using a rare earth metal ion-mediated strategy with europium(<span>iii</span>) acetate hydrate (Eu(CH<sub>3</sub>COO)<sub>3</sub>·4H<sub>2</sub>O) as the mediator, DHA as the template molecule, and methacrylic acid (MAA) as the functional monomer. The imprinted polymer microsphere was used for the enrichment and purification of DHA from Antarctic krill meal (AKM). Through systematic optimization of key synthesis parameters, including mediating ion species and concentration, functional monomer content, <em>etc.</em>, the adsorption capacity of the developed molecular-imprinted polymers (MIPs) has been enhanced to 0.054 g g<sup>−1</sup>, with an imprinting factor reaching 4.203. Physical characterization methods, such as scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy, were used to confirm the successful preparation of the porous imprinted microspheres. The solid phase extraction of AKM under the optimal adsorption conditions yielded DHA with 62.18% purity, while the total purity of DHA + EPA could reach 95.98%, which was a 2.4-fold increase in purity, and the recoveries of MIPs ranged from 86.58% to 93.35% (RSD = 3.19%). The linear range of the method was 58.77–100 000 μg mL<sup>−1</sup>, the limit of detection was 19.40 μg mL<sup>−1</sup>, and the limit of quantification was 58.77 μg mL<sup>−1</sup>. In summary, the imprinted microspheres prepared in this experiment demonstrate the selective enrichment and purification of DHA from AKM, offering a novel extraction method for isolating DHA.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 48","pages":"Pages 5132-5142"},"PeriodicalIF":3.9,"publicationDate":"2025-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145583655","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}
Lang Shuai , Guangwei Xu , Jianglong Li , Jianlong Wen , Boyu Ding , Shui Yu , Yingying Xu , Yijing Nie
To address environmental challenges and advance sustainable development, it has become imperative to develop engineering glassy polymers with autonomous and room-temperature self-healing capability. Although several strategies for achieving self-healing in glassy polymers have been reported, the underlying mechanism dominating the self-healing process below glass transition temperature (Tg) remains elusive. Herein, we synthesized hyperbranched polyurethanes (HPUs) to leverage their abundant hydroxyl end groups for constructing a dense hydrogen-bonding network. The HPUs exhibit a good self-healing ability below Tg (the self-healing efficiency can reach ∼50% and ∼90% after 0.5 h and 48 h of self-healing, respectively). Both experimental and simulation results revealed that a large number of end groups and branching units in the HPUs undergo secondary relaxation and can move locally at temperatures below Tg, which is beneficial for sub-Tg self-healing. In addition, the HPUs containing lower hydrogen bond contents exhibit stronger sub-segment mobility and higher self-healing efficiency, indicating that the mobility of sub-segmental units plays a more important role in promoting the self-healing of glassy hyperbranched polymers rather than the recombination of hydrogen bond content.
{"title":"Sub-Tg self-healing in glassy hyperbranched polyurethanes governed by mobile peripheral sub-segment units","authors":"Lang Shuai , Guangwei Xu , Jianglong Li , Jianlong Wen , Boyu Ding , Shui Yu , Yingying Xu , Yijing Nie","doi":"10.1039/d5py00821b","DOIUrl":"10.1039/d5py00821b","url":null,"abstract":"<div><div>To address environmental challenges and advance sustainable development, it has become imperative to develop engineering glassy polymers with autonomous and room-temperature self-healing capability. Although several strategies for achieving self-healing in glassy polymers have been reported, the underlying mechanism dominating the self-healing process below glass transition temperature (<em>T</em><sub>g</sub>) remains elusive. Herein, we synthesized hyperbranched polyurethanes (HPUs) to leverage their abundant hydroxyl end groups for constructing a dense hydrogen-bonding network. The HPUs exhibit a good self-healing ability below <em>T</em><sub>g</sub> (the self-healing efficiency can reach ∼50% and ∼90% after 0.5 h and 48 h of self-healing, respectively). Both experimental and simulation results revealed that a large number of end groups and branching units in the HPUs undergo secondary relaxation and can move locally at temperatures below <em>T</em><sub>g</sub>, which is beneficial for sub-<em>T</em><sub>g</sub> self-healing. In addition, the HPUs containing lower hydrogen bond contents exhibit stronger sub-segment mobility and higher self-healing efficiency, indicating that the mobility of sub-segmental units plays a more important role in promoting the self-healing of glassy hyperbranched polymers rather than the recombination of hydrogen bond content.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 48","pages":"Pages 5166-5181"},"PeriodicalIF":3.9,"publicationDate":"2025-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145478491","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}
We report the synthesis of sterically unhindered boron-doped π-conjugated polymers via polymerization of organo-dilithium reagents with boron trichloride. The resulting polymer exhibits Lewis acidity and catalyzes the transesterification of methyl benzoate. This performance is attributed to the electron-accepting ability, and thermally labile Lewis acid–base interactions, facilitating catalytic turnover.
{"title":"Synthesis of sterically unhindered Lewis acidic boron-doped π-conjugated polymers","authors":"Naoki Takahashi , Yuta Nishina","doi":"10.1039/d5py00783f","DOIUrl":"10.1039/d5py00783f","url":null,"abstract":"<div><div>We report the synthesis of sterically unhindered boron-doped π-conjugated polymers <em>via</em> polymerization of organo-dilithium reagents with boron trichloride. The resulting polymer exhibits Lewis acidity and catalyzes the transesterification of methyl benzoate. This performance is attributed to the electron-accepting ability, and thermally labile Lewis acid–base interactions, facilitating catalytic turnover.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 47","pages":"Pages 5035-5039"},"PeriodicalIF":3.9,"publicationDate":"2025-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145531745","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}
The kinetics of ureate anion-catalyzed ring-opening polymerization (ROP) of 3,6-diethyltetrahydro-2H-pyran-2-one () and 3-ethyl-6-vinyltetrahydro-2H-pyran-2-one (), CO2-derived lactones, is reported. Polymerization rates were significantly enhanced by matching the pKa of a particular urea and the pKa-H of the base, with stronger bases and more weakly acidic ureas leading to universally fast catalysis—reducing reaction times from earlier-reported days to minutes/seconds. In parallel, 2-ethylheptanoic acid (), a byproduct from monomer synthesis, was discovered to completely suppress polymerization, even in trace amounts. This highlights the need for rigorous purification protocols to ensure high monomer purity. These results demonstrate the dual importance of chemical purity and rational catalyst design for achieving rapid ROP of CO2-derived and offer a framework for advancing sustainable polymer synthesis.
{"title":"Ureate anion-catalyzed ring-opening polymerization (ROP) of CO2-derived lactones: rapid catalysis through pKa matching","authors":"Madhur M. Bhatt , Arron C. Deacy , Ian A. Tonks","doi":"10.1039/d5py00950b","DOIUrl":"10.1039/d5py00950b","url":null,"abstract":"<div><div>The kinetics of ureate anion-catalyzed ring-opening polymerization (ROP) of 3,6-diethyltetrahydro-2<em>H</em>-pyran-2-one () and 3-ethyl-6-vinyltetrahydro-2<em>H</em>-pyran-2-one (), CO<sub>2</sub>-derived lactones, is reported. Polymerization rates were significantly enhanced by matching the p<em>K</em><sub>a</sub> of a particular urea and the p<em>K</em><sub>a-H</sub> of the base, with stronger bases and more weakly acidic ureas leading to universally fast catalysis—reducing reaction times from earlier-reported days to minutes/seconds. In parallel, 2-ethylheptanoic acid (), a byproduct from monomer synthesis, was discovered to completely suppress polymerization, even in trace amounts. This highlights the need for rigorous purification protocols to ensure high monomer purity. These results demonstrate the dual importance of chemical purity and rational catalyst design for achieving rapid ROP of CO<sub>2</sub>-derived and offer a framework for advancing sustainable polymer synthesis.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 47","pages":"Pages 5064-5069"},"PeriodicalIF":3.9,"publicationDate":"2025-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145448193","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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