Pub Date : 2025-08-14DOI: 10.1038/s41428-025-01089-7
Yuta Akagi, Kazushi Fujimoto, Yusuke Yasuda
Crosslinked rubbers and gels derive their softness and toughness from a three-dimensional network of junction points connected by polymer strands. Classical affine and phantom network models qualitatively relate the network architecture to the shear modulus but fail to predict absolute values owing to elastically ineffective defects such as loops and dangling chains. In the present study, we employed coarse-grained molecular dynamics simulations combined with an iterative defect-removal algorithm to compare four model networks formed under various cross-linking protocols and binding ratios: three-/four-armed star polymer networks (SPNs) and three-/four-armed telechelic polymer networks (TPNs). We directly counted elastically effective junctions and eliminated primitive and even higher-order defects. The SPNs exhibited higher shear moduli than the TPNs did, which was a consequence of more rapid generation and greater density of effective junctions as well as suppressed loop formation. Remarkably, in both network types, the simulated modulus G obeyed: $$Gapprox {2G}_{{{{rm{ph}}}}},$$ where Gph represents the prediction by the phantom network model using the actual effective junction, which is independent of the cross-linking protocols, binding ratio, or functionality. In this study, we used coarse-grained molecular dynamics simulations with iterative defect removal algorithm to investigate structure-properties relationship of star polymer networks (SPNs) and telechelic polymer networks (TPNs). SPNs possess a mechanism that eliminates loop defects during network formation, resulting in a greater number of elastically effective junctions than in TPNs. Despite the differences in cross-linking mechanisms, both network types exhibit shear moduli approximately twice the value predicted by the phantom network model using the effective closed cycle density, independently on the number of branches or the binding ratios.
{"title":"Coarse-grained molecular dynamics simulations and structural analysis of end-linked polymer networks under different cross-linking protocols","authors":"Yuta Akagi, Kazushi Fujimoto, Yusuke Yasuda","doi":"10.1038/s41428-025-01089-7","DOIUrl":"10.1038/s41428-025-01089-7","url":null,"abstract":"Crosslinked rubbers and gels derive their softness and toughness from a three-dimensional network of junction points connected by polymer strands. Classical affine and phantom network models qualitatively relate the network architecture to the shear modulus but fail to predict absolute values owing to elastically ineffective defects such as loops and dangling chains. In the present study, we employed coarse-grained molecular dynamics simulations combined with an iterative defect-removal algorithm to compare four model networks formed under various cross-linking protocols and binding ratios: three-/four-armed star polymer networks (SPNs) and three-/four-armed telechelic polymer networks (TPNs). We directly counted elastically effective junctions and eliminated primitive and even higher-order defects. The SPNs exhibited higher shear moduli than the TPNs did, which was a consequence of more rapid generation and greater density of effective junctions as well as suppressed loop formation. Remarkably, in both network types, the simulated modulus G obeyed: $$Gapprox {2G}_{{{{rm{ph}}}}},$$ where Gph represents the prediction by the phantom network model using the actual effective junction, which is independent of the cross-linking protocols, binding ratio, or functionality. In this study, we used coarse-grained molecular dynamics simulations with iterative defect removal algorithm to investigate structure-properties relationship of star polymer networks (SPNs) and telechelic polymer networks (TPNs). SPNs possess a mechanism that eliminates loop defects during network formation, resulting in a greater number of elastically effective junctions than in TPNs. Despite the differences in cross-linking mechanisms, both network types exhibit shear moduli approximately twice the value predicted by the phantom network model using the effective closed cycle density, independently on the number of branches or the binding ratios.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 11","pages":"1183-1194"},"PeriodicalIF":2.7,"publicationDate":"2025-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01089-7.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145436554","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The structural integrity of microparticle-based films is maintained through interpenetration of the superficial polymer chains of the microparticles that physically crosslink neighboring microparticles. This structural feature is fundamentally different from those of conventional polymers prepared by solvent casting or bulk polymerization. To understand the mechanical properties of such microparticle-based films, it is necessary to investigate the behavior of their constituent particles. However, methods are still being developed to evaluate microscale structural changes in microparticle-based films during the stretching process leading to film fracture. In this study, we propose a method that combines a stretching stage with optical microscopy to investigate the changes in particle morphology and its positional relationship with surrounding particles during uniaxial tensile tests on microparticle-based films. In a film consisting of cross-linked poly(methyl acrylate) microparticles, the deformation of the particles deviated from affine deformation due to the cross-linked structure. However, the deformation of a group of several (local) particles was confirmed to be location-dependent and larger than that of each particle forming the film. The method established here can be used to contribute to the design of tough microparticle-based films. Optical microscopy combined with a stretching stage allows the comparison of stress‒strain curves and real-time visualization of microscale structural changes in a microparticle-based polymer film under tensile testing. In films composed of inter-crosslinked microparticles, particle deformation deviated from affine behavior due to limited deformability. Local clusters of microparticles exhibited more location-dependent deformation, suggesting that the separation of neighboring particles contribute to film fracture.
{"title":"The stress‒strain behavior of poly(methyl acrylate) microparticle-based polymers determined via optical microscopy","authors":"Yuichiro Nishizawa, Yuto Kawamura, Yuma Sasaki, Daisuke Suzuki","doi":"10.1038/s41428-025-01076-y","DOIUrl":"10.1038/s41428-025-01076-y","url":null,"abstract":"The structural integrity of microparticle-based films is maintained through interpenetration of the superficial polymer chains of the microparticles that physically crosslink neighboring microparticles. This structural feature is fundamentally different from those of conventional polymers prepared by solvent casting or bulk polymerization. To understand the mechanical properties of such microparticle-based films, it is necessary to investigate the behavior of their constituent particles. However, methods are still being developed to evaluate microscale structural changes in microparticle-based films during the stretching process leading to film fracture. In this study, we propose a method that combines a stretching stage with optical microscopy to investigate the changes in particle morphology and its positional relationship with surrounding particles during uniaxial tensile tests on microparticle-based films. In a film consisting of cross-linked poly(methyl acrylate) microparticles, the deformation of the particles deviated from affine deformation due to the cross-linked structure. However, the deformation of a group of several (local) particles was confirmed to be location-dependent and larger than that of each particle forming the film. The method established here can be used to contribute to the design of tough microparticle-based films. Optical microscopy combined with a stretching stage allows the comparison of stress‒strain curves and real-time visualization of microscale structural changes in a microparticle-based polymer film under tensile testing. In films composed of inter-crosslinked microparticles, particle deformation deviated from affine behavior due to limited deformability. Local clusters of microparticles exhibited more location-dependent deformation, suggesting that the separation of neighboring particles contribute to film fracture.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 11","pages":"1207-1214"},"PeriodicalIF":2.7,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01076-y.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145436555","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Molecular doping has emerged as a powerful strategy to tune the charge transport and mechanical properties of polymer semiconductors. However, the lack of structural diversity among dopants often limits the potential to improve both mobility and stretchability. Herein, we report a rationally designed Lewis acid dopant, i.e., branched octyloxy borane (BOB), which incorporates π-conjugated segments and branched alkoxy side chains to modulate polymer aggregation and crystallinity. When applied to a brittle diketopyrrolopyrrole-based polymer, BOB induces moderate p-type doping while suppressing long-range crystallinity in the solid state. At 1 wt% doping, the films show a 5-fold increase in crack onset strain (from 20 to 100%) and maintain a high mobility of 1.02 cm2 V–1 s–1. The films retain more than 30% of their initial mobility at 100% strain and show excellent stability under repeated mechanical deformation. These findings provide insights into dopant‒polymer interactions and offer molecular design principles for dopants aimed at increasing the stretchability of polymer semiconductors. A π-conjugated Lewis acid dopant, branched octyloxy borane (BOB), was designed to modulate the solid-state microstructure of DPP-based polymers. BOB suppresses long-range crystallinity and promotes short-range aggregation via non-covalent interactions. At 1 wt%, it improves the crack onset strain from 20 to 100%, while retaining high carrier mobility over 1.0 cm2 V–1 s–1. This strategy enables simultaneous enhancement of mechanical and electronic performance through dopant-induced morphology tuning.
{"title":"Tailoring aggregation behavior and crystalline structure of stretchable polymer semiconductors via a novel Lewis acid dopant","authors":"Tzu-Ming Hung, Chung-Chieh Kang, Ta-Chung Lu, Chien-Chung Shih","doi":"10.1038/s41428-025-01080-2","DOIUrl":"10.1038/s41428-025-01080-2","url":null,"abstract":"Molecular doping has emerged as a powerful strategy to tune the charge transport and mechanical properties of polymer semiconductors. However, the lack of structural diversity among dopants often limits the potential to improve both mobility and stretchability. Herein, we report a rationally designed Lewis acid dopant, i.e., branched octyloxy borane (BOB), which incorporates π-conjugated segments and branched alkoxy side chains to modulate polymer aggregation and crystallinity. When applied to a brittle diketopyrrolopyrrole-based polymer, BOB induces moderate p-type doping while suppressing long-range crystallinity in the solid state. At 1 wt% doping, the films show a 5-fold increase in crack onset strain (from 20 to 100%) and maintain a high mobility of 1.02 cm2 V–1 s–1. The films retain more than 30% of their initial mobility at 100% strain and show excellent stability under repeated mechanical deformation. These findings provide insights into dopant‒polymer interactions and offer molecular design principles for dopants aimed at increasing the stretchability of polymer semiconductors. A π-conjugated Lewis acid dopant, branched octyloxy borane (BOB), was designed to modulate the solid-state microstructure of DPP-based polymers. BOB suppresses long-range crystallinity and promotes short-range aggregation via non-covalent interactions. At 1 wt%, it improves the crack onset strain from 20 to 100%, while retaining high carrier mobility over 1.0 cm2 V–1 s–1. This strategy enables simultaneous enhancement of mechanical and electronic performance through dopant-induced morphology tuning.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 11","pages":"1227-1237"},"PeriodicalIF":2.7,"publicationDate":"2025-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01080-2.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145436559","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Coated slow-release fertilizers have good slow-release effects, can be effectively utilized, and are important new types of fertilizers. Compared with single-layer coatings, double-layer coatings have more durable slow-release effects. A double-layer-coated slow-release fertilizer (DCSRF) was prepared with urea as the core, citric acid-modified starch and polyvinyl alcohol as the inner coating, and sodium alginate as the outer coating. Compared with the single-layer coated fertilizer (SCSRF), the DCSRF demonstrated superior slow-release effects, releasing 69.2% of the nutrients within 38 days in water. Additionally, adding 2% DCSRF to soil increased its maximum water-holding capacity by 8%. Pot trials revealed that the DCSRF considerably improved target crop growth, including tiller number, plant height, root depth, and leaf width, outperforming the other methods. The DCSRF, which is made from eco-friendly, low-cost, and widely available materials, exhibits excellent water-retention and slow-release properties, offering a promising theoretical foundation for the development of new fertilizers. A double-layer-coated slow-release fertilizer (DCSRF) was prepared with urea as the core, citric acid-modified starch and polyvinyl alcohol as the inner coating, and sodium alginate as the outer coating. Compared with the single-layer coated fertilizer (SCSRF), the DCSRF demonstrated superior slow-release effects, releasing 69.2% of the nutrients within 38 days in water. Additionally, adding 2% DCSRF to soil increased its maximum water-holding capacity by 8%. Pot trials revealed that the DCSRF considerably improved target crop growth, including tiller number, plant height, root depth, and leaf width, outperforming the other methods.
{"title":"Preparation of a citric acid-modified starch/sodium alginate double-layer-coated slow-release fertilizer and its slow-release performance","authors":"Hui Li, Haotan Yan, Xunhua Liao, Shuai Zhang, Jiaqi Luo, Zijian Xue, Shiyu Wang, Wen Li, Zhenbin Chen, Qiaoli Lin, Hong Liu","doi":"10.1038/s41428-025-01082-0","DOIUrl":"10.1038/s41428-025-01082-0","url":null,"abstract":"Coated slow-release fertilizers have good slow-release effects, can be effectively utilized, and are important new types of fertilizers. Compared with single-layer coatings, double-layer coatings have more durable slow-release effects. A double-layer-coated slow-release fertilizer (DCSRF) was prepared with urea as the core, citric acid-modified starch and polyvinyl alcohol as the inner coating, and sodium alginate as the outer coating. Compared with the single-layer coated fertilizer (SCSRF), the DCSRF demonstrated superior slow-release effects, releasing 69.2% of the nutrients within 38 days in water. Additionally, adding 2% DCSRF to soil increased its maximum water-holding capacity by 8%. Pot trials revealed that the DCSRF considerably improved target crop growth, including tiller number, plant height, root depth, and leaf width, outperforming the other methods. The DCSRF, which is made from eco-friendly, low-cost, and widely available materials, exhibits excellent water-retention and slow-release properties, offering a promising theoretical foundation for the development of new fertilizers. A double-layer-coated slow-release fertilizer (DCSRF) was prepared with urea as the core, citric acid-modified starch and polyvinyl alcohol as the inner coating, and sodium alginate as the outer coating. Compared with the single-layer coated fertilizer (SCSRF), the DCSRF demonstrated superior slow-release effects, releasing 69.2% of the nutrients within 38 days in water. Additionally, adding 2% DCSRF to soil increased its maximum water-holding capacity by 8%. Pot trials revealed that the DCSRF considerably improved target crop growth, including tiller number, plant height, root depth, and leaf width, outperforming the other methods.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 12","pages":"1399-1408"},"PeriodicalIF":2.7,"publicationDate":"2025-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145666281","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-08-04DOI: 10.1038/s41428-025-01081-1
Tatsuki Abe, Chihiro Ikeda, Keiji Tanaka
Engineering plastics have received increasing attention because of their excellent mechanical strength, thermal stability, and chemical resistance. In this study, poly(ether ether ketone) (PEEK), a representative super engineering plastic, was investigated to evaluate the effects of the crystallization pathway and temperature on its aggregation structure. Although the crystalline structure of PEEK has been widely studied, limited discussion exists regarding how different crystallization pathways, specifically cold crystallization from the glassy state versus melt crystallization, affect structural development. Here, we examined the influence of both the crystallization pathway and the crystallization temperature on the degree of crystallinity and crystallographic lattice distortion. Under the experimental conditions employed in this study, regardless of the crystallization pathway, the degree of crystallinity increased with increasing crystallization temperature, whereas the degree of lattice distortion decreased monotonically. These results indicate that the aggregation structure of PEEK is governed by the crystallization temperature rather than by whether crystallization occurs from the glassy or molten state. This study highlights the critical role of thermal molecular motion during crystallization in determining the final structure. These insights provide a foundation for the more rational processing and design of high-performance thermoplastic components based on semicrystalline engineering plastics such as PEEK. Poly(ether ether ketone) (PEEK), a high-performance engineering plastic, was investigated to evaluate how its aggregation structure is influenced by crystallization pathway, cold crystallization and melt crystallization, and temperature affect. The degree of crystallinity increased with increasing crystallization temperature, while crystallographic lattice distortion decreased, regardless of the crystallization pathway. These results indicate that crystallization temperature plays a more dominant role than the pathway in determining the structure. The findings highlight the importance of thermal molecular motion during crystallization and provide valuable insights for optimizing the processing and design of semicrystalline engineering plastics.
{"title":"Crystallization temperature as a dominant factor governing the aggregation structure and mechanical properties of poly(ether ether ketone)","authors":"Tatsuki Abe, Chihiro Ikeda, Keiji Tanaka","doi":"10.1038/s41428-025-01081-1","DOIUrl":"10.1038/s41428-025-01081-1","url":null,"abstract":"Engineering plastics have received increasing attention because of their excellent mechanical strength, thermal stability, and chemical resistance. In this study, poly(ether ether ketone) (PEEK), a representative super engineering plastic, was investigated to evaluate the effects of the crystallization pathway and temperature on its aggregation structure. Although the crystalline structure of PEEK has been widely studied, limited discussion exists regarding how different crystallization pathways, specifically cold crystallization from the glassy state versus melt crystallization, affect structural development. Here, we examined the influence of both the crystallization pathway and the crystallization temperature on the degree of crystallinity and crystallographic lattice distortion. Under the experimental conditions employed in this study, regardless of the crystallization pathway, the degree of crystallinity increased with increasing crystallization temperature, whereas the degree of lattice distortion decreased monotonically. These results indicate that the aggregation structure of PEEK is governed by the crystallization temperature rather than by whether crystallization occurs from the glassy or molten state. This study highlights the critical role of thermal molecular motion during crystallization in determining the final structure. These insights provide a foundation for the more rational processing and design of high-performance thermoplastic components based on semicrystalline engineering plastics such as PEEK. Poly(ether ether ketone) (PEEK), a high-performance engineering plastic, was investigated to evaluate how its aggregation structure is influenced by crystallization pathway, cold crystallization and melt crystallization, and temperature affect. The degree of crystallinity increased with increasing crystallization temperature, while crystallographic lattice distortion decreased, regardless of the crystallization pathway. These results indicate that crystallization temperature plays a more dominant role than the pathway in determining the structure. The findings highlight the importance of thermal molecular motion during crystallization and provide valuable insights for optimizing the processing and design of semicrystalline engineering plastics.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 11","pages":"1177-1182"},"PeriodicalIF":2.7,"publicationDate":"2025-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01081-1.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145436553","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-08-04DOI: 10.1038/s41428-025-01086-w
Michelle Gross, Autumn M. Mineo, Reika Katsumata
Existing recycling approaches for vinyl-derived polymers, which constitute approximately 50% of global plastic production, rely heavily on energy-intensive incineration and pyrolysis, whereas laboratory-scale chemical recycling is material specific. To enable more universal chemical recyclability in vinyl polymers, ring-opening copolymerization with the cyclic comonomer 3,7-bis(methylene)-1,5-dithiacyclooctane (BMDTO) is an emerging solution that involves the integration of cleavable C–S bonds in the backbone. However, bulk free radical polymerization (FRP) with BMDTO limits the molar mass because of undesired radical transfer, prohibiting access to the desired mechanical properties. In this study, we employ emulsion polymerization to synthesize PS-BMDTO (PSB) copolymers with 1–7 mol% BMDTO. Compared with bulk FRP, size exclusion chromatography reveals that emulsion polymerization yields a greater molar mass (81 kg mol−1 vs. 17 kg mol−1) at 2.4 mol% BMDTO. The incorporation of BMDTO is observed by 1H nuclear magnetic resonance spectroscopy and further confirmed by a chain scission reaction with allyl dithiol. The molar mass of 3.9 mol% PSB decreases from 33 kg mol−1 to 10 kg mol−1, while the molar mass of PS without BMDTO remains unchanged. These results reveal that emulsion polymerization effectively prevents undesired radical transfer and extends radical lifetime, offering a suitable synthesis route for high-performance, recyclable vinyl copolymers. Ring-opening copolymerization using the cyclic comonomer 3,7-bis(methylene)-1,5-dithiacyclooctane (BMDTO) introduces cleavable C–S bonds for chemical recyclability; however, it suffers from low molar mass via bulk free radical polymerization due to undesired radical transfer. To this end, this study leverages emulsion polymerization to produce polystyrene-BMDTO copolymers (1–7 mol% BMDTO), achieving higher molar mass (81 vs. 17 kg/mol) at 2.4 mol% BMDTO. Nuclear magnetic resonance spectroscopy and size exclusion chromatography confirm the incorporation and cleavability of BMDTO, establishing emulsion polymerization as a viable method for producing recyclable, high-performance vinyl copolymers.
乙烯基衍生聚合物占全球塑料产量的50%左右，现有的回收方法严重依赖于能源密集型的焚烧和热解，而实验室规模的化学回收则是针对特定材料的。为了使乙烯基聚合物具有更普遍的化学可回收性，与环共聚单体3,7-双（亚甲基）-1,5-二硫代环辛烷（BMDTO）开环共聚是一种新兴的解决方案，该解决方案涉及在主链中整合可切割的C-S键。然而，体自由基聚合（FRP）与BMDTO限制了摩尔质量，因为不希望自由基转移，禁止获得所需的机械性能。在本研究中，我们采用乳液聚合的方法合成了含有1 - 7mol % BMDTO的PS-BMDTO （PSB）共聚物。与散装FRP相比，粒径排除色谱显示，在2.4 mol% BMDTO时，乳液聚合产生更大的摩尔质量（81 kg mol - 1 vs. 17 kg mol - 1）。1H核磁共振波谱观察到BMDTO的掺入，并通过与烯丙基二硫醇的链裂反应进一步证实了BMDTO的掺入。3.9 mol% PSB的摩尔质量从33 kg mol−1下降到10 kg mol−1，而没有BMDTO的PS的摩尔质量保持不变。这些结果表明，乳液聚合有效地防止了自由基转移，延长了自由基寿命，为高性能、可回收的乙烯基共聚物的合成提供了一条合适的途径。利用环共聚物3,7-双（亚甲基）-1,5-二硫代环辛烷（BMDTO）开环共聚，引入可切割的C-S键，具有化学可回收性；然而，由于不期望的自由基转移，它遭受通过散装自由基聚合的低摩尔质量。为此，本研究利用乳液聚合生产聚苯乙烯-BMDTO共聚物（1-7 mol% BMDTO），在2.4 mol% BMDTO下获得更高的摩尔质量（81 vs. 17 kg/mol）。核磁共振波谱和粒径排除色谱证实了BMDTO的掺入和可切割性，建立了乳液聚合作为生产可回收的高性能乙烯基共聚物的可行方法。
{"title":"Emulsion polymerization of allyl sulfide copolymers for enhanced molar mass","authors":"Michelle Gross, Autumn M. Mineo, Reika Katsumata","doi":"10.1038/s41428-025-01086-w","DOIUrl":"10.1038/s41428-025-01086-w","url":null,"abstract":"Existing recycling approaches for vinyl-derived polymers, which constitute approximately 50% of global plastic production, rely heavily on energy-intensive incineration and pyrolysis, whereas laboratory-scale chemical recycling is material specific. To enable more universal chemical recyclability in vinyl polymers, ring-opening copolymerization with the cyclic comonomer 3,7-bis(methylene)-1,5-dithiacyclooctane (BMDTO) is an emerging solution that involves the integration of cleavable C–S bonds in the backbone. However, bulk free radical polymerization (FRP) with BMDTO limits the molar mass because of undesired radical transfer, prohibiting access to the desired mechanical properties. In this study, we employ emulsion polymerization to synthesize PS-BMDTO (PSB) copolymers with 1–7 mol% BMDTO. Compared with bulk FRP, size exclusion chromatography reveals that emulsion polymerization yields a greater molar mass (81 kg mol−1 vs. 17 kg mol−1) at 2.4 mol% BMDTO. The incorporation of BMDTO is observed by 1H nuclear magnetic resonance spectroscopy and further confirmed by a chain scission reaction with allyl dithiol. The molar mass of 3.9 mol% PSB decreases from 33 kg mol−1 to 10 kg mol−1, while the molar mass of PS without BMDTO remains unchanged. These results reveal that emulsion polymerization effectively prevents undesired radical transfer and extends radical lifetime, offering a suitable synthesis route for high-performance, recyclable vinyl copolymers. Ring-opening copolymerization using the cyclic comonomer 3,7-bis(methylene)-1,5-dithiacyclooctane (BMDTO) introduces cleavable C–S bonds for chemical recyclability; however, it suffers from low molar mass via bulk free radical polymerization due to undesired radical transfer. To this end, this study leverages emulsion polymerization to produce polystyrene-BMDTO copolymers (1–7 mol% BMDTO), achieving higher molar mass (81 vs. 17 kg/mol) at 2.4 mol% BMDTO. Nuclear magnetic resonance spectroscopy and size exclusion chromatography confirm the incorporation and cleavability of BMDTO, establishing emulsion polymerization as a viable method for producing recyclable, high-performance vinyl copolymers.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 11","pages":"1145-1151"},"PeriodicalIF":2.7,"publicationDate":"2025-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01086-w.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145436551","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-31DOI: 10.1038/s41428-025-01070-4
Yasuhiro Kohsaka, Hanae Torisawa, Akane Kazama
2-Methylene-4H-benzo[d][1,3]dioxin-4-one, a cyclic hemiacetal ester prepared via the intramolecular esterification of acetyl salicylic acid, is an electron-rich vinyl monomer that can undergo radical polymerization to afford vinyl polymers with excellent thermal and mechanical properties. In this study, the aromatic ring was substituted with various substituents. Substitution with electron-donating groups resulted in instability and low yields, whereas substitution with two tert-butyl groups at the 6- and 8-positions increased the stability against moisture and reduced the reactivity in radical polymerization. Thus, the monomer afforded an almost ideal alternating copolymer with dimethyl maleate. Compared with the copolymers with nonsubstituted monomers, the copolymers with vinyl acetate presented a higher glass transition temperature, suggesting that the two tert-butyl groups effectively increased the thermal stability. Cyclic ketene acetal esters derived from acetylsalicylic acid with various substituents on their aromatic rings were investigated. Substitution by two tert-butyl groups improved the stability of the monomer against moisture. Furthermore, the polymer solubility was increased by the flexible substituents, and the glass transition temperature was significantly increased owing to restricted bond rotation. The bulkiness of the tert-butyl group reduces the monomer reactivity, resulting in an almost ideal alternating copolymer with dimethyl maleate.
{"title":"Synthesis and polymerization of modified dehydroaspirin with increased stability and polymer solubility","authors":"Yasuhiro Kohsaka, Hanae Torisawa, Akane Kazama","doi":"10.1038/s41428-025-01070-4","DOIUrl":"10.1038/s41428-025-01070-4","url":null,"abstract":"2-Methylene-4H-benzo[d][1,3]dioxin-4-one, a cyclic hemiacetal ester prepared via the intramolecular esterification of acetyl salicylic acid, is an electron-rich vinyl monomer that can undergo radical polymerization to afford vinyl polymers with excellent thermal and mechanical properties. In this study, the aromatic ring was substituted with various substituents. Substitution with electron-donating groups resulted in instability and low yields, whereas substitution with two tert-butyl groups at the 6- and 8-positions increased the stability against moisture and reduced the reactivity in radical polymerization. Thus, the monomer afforded an almost ideal alternating copolymer with dimethyl maleate. Compared with the copolymers with nonsubstituted monomers, the copolymers with vinyl acetate presented a higher glass transition temperature, suggesting that the two tert-butyl groups effectively increased the thermal stability. Cyclic ketene acetal esters derived from acetylsalicylic acid with various substituents on their aromatic rings were investigated. Substitution by two tert-butyl groups improved the stability of the monomer against moisture. Furthermore, the polymer solubility was increased by the flexible substituents, and the glass transition temperature was significantly increased owing to restricted bond rotation. The bulkiness of the tert-butyl group reduces the monomer reactivity, resulting in an almost ideal alternating copolymer with dimethyl maleate.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 12","pages":"1339-1346"},"PeriodicalIF":2.7,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01070-4.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145666270","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-31DOI: 10.1038/s41428-025-01077-x
Kozo Matsumoto, Takeo Mitoma, Iku Yamashita, Tatsuki Watanabe
A trifunctional five-membered cyclic carbonate resin synthesized from resveratrol (Res-TC) was thermally cured with various diamines: trioxyethylene diamine (TODA), dioxyethylene diamine (DODA), m-xylene diamine (mXDA), pentamethylene diamine (PMDA), and Jeffamine ED-600. Thermogravimetric analysis (TGA) revealed that the cured Res-TC/TODA, Res-TC/DODA, Res-TC/mXDA, and Res-TC/PMDA were easily thermally decomposed, whereas the cured Res-TC/Jeffamine was relatively stable. Differential scanning calorimetry (DSC) indicated that the cured Res-TC/TODA and Res-TC/Jeffamine samples were rubbery, whereas the cured Res-TC/DODA, Res-TC/mXDA, and Res-TC/PMDA samples were glassy at room temperature. Tensile tests of the cured resin films revealed that Res-TC/TODA, Res-TC/DODA, and Res-TC/PMDA had high elastic moduli of approximately 1 GPa with moderate tensile strengths, whereas Res-TC/mXDA had low tensile strength, indicating that it was a brittle material. Cured Res-TC/Jeffamine was a very soft material with poor mechanical properties. An adhesion test of the metal substrates revealed that cured Res-TC/TODA adhered strongly to both aluminum and stainless steel. After treatment with enzymes such as lipase and protease, some cured resins exhibited greater water uptake than did those treated with pure water, indicating that the enzymes cleaved the network of the cured resins and gradually decomposed the materials. A trifunctional five-membered cyclic carbonate resin synthesized from resveratrol (Res-TC) was thermally cured with diamines: trioxyethylene diamine (TODA), dioxyethylene diamine (DODA), m-xylene diamine (mXDA), pentamethylene diamine (PMDA), and Jeffamine ED-600. An adhesion test of the metal substrates revealed that cured Res-TC/TODA adhered strongly to metal substrates. After treatment with enzymes such as lipase and protease, some cured resins exhibited greater water uptake than did those treated with pure water, indicating that the enzymes cleaved the network of the cured resins and gradually decomposed the materials.
{"title":"Curing of resveratrol-based trifunctional five-membered cyclic carbonate with various diamines and properties of the cured resins","authors":"Kozo Matsumoto, Takeo Mitoma, Iku Yamashita, Tatsuki Watanabe","doi":"10.1038/s41428-025-01077-x","DOIUrl":"10.1038/s41428-025-01077-x","url":null,"abstract":"A trifunctional five-membered cyclic carbonate resin synthesized from resveratrol (Res-TC) was thermally cured with various diamines: trioxyethylene diamine (TODA), dioxyethylene diamine (DODA), m-xylene diamine (mXDA), pentamethylene diamine (PMDA), and Jeffamine ED-600. Thermogravimetric analysis (TGA) revealed that the cured Res-TC/TODA, Res-TC/DODA, Res-TC/mXDA, and Res-TC/PMDA were easily thermally decomposed, whereas the cured Res-TC/Jeffamine was relatively stable. Differential scanning calorimetry (DSC) indicated that the cured Res-TC/TODA and Res-TC/Jeffamine samples were rubbery, whereas the cured Res-TC/DODA, Res-TC/mXDA, and Res-TC/PMDA samples were glassy at room temperature. Tensile tests of the cured resin films revealed that Res-TC/TODA, Res-TC/DODA, and Res-TC/PMDA had high elastic moduli of approximately 1 GPa with moderate tensile strengths, whereas Res-TC/mXDA had low tensile strength, indicating that it was a brittle material. Cured Res-TC/Jeffamine was a very soft material with poor mechanical properties. An adhesion test of the metal substrates revealed that cured Res-TC/TODA adhered strongly to both aluminum and stainless steel. After treatment with enzymes such as lipase and protease, some cured resins exhibited greater water uptake than did those treated with pure water, indicating that the enzymes cleaved the network of the cured resins and gradually decomposed the materials. A trifunctional five-membered cyclic carbonate resin synthesized from resveratrol (Res-TC) was thermally cured with diamines: trioxyethylene diamine (TODA), dioxyethylene diamine (DODA), m-xylene diamine (mXDA), pentamethylene diamine (PMDA), and Jeffamine ED-600. An adhesion test of the metal substrates revealed that cured Res-TC/TODA adhered strongly to metal substrates. After treatment with enzymes such as lipase and protease, some cured resins exhibited greater water uptake than did those treated with pure water, indicating that the enzymes cleaved the network of the cured resins and gradually decomposed the materials.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 12","pages":"1391-1397"},"PeriodicalIF":2.7,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145666276","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-31DOI: 10.1038/s41428-025-01073-1
Yuta Yoshizaki, Koki Onoda, Tomohiro Konno
Protein therapeutics have gained market share in the medical community worldwide. However, proteins cannot cross cell membranes, and they can be degraded in the intracellular or extracellular environment. Materials that are used in pharmaceutical formulations play crucial roles in allowing the proteins they deliver to perform the appropriate functions. The copolymer of 2-methacryloyloxyethyl phosphorylcholine (MPC) and n-butyl methacrylate (BMA) is a phospholipid-mimicking polymer that has excellent biocompatibility and direct cell-penetrating properties. In this study, the phospholipid polymer-based bioconjugation polymer poly[MPC-co-BMA-co-N-succinimidyloxycarbonyl tetra(ethylene glycol) methacrylate (MENHS)] (PMBS) was synthesized and conjugated with OVA: ovalbumin (as a model protein). We investigated the effect of the PMBS and OVA mixing ratio on the cellular internalization of OVA to evaluate the ability of this formulation to control immune responses in a murine dendritic cell line. The bioconjugate of PMBS-OVA formed polymolecular associations in aqueous solution. The PMBS-OVA conjugate that contained a greater amount of PMBS delivered OVA into the cytosol at 4 °C, which is a condition that inhibits the endocytic pathway. Although the PMBS-OVA conjugate did not affect cytokine production, it increased antigen presentation via major histocompatibility complex class I. Therefore, we successfully prepared a bioconjugate that exhibits excellent biocompatibility and cans directly deliver a protein into the cytosol using phospholipid polymers. Phospholipid polymers with amphiphilic nature can non-invasively permeate into the plasma membrane. We prepared protein-polymer conjugation using the bioconjugate technique. We found that the amount of phospholipid polymer in the bioconjugation affected the internalization route to the antigen-presenting cells (APCs). The bioconjugations that have a large quantity of phospholipid polymer chains were internalized via a non-endocytic route. Cytosolic protein delivery by the phospholipid-protein conjugate enabled APCs to recognize the delivered protein as an endogenous antigen, facilitating antigen presentation. Therefore, phospholipid polymer-based bioconjugation attained direct cytosolic delivery of proteins
蛋白质疗法在全球医学界获得了市场份额。然而，蛋白质不能穿过细胞膜，它们可以在细胞内或细胞外环境中降解。在药物配方中使用的材料在允许它们递送的蛋白质执行适当的功能方面起着至关重要的作用。2-甲基丙烯酰氧乙基磷酸胆碱（MPC）与甲基丙烯酸正丁酯（BMA）的共聚物是一种具有良好生物相容性和直接穿透细胞性能的磷脂模拟聚合物。本研究合成了基于磷脂聚合物的生物偶联聚合物[mpc -co- bma -co- n -琥珀酰酰氧羰基四（乙二醇）甲基丙烯酸酯（MENHS）] (PMBS)，并与OVA：卵清蛋白（作为模型蛋白）偶联。我们研究了PMBS和OVA混合比例对OVA细胞内化的影响，以评估该配方控制小鼠树突状细胞系免疫反应的能力。PMBS-OVA生物偶联物在水溶液中形成多分子结合。含有更大量PMBS的PMBS-OVA偶联物在4°C时将OVA送入胞浆，这是抑制内吞途径的条件。虽然PMBS-OVA偶联物不影响细胞因子的产生，但它通过主要的组织相容性复合体i类增加了抗原呈递。因此，我们成功制备了一种生物偶联物，它具有优异的生物相容性，可以使用磷脂聚合物直接将蛋白质递送到细胞质中。具有两亲性质的磷脂聚合物可以无创地渗透到质膜中。利用生物偶联技术制备蛋白-聚合物偶联物。我们发现生物偶联中磷脂聚合物的数量影响到抗原呈递细胞（APCs）的内化途径。具有大量磷脂聚合物链的生物偶联物通过非内吞途径内化。磷脂-蛋白偶联物的细胞质蛋白递送使apc能够识别被递送的蛋白为内源性抗原，促进抗原呈递。因此，基于磷脂聚合物的生物偶联实现了蛋白质的直接胞质递送
{"title":"Direct cytosolic delivery of antigenic proteins via phospholipid polymer bioconjugates","authors":"Yuta Yoshizaki, Koki Onoda, Tomohiro Konno","doi":"10.1038/s41428-025-01073-1","DOIUrl":"10.1038/s41428-025-01073-1","url":null,"abstract":"Protein therapeutics have gained market share in the medical community worldwide. However, proteins cannot cross cell membranes, and they can be degraded in the intracellular or extracellular environment. Materials that are used in pharmaceutical formulations play crucial roles in allowing the proteins they deliver to perform the appropriate functions. The copolymer of 2-methacryloyloxyethyl phosphorylcholine (MPC) and n-butyl methacrylate (BMA) is a phospholipid-mimicking polymer that has excellent biocompatibility and direct cell-penetrating properties. In this study, the phospholipid polymer-based bioconjugation polymer poly[MPC-co-BMA-co-N-succinimidyloxycarbonyl tetra(ethylene glycol) methacrylate (MENHS)] (PMBS) was synthesized and conjugated with OVA: ovalbumin (as a model protein). We investigated the effect of the PMBS and OVA mixing ratio on the cellular internalization of OVA to evaluate the ability of this formulation to control immune responses in a murine dendritic cell line. The bioconjugate of PMBS-OVA formed polymolecular associations in aqueous solution. The PMBS-OVA conjugate that contained a greater amount of PMBS delivered OVA into the cytosol at 4 °C, which is a condition that inhibits the endocytic pathway. Although the PMBS-OVA conjugate did not affect cytokine production, it increased antigen presentation via major histocompatibility complex class I. Therefore, we successfully prepared a bioconjugate that exhibits excellent biocompatibility and cans directly deliver a protein into the cytosol using phospholipid polymers. Phospholipid polymers with amphiphilic nature can non-invasively permeate into the plasma membrane. We prepared protein-polymer conjugation using the bioconjugate technique. We found that the amount of phospholipid polymer in the bioconjugation affected the internalization route to the antigen-presenting cells (APCs). The bioconjugations that have a large quantity of phospholipid polymer chains were internalized via a non-endocytic route. Cytosolic protein delivery by the phospholipid-protein conjugate enabled APCs to recognize the delivered protein as an endogenous antigen, facilitating antigen presentation. Therefore, phospholipid polymer-based bioconjugation attained direct cytosolic delivery of proteins","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 11","pages":"1245-1255"},"PeriodicalIF":2.7,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01073-1.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145436505","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：