Organic redox polymers, composed of earth-abundant elements, offer rapid charge storage and are promising electrode-active materials for aqueous batteries, potentially replacing metals and overcoming their resource and performance limitations. However, the hydrophobicity of many organic redox molecules hinders their application using aqueous electrolytes. This necessitates molecular designs that impart hydrophilicity while immobilizing redox-active moieties onto electrodes. Polyallylamine, with its high density of hydrophilic amino groups, serves as an effective backbone. In this work, functionalizing it with hydroquinone enabled the use of the polymer in aqueous batteries. While hydroquinone provides high theoretical capacity, irreversible quinhydrone formation limits its reversible and thorough charge storage. We addressed this by covalently attaching hydroquinone to polyallylamine via condensation. The resulting polymer exhibited reversible and thorough charge storage, which was attributed to electrostatic repulsion between amino groups that suppressed quinhydrone formation. A polymer–air secondary battery was fabricated with the polymer, Pt/C, and a 0.5 M H2SO4 aqueous solution as the anode, cathode, and electrolyte, respectively, without any separator. This polymer–air secondary battery displayed a constant discharge voltage with high cyclability (>99% capacity retention after 100 cycles) and high-rate capability. Moreover, the polymer demonstrated recyclability, as raw materials were generated simply by acid treatment. This work demonstrates a polymer design strategy for integrating typically hydrophobic organic redox molecules into recyclable aqueous batteries. Substituting hydroquinone into polyallylamine allows the resulting organic redox polymer to achieve 99% of its theoretical capacity in aqueous electrolytes. A polymer-air secondary battery fabricated with this redox polymer as the electrode-active material exhibited a constant discharge voltage, high cyclability, and high rate capability. In addition, facile acid treatment decomposes the redox polymer into its raw materials. This work demonstrates a polymer design strategy for integrating typically hydrophobic organic redox molecules into recyclable aqueous batteries.
有机氧化还原聚合物由地球上丰富的元素组成，提供快速充电存储，是很有前途的水电池电极活性材料，有可能取代金属并克服其资源和性能限制。然而，许多有机氧化还原分子的疏水性阻碍了它们在水电解质中的应用。这就需要在将氧化还原活性部分固定在电极上的同时赋予亲水性的分子设计。聚烯丙胺具有高密度的亲水性氨基，可作为有效的骨架。在这项工作中，用对苯二酚使其功能化，使聚合物在水性电池中的使用成为可能。虽然对苯二酚提供了很高的理论容量，但不可逆的对苯二酚形成限制了其可逆和彻底的电荷储存。我们通过缩合将对苯二酚共价连接到聚烯丙胺上来解决这个问题。所得到的聚合物表现出可逆和彻底的电荷存储，这是由于氨基之间的静电排斥抑制了醌的形成。采用该聚合物、Pt/C和0.5 M H2SO4水溶液分别作为阳极、阴极和电解液制备了聚合物-空气二次电池，无需任何分离器。该聚合物-空气二次电池具有恒定的放电电压、高可循环性（100次循环后容量保持率达99%）和高倍率性能。此外，聚合物证明了可回收性，因为原料是由酸处理产生的。这项工作展示了一种聚合物设计策略，可以将典型的疏水性有机氧化还原分子整合到可回收的水性电池中。将对苯二酚取代为聚烯丙胺可以使所得的有机氧化还原聚合物在水溶液中达到其理论容量的99%。以该氧化还原聚合物为电极活性材料制备的聚合物-空气二次电池具有恒定的放电电压、高可循环性和高倍率性能。此外，易酸处理将氧化还原聚合物分解为其原料。这项工作展示了一种聚合物设计策略，可以将典型的疏水性有机氧化还原分子整合到可回收的水性电池中。
{"title":"Hydroquinone-substituted polyallylamine: redox capability for aqueous polymer–air secondary batteries and recyclability","authors":"Kouki Oka, Showa Kitajima, Kohei Okubo, Kiyotaka Maruoka, Yuta Takahashi, Yoko Teruchi, Minoru Takeuchi, Kazuhiko Igarashi, Hitoshi Kasai","doi":"10.1038/s41428-025-01085-x","DOIUrl":"10.1038/s41428-025-01085-x","url":null,"abstract":"Organic redox polymers, composed of earth-abundant elements, offer rapid charge storage and are promising electrode-active materials for aqueous batteries, potentially replacing metals and overcoming their resource and performance limitations. However, the hydrophobicity of many organic redox molecules hinders their application using aqueous electrolytes. This necessitates molecular designs that impart hydrophilicity while immobilizing redox-active moieties onto electrodes. Polyallylamine, with its high density of hydrophilic amino groups, serves as an effective backbone. In this work, functionalizing it with hydroquinone enabled the use of the polymer in aqueous batteries. While hydroquinone provides high theoretical capacity, irreversible quinhydrone formation limits its reversible and thorough charge storage. We addressed this by covalently attaching hydroquinone to polyallylamine via condensation. The resulting polymer exhibited reversible and thorough charge storage, which was attributed to electrostatic repulsion between amino groups that suppressed quinhydrone formation. A polymer–air secondary battery was fabricated with the polymer, Pt/C, and a 0.5 M H2SO4 aqueous solution as the anode, cathode, and electrolyte, respectively, without any separator. This polymer–air secondary battery displayed a constant discharge voltage with high cyclability (>99% capacity retention after 100 cycles) and high-rate capability. Moreover, the polymer demonstrated recyclability, as raw materials were generated simply by acid treatment. This work demonstrates a polymer design strategy for integrating typically hydrophobic organic redox molecules into recyclable aqueous batteries. Substituting hydroquinone into polyallylamine allows the resulting organic redox polymer to achieve 99% of its theoretical capacity in aqueous electrolytes. A polymer-air secondary battery fabricated with this redox polymer as the electrode-active material exhibited a constant discharge voltage, high cyclability, and high rate capability. In addition, facile acid treatment decomposes the redox polymer into its raw materials. This work demonstrates a polymer design strategy for integrating typically hydrophobic organic redox molecules into recyclable aqueous batteries.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 11","pages":"1239-1244"},"PeriodicalIF":2.7,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01085-x.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145436540","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}
Mucin is a biological compound that consists of high-molecular-weight glycoproteins and plays an important role in the evaporation of water from respiratory droplets. Accurate characterization of the molecular structure of mucin in aqueous solution was performed using light scattering measurements. The molecular weight, M = 2.92 × 107, and the radius of gyration, Rg = 289 nm, were determined from static light scattering, and the hydrodynamic radius, Rh = 198 nm, was determined from dynamic light scattering. The Rg/Rh ratio of 1.46 and the observed particle scattering function reveal that the molecular structure of mucin is elongated rather than spherical. As the size of molecules approaches the wavelength of the detected light, the analysis of light scattering measurements requires careful consideration. The calculation method devised by H. Fujita enables measurement of the molecular structure with extremely high accuracy. Mucin is a biological compound that consists of high-molecular-weight glycoproteins and plays an important role in the evaporation of water from respiratory droplets. The detailed structure of mucin has been clarified by static light scattering and the Fujita plot. The molecular weight is 2.92 × 107, and the radius of gyration is 289 nm. The hydrodynamic radius is 198 nm, which was determined from multiangle dynamic light scattering. The scattering function reveals that mucin has a chain-like, elongated structure.
{"title":"Structural characterization of mucin in aqueous solution by static and dynamic light scattering measurements","authors":"Kayori Takahashi, Kenjiro Iida, Hiromu Sakurai, Nobuyuki Takegawa","doi":"10.1038/s41428-025-01096-8","DOIUrl":"10.1038/s41428-025-01096-8","url":null,"abstract":"Mucin is a biological compound that consists of high-molecular-weight glycoproteins and plays an important role in the evaporation of water from respiratory droplets. Accurate characterization of the molecular structure of mucin in aqueous solution was performed using light scattering measurements. The molecular weight, M = 2.92 × 107, and the radius of gyration, Rg = 289 nm, were determined from static light scattering, and the hydrodynamic radius, Rh = 198 nm, was determined from dynamic light scattering. The Rg/Rh ratio of 1.46 and the observed particle scattering function reveal that the molecular structure of mucin is elongated rather than spherical. As the size of molecules approaches the wavelength of the detected light, the analysis of light scattering measurements requires careful consideration. The calculation method devised by H. Fujita enables measurement of the molecular structure with extremely high accuracy. Mucin is a biological compound that consists of high-molecular-weight glycoproteins and plays an important role in the evaporation of water from respiratory droplets. The detailed structure of mucin has been clarified by static light scattering and the Fujita plot. The molecular weight is 2.92 × 107, and the radius of gyration is 289 nm. The hydrodynamic radius is 198 nm, which was determined from multiangle dynamic light scattering. The scattering function reveals that mucin has a chain-like, elongated structure.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 12","pages":"1375-1382"},"PeriodicalIF":2.7,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145666277","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 : 2025-08-22DOI: 10.1038/s41428-025-01095-9
Takuya Yamamoto, Jo Tazuke
The effects of the topology of cyclic polymers at surfaces and interfaces are described and discussed in this review. The topics include those at the air‒water interface, micellization, phase transition, and adsorption to nanoparticles. Surface tension studies revealed that the interfacial activity of cyclized polymers is greater than that of their linear counterparts because of an increase in the molecular density at the air‒water interface. Moreover, the micellization enthalpy and entropy (ΔHmic and ΔSmic) and lower critical micelle temperature (TCMT) were found for cyclic polymers, where the hydrophilic/hydrophobic ratio also significantly influenced. In addition, cyclic poly(ethylene glycol), c-PEG, can interact strongly with gold nanoparticles (AuNPs) and bovine serum albumin (BSA), whereas no such effects were found for linear PEG. The red color of an AuNPs dispersion vanished when BSA was added to complexes of AuNPs/c-PEG to form aggregates. In this context, silver nanoparticles (AgNPs) have not been proven to be capable of consistent PEGylation despite their usefulness in biological applications. c-PEG was found to physisorb onto AgNPs to effectively PEGylate and improve dispersion stability under physiological circumstances, long-term exposure to white light, and high temperature. Consequently, the generation of new functional materials and their applications can be facilitated by the effects of cyclization, which makes the use of a polymer topology feasible for the logical design of polymeric materials. Structural and steric restrictions in polymer chains resulted in significant differences between cyclic polymers and their linear counterparts in the interfacial properties. The topological influences on the air–water interfacial activity and aggregation behavior of PEG and Pluronic surfactants were investigated. Silver nanoparticles adsorbed with cyclic PEG exhibited high dispersion stability under physiological and various conditions. This study successfully combined the biocompatibility of PEG with the antibacterial activity of silver nanoparticles. These results demonstrate that utilizing polymer topology can serve as a useful tool for designing new functional materials.
{"title":"Unique properties of cyclic polymers at interfaces and their applications to nanomaterials","authors":"Takuya Yamamoto, Jo Tazuke","doi":"10.1038/s41428-025-01095-9","DOIUrl":"10.1038/s41428-025-01095-9","url":null,"abstract":"The effects of the topology of cyclic polymers at surfaces and interfaces are described and discussed in this review. The topics include those at the air‒water interface, micellization, phase transition, and adsorption to nanoparticles. Surface tension studies revealed that the interfacial activity of cyclized polymers is greater than that of their linear counterparts because of an increase in the molecular density at the air‒water interface. Moreover, the micellization enthalpy and entropy (ΔHmic and ΔSmic) and lower critical micelle temperature (TCMT) were found for cyclic polymers, where the hydrophilic/hydrophobic ratio also significantly influenced. In addition, cyclic poly(ethylene glycol), c-PEG, can interact strongly with gold nanoparticles (AuNPs) and bovine serum albumin (BSA), whereas no such effects were found for linear PEG. The red color of an AuNPs dispersion vanished when BSA was added to complexes of AuNPs/c-PEG to form aggregates. In this context, silver nanoparticles (AgNPs) have not been proven to be capable of consistent PEGylation despite their usefulness in biological applications. c-PEG was found to physisorb onto AgNPs to effectively PEGylate and improve dispersion stability under physiological circumstances, long-term exposure to white light, and high temperature. Consequently, the generation of new functional materials and their applications can be facilitated by the effects of cyclization, which makes the use of a polymer topology feasible for the logical design of polymeric materials. Structural and steric restrictions in polymer chains resulted in significant differences between cyclic polymers and their linear counterparts in the interfacial properties. The topological influences on the air–water interfacial activity and aggregation behavior of PEG and Pluronic surfactants were investigated. Silver nanoparticles adsorbed with cyclic PEG exhibited high dispersion stability under physiological and various conditions. This study successfully combined the biocompatibility of PEG with the antibacterial activity of silver nanoparticles. These results demonstrate that utilizing polymer topology can serve as a useful tool for designing new functional materials.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 12","pages":"1313-1321"},"PeriodicalIF":2.7,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01095-9.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145666278","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}
About 70 years ago, the crystal structure of the nylon 6 α form was proposed by Bunn et al. (Bunn’s model) on the basis of wide-angle X-ray diffraction (WAXD) data analysis. The nearly extended planar-zigzag chains with alternating upward and downward orientations are regularly connected by intermolecular hydrogen bonds to form a sheet plane. These sheets are stacked regularly under the space group symmetry of P21. The quantitative analyses of WAXD and WAND data, which were measured for the first time in the present study, revealed the following. (i) Bunn’s model can be constructed using the space group P21/n of higher symmetry (this revision is important in the structure‒property discussion), (ii) but their regular model cannot reproduce both WAXD and WAND data without any issues. Moreover, (iii) the introduction of a statistically disordered up/down chain packing concept can reproduce these observed diffraction data consistently. As one local structure, the aggregation of domains has been proposed, where the domain itself consists of regular chain packing, but these domains are randomly aggregated together with the ±a/2 shift and a small c-axial shift to form a crystalline lamella. In this way, the crystal structure of the nylon-6 α form has been conclusively established. The crystal structure of the nylon-6 α form has been established on the basis of wide-angle X-ray diffraction data analysis. We have believed it for the past 70 years. However, the combination of X-ray and neutron diffraction data has required us to introduce the statistical disorderliness to the chain-packing mode as well as revise the space group to that of a higher symmetry. The refined crystal structure makes it possible to perform a more reliable quantitative analysis of the structure‒property relationship of the α form.
{"title":"Crystal structure of the nylon-6 α form as established by wide-angle X-ray and neutron diffraction data analyses","authors":"Kohji Tashiro, Kazuo Kurihara, Taro Tamada, Katsuhiro Kusaka, Terutoshi Sakakura","doi":"10.1038/s41428-025-01094-w","DOIUrl":"10.1038/s41428-025-01094-w","url":null,"abstract":"About 70 years ago, the crystal structure of the nylon 6 α form was proposed by Bunn et al. (Bunn’s model) on the basis of wide-angle X-ray diffraction (WAXD) data analysis. The nearly extended planar-zigzag chains with alternating upward and downward orientations are regularly connected by intermolecular hydrogen bonds to form a sheet plane. These sheets are stacked regularly under the space group symmetry of P21. The quantitative analyses of WAXD and WAND data, which were measured for the first time in the present study, revealed the following. (i) Bunn’s model can be constructed using the space group P21/n of higher symmetry (this revision is important in the structure‒property discussion), (ii) but their regular model cannot reproduce both WAXD and WAND data without any issues. Moreover, (iii) the introduction of a statistically disordered up/down chain packing concept can reproduce these observed diffraction data consistently. As one local structure, the aggregation of domains has been proposed, where the domain itself consists of regular chain packing, but these domains are randomly aggregated together with the ±a/2 shift and a small c-axial shift to form a crystalline lamella. In this way, the crystal structure of the nylon-6 α form has been conclusively established. The crystal structure of the nylon-6 α form has been established on the basis of wide-angle X-ray diffraction data analysis. We have believed it for the past 70 years. However, the combination of X-ray and neutron diffraction data has required us to introduce the statistical disorderliness to the chain-packing mode as well as revise the space group to that of a higher symmetry. The refined crystal structure makes it possible to perform a more reliable quantitative analysis of the structure‒property relationship of the α form.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 12","pages":"1359-1373"},"PeriodicalIF":2.7,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01094-w.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145666273","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}
Practical applications of viral- and cell-based therapeutics require precise targeted delivery to minimize off-target effects. Conventional hydrogel-based drug delivery carriers may undergo a sol‒gel phase transition upon in vivo degradation, leading to a burst release of encapsulated substances. Transient-network materials have been proposed to overcome this challenge. However, the relationship between the network structure and release mechanisms remains unclear, mainly due to the lack of control over structural heterogeneity in typical transient networks. This study aimed to elucidate the mechanism underlying the release of micrometer-scale particles from transient networks using a systematically controlled model system composed of tetra-armed polyethylene glycol (Tetra-PEG slime). The system features a well-defined structure with uniform strand lengths and consistent functionalities. Our results demonstrate that particle release is driven by the dissolution of the matrix and that the release barrier depends on the surrounding network topology. This release behavior is primarily determined by network connectivity and is independent of the polymer concentration and strand length. These insights advance our understanding of the sustainable release of microparticles from transient networks and provide broadly applicable guidelines for the development of effective drug delivery systems. This study aimed to elucidate the mechanism underlying the release of micrometer-scale particles from transient networks using a systematically controlled model system composed of tetra-armed polyethylene glycol (Tetra-PEG slime). The system features a well-defined structure with uniform strand lengths and functionalities. Our results demonstrate that particle release is governed by the dissolution of the matrix and that the release barrier depends on the surrounding network topology. This release behavior is primarily determined by network connectivity and is independent of polymer concentration and strand length.
{"title":"Release mechanism of micrometer-scale particles from transient networks with well-controlled structures","authors":"Sayuri Tanaka, Kyohhei Fujita, Yuta Yamamoto, Farah Aqilah Md Zulkiflie, Taichi Suzuki, Mitsuru Naito, Ung-il Chung, Takuya Katashima","doi":"10.1038/s41428-025-01097-7","DOIUrl":"10.1038/s41428-025-01097-7","url":null,"abstract":"Practical applications of viral- and cell-based therapeutics require precise targeted delivery to minimize off-target effects. Conventional hydrogel-based drug delivery carriers may undergo a sol‒gel phase transition upon in vivo degradation, leading to a burst release of encapsulated substances. Transient-network materials have been proposed to overcome this challenge. However, the relationship between the network structure and release mechanisms remains unclear, mainly due to the lack of control over structural heterogeneity in typical transient networks. This study aimed to elucidate the mechanism underlying the release of micrometer-scale particles from transient networks using a systematically controlled model system composed of tetra-armed polyethylene glycol (Tetra-PEG slime). The system features a well-defined structure with uniform strand lengths and consistent functionalities. Our results demonstrate that particle release is driven by the dissolution of the matrix and that the release barrier depends on the surrounding network topology. This release behavior is primarily determined by network connectivity and is independent of the polymer concentration and strand length. These insights advance our understanding of the sustainable release of microparticles from transient networks and provide broadly applicable guidelines for the development of effective drug delivery systems. This study aimed to elucidate the mechanism underlying the release of micrometer-scale particles from transient networks using a systematically controlled model system composed of tetra-armed polyethylene glycol (Tetra-PEG slime). The system features a well-defined structure with uniform strand lengths and functionalities. Our results demonstrate that particle release is governed by the dissolution of the matrix and that the release barrier depends on the surrounding network topology. This release behavior is primarily determined by network connectivity and is independent of polymer concentration and strand length.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 12","pages":"1383-1390"},"PeriodicalIF":2.7,"publicationDate":"2025-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01097-7.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145666271","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}
Owing to the increase in global concern, the replacement of fossil fuel-derived plastics with biomass polymers has attracted the interest of many researchers in both academia and industry. Levoglucosenone (LGO; 1), which is a biomass compound obtained from cellulose in wood or waste paper, has been used as a feedstock for biomass polymers. We recently discovered the stereoselective formation of tricomponent polymers, including LGO fragments, dicarboxylic dihydrazides and aromatic dithiol. In this report, the syntheses and properties of their analogs using aliphatic dithiol instead of aromatic dithiol are reported. The LGO monomer linked with 1,4-butanedithiol was prepared by the addition of K2CO3. Polycondensation of the monomer with several dicarboxylic dihydrazides proceeded to form the corresponding polyhydrazones. All the C-S and C = N bonds were formed stereoselectively. The obtained polymers showed negative optical rotations, which were complementary to those of aromatic analogs. When the polymerization time increased, DMF-insoluble polymers were obtained, which formed organogels with DMF. The degree of swelling varied between 170% and 469% depending on the carbon number of the dicarboxylic dihydrazide. The elongation of the aliphatic carbon chains was assumed to promote intermolecular entanglement, and the resulting polymers were assumed to behave as network polymers despite the linear chains. Biomass-derived tricomponent polymers were synthesized consisting of Levoglucosenone, aliphatic dithiol, and dicarboxylic dihydrazide. Sequential treatment of LGO with 1,4-butanedithiol followed by polycondensation with several dicarboxylic dihydrazides resulted in the formation of the corresponding polyhydrazones. All the C-S and C = N bonds were formed stereoselectively, which provided us their optical properties. In addition, these polymers also formed organogels with DMF after further heating. The degree of swelling varied between 170% and 469% depending on the carbon number of the dicarboxylic dihydrazide.
{"title":"Stereoselective syntheses and properties of levoglucosenone-containing polymers linked with 1,4-butanedithiol and their application as organogels","authors":"Shogo Yashiro, Honoka Ishikawa, Toshio Hokajo, Kerem Bolukbasi, Takashi Itoh, Shinji Kudo, Takayuki Doi, Atsushi Tahara","doi":"10.1038/s41428-025-01088-8","DOIUrl":"10.1038/s41428-025-01088-8","url":null,"abstract":"Owing to the increase in global concern, the replacement of fossil fuel-derived plastics with biomass polymers has attracted the interest of many researchers in both academia and industry. Levoglucosenone (LGO; 1), which is a biomass compound obtained from cellulose in wood or waste paper, has been used as a feedstock for biomass polymers. We recently discovered the stereoselective formation of tricomponent polymers, including LGO fragments, dicarboxylic dihydrazides and aromatic dithiol. In this report, the syntheses and properties of their analogs using aliphatic dithiol instead of aromatic dithiol are reported. The LGO monomer linked with 1,4-butanedithiol was prepared by the addition of K2CO3. Polycondensation of the monomer with several dicarboxylic dihydrazides proceeded to form the corresponding polyhydrazones. All the C-S and C = N bonds were formed stereoselectively. The obtained polymers showed negative optical rotations, which were complementary to those of aromatic analogs. When the polymerization time increased, DMF-insoluble polymers were obtained, which formed organogels with DMF. The degree of swelling varied between 170% and 469% depending on the carbon number of the dicarboxylic dihydrazide. The elongation of the aliphatic carbon chains was assumed to promote intermolecular entanglement, and the resulting polymers were assumed to behave as network polymers despite the linear chains. Biomass-derived tricomponent polymers were synthesized consisting of Levoglucosenone, aliphatic dithiol, and dicarboxylic dihydrazide. Sequential treatment of LGO with 1,4-butanedithiol followed by polycondensation with several dicarboxylic dihydrazides resulted in the formation of the corresponding polyhydrazones. All the C-S and C = N bonds were formed stereoselectively, which provided us their optical properties. In addition, these polymers also formed organogels with DMF after further heating. The degree of swelling varied between 170% and 469% depending on the carbon number of the dicarboxylic dihydrazide.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 11","pages":"1165-1175"},"PeriodicalIF":2.7,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01088-8.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145436541","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}
In this study, we investigated the graft copolymerization of triethylene glycol dimethacrylate (TEGDMA), a dimethacrylate monomer, onto natural rubber in its latex form. Graft copolymerization involves the reaction of TEGDMA with deproteinized natural rubber (DPNR) in the presence of a tetraethylenepentamine/tert-butyl hydroperoxide redox initiator. Two different initiator concentrations, 0.033 and 0.066 mol/kg rubber, as well as two monomer concentrations, 0.25 and 0.5 mol/kg rubber, were used. The resulting graft copolymers were characterized using X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance (NMR) spectroscopy. Both FTIR and NMR analyses confirmed the successful grafting of TEGDMA onto DPNR, resulting in the formation of DPNR-graft-poly(TEGDMA). The properties of the graft copolymer were evaluated through various methods, including swelling tests, differential scanning calorimetry (DSC), tensile strength measurements, dynamic mechanical analysis (DMA), and thermogravimetric analysis (TGA). The gel content of DPNR increased dramatically after graft copolymerization, reaching 80–90%. Additionally, the glass transition temperature (Tg) shifted from −65.9 °C for DPNR to −67.7 °C for DPNR-graft-poly(TEGDMA) 0.033-0.5. Transmission electron microscopy (TEM) images revealed the formation of a poly(TEGDMA) layer surrounding the rubber molecules, creating a nanomatrix structure. Graft copolymerization of a bifunctional monomer, triethylene glycol dimethacrylate (TEGDMA), onto deproteinized natural rubber (DPNR) was performed in latex stage using a redox initiator. It was found that TEGDMA could be grafted onto NR chain with low conversion and grafting efficiency. TEM revealed the formation of a continuous nanomatrix of poly(TEGDMA) surrounding the rubber particles. This nanomatrix enhanced structural integrity, gel content and slightly shifted the glass transition temperature. Thermal and mechanical properties, assessed by DSC, TGA, DMA, and swelling tests, demonstrated that polyTEGDMA significantly influenced the graft copolymer’s performance.
{"title":"Graft copolymerization of triethylene glycol dimethacrylate onto natural rubber","authors":"Thuong Thi Nghiem, Trang Nguyen Thu, Nurul Hayati Yusof, Seiichi Kawahara","doi":"10.1038/s41428-025-01084-y","DOIUrl":"10.1038/s41428-025-01084-y","url":null,"abstract":"In this study, we investigated the graft copolymerization of triethylene glycol dimethacrylate (TEGDMA), a dimethacrylate monomer, onto natural rubber in its latex form. Graft copolymerization involves the reaction of TEGDMA with deproteinized natural rubber (DPNR) in the presence of a tetraethylenepentamine/tert-butyl hydroperoxide redox initiator. Two different initiator concentrations, 0.033 and 0.066 mol/kg rubber, as well as two monomer concentrations, 0.25 and 0.5 mol/kg rubber, were used. The resulting graft copolymers were characterized using X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance (NMR) spectroscopy. Both FTIR and NMR analyses confirmed the successful grafting of TEGDMA onto DPNR, resulting in the formation of DPNR-graft-poly(TEGDMA). The properties of the graft copolymer were evaluated through various methods, including swelling tests, differential scanning calorimetry (DSC), tensile strength measurements, dynamic mechanical analysis (DMA), and thermogravimetric analysis (TGA). The gel content of DPNR increased dramatically after graft copolymerization, reaching 80–90%. Additionally, the glass transition temperature (Tg) shifted from −65.9 °C for DPNR to −67.7 °C for DPNR-graft-poly(TEGDMA) 0.033-0.5. Transmission electron microscopy (TEM) images revealed the formation of a poly(TEGDMA) layer surrounding the rubber molecules, creating a nanomatrix structure. Graft copolymerization of a bifunctional monomer, triethylene glycol dimethacrylate (TEGDMA), onto deproteinized natural rubber (DPNR) was performed in latex stage using a redox initiator. It was found that TEGDMA could be grafted onto NR chain with low conversion and grafting efficiency. TEM revealed the formation of a continuous nanomatrix of poly(TEGDMA) surrounding the rubber particles. This nanomatrix enhanced structural integrity, gel content and slightly shifted the glass transition temperature. Thermal and mechanical properties, assessed by DSC, TGA, DMA, and swelling tests, demonstrated that polyTEGDMA significantly influenced the graft copolymer’s performance.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 12","pages":"1347-1357"},"PeriodicalIF":2.7,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145666274","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}
Macromolecules with cyclic topologies have attracted significant attention because of the absence of polymer chain ends that clearly distinguishes them from linear or branched polymers. However, the synthesis of macrocyclic polymers, particularly those possessing multiple cyclic units, remains challenging. Recently, our research group established a highly efficient method for the synthesis of multicyclic polymers without the use of cyclic precursors. This review provides a comprehensive overview of our recent studies and relevant research on the precise synthesis of multicyclic polymers, including cage-shaped polymers, spiro-multicyclic polymers, and graft polymers with macromolecular cyclic or cage side chains, via intramolecular ring-opening metathesis oligomerization or the cyclopolymerization of norbornenyl-functionalized macromonomers, mediated by third-generation Grubbs catalysts. In addition, their fundamental properties and potential applications are briefly discussed. Macromolecules with cyclic topologies exhibit unique structural properties, but synthesizing macrocyclic polymers—especially multicyclic ones—remains challenging. Our group has developed an efficient method to access multicyclic polymers without using cyclic precursors. This review highlights recent progress in the precise synthesis of multicyclic architectures, including cage-shaped, spiro-multicyclic, and graft polymers with cyclic or cage-like side chains, via intramolecular ring-opening metathesis oligomerization or cyclopolymerization of norbornenyl-functionalized macromonomers using Grubbs third-generation catalysts. Their fundamental properties and potential applications are also briefly summarized.
{"title":"Multicyclic polymer synthesis via a consecutive cyclization approach","authors":"Yamato Ebii, Minami Ebe, Feng Li, Takuya Isono, Toshifumi Satoh","doi":"10.1038/s41428-025-01078-w","DOIUrl":"10.1038/s41428-025-01078-w","url":null,"abstract":"Macromolecules with cyclic topologies have attracted significant attention because of the absence of polymer chain ends that clearly distinguishes them from linear or branched polymers. However, the synthesis of macrocyclic polymers, particularly those possessing multiple cyclic units, remains challenging. Recently, our research group established a highly efficient method for the synthesis of multicyclic polymers without the use of cyclic precursors. This review provides a comprehensive overview of our recent studies and relevant research on the precise synthesis of multicyclic polymers, including cage-shaped polymers, spiro-multicyclic polymers, and graft polymers with macromolecular cyclic or cage side chains, via intramolecular ring-opening metathesis oligomerization or the cyclopolymerization of norbornenyl-functionalized macromonomers, mediated by third-generation Grubbs catalysts. In addition, their fundamental properties and potential applications are briefly discussed. Macromolecules with cyclic topologies exhibit unique structural properties, but synthesizing macrocyclic polymers—especially multicyclic ones—remains challenging. Our group has developed an efficient method to access multicyclic polymers without using cyclic precursors. This review highlights recent progress in the precise synthesis of multicyclic architectures, including cage-shaped, spiro-multicyclic, and graft polymers with cyclic or cage-like side chains, via intramolecular ring-opening metathesis oligomerization or cyclopolymerization of norbornenyl-functionalized macromonomers using Grubbs third-generation catalysts. Their fundamental properties and potential applications are also briefly summarized.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 12","pages":"1295-1311"},"PeriodicalIF":2.7,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145666275","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 : 2025-08-15DOI: 10.1038/s41428-025-01079-9
Atsushi Matsumoto, Ikuto Kato, Chi Zhang, Shinji Sugihara, Yasushi Maeda, Frank Scheffold, Amy Q. Shen
We investigate the entanglement dynamics of salt-free aqueous solutions of poly(sodium styrenesulfonate) (NaPSS) across a range of molecular weights, focusing on the semidilute entangled regime. By combining conventional bulk shear rheometry with diffusing wave spectroscopy (DWS) microrheometry, we characterize key parameters, including the entanglement concentration, plateau modulus, reptation time, and Rouse time of entanglement strands. A clear crossover from polyelectrolyte-like to neutral polymer-like behavior is identified as the degree of polymerization decreases, corresponding to a critical monomer concentration cD ~ 0.3 M and a critical degree of polymerization N* ~ 6000. The experimental scaling relationships closely agree with the predictions from the Dobrynin model. Our findings provide new insights into the long-standing debate on the entanglement dynamics of polyelectrolytes and establish a framework for analyzing and controlling the solution properties of salt-free polyelectrolytes in the semidilute entangled regime. Moreover, they demonstrate the power of DWS microrheology for probing complex rheological behavior in polyelectrolyte systems. The entanglement dynamics of salt-free aqueous solutions of poly(sodium styrenesulfonate) was investigated using conventional bulk shear rheometry and diffusing wave spectroscopy microrheometry. Our scaling analysis of the entanglement concentration, plateau modulus, and relaxation time revealed a clear crossover from polyelectrolyte-like to neutral polymer-like behavior at a critical monomer concentration cD ~ 0.3 M and a critical degree of polymerization N* ~ 6000. We also found that the polymer concentration and molecular weight dependence of the tested entanglement parameters showed good agreement with the Dobrynin model.
{"title":"Microrheological study on the entanglement dynamics of salt-free polyelectrolyte solutions in the semidilute entangled regime","authors":"Atsushi Matsumoto, Ikuto Kato, Chi Zhang, Shinji Sugihara, Yasushi Maeda, Frank Scheffold, Amy Q. Shen","doi":"10.1038/s41428-025-01079-9","DOIUrl":"10.1038/s41428-025-01079-9","url":null,"abstract":"We investigate the entanglement dynamics of salt-free aqueous solutions of poly(sodium styrenesulfonate) (NaPSS) across a range of molecular weights, focusing on the semidilute entangled regime. By combining conventional bulk shear rheometry with diffusing wave spectroscopy (DWS) microrheometry, we characterize key parameters, including the entanglement concentration, plateau modulus, reptation time, and Rouse time of entanglement strands. A clear crossover from polyelectrolyte-like to neutral polymer-like behavior is identified as the degree of polymerization decreases, corresponding to a critical monomer concentration cD ~ 0.3 M and a critical degree of polymerization N* ~ 6000. The experimental scaling relationships closely agree with the predictions from the Dobrynin model. Our findings provide new insights into the long-standing debate on the entanglement dynamics of polyelectrolytes and establish a framework for analyzing and controlling the solution properties of salt-free polyelectrolytes in the semidilute entangled regime. Moreover, they demonstrate the power of DWS microrheology for probing complex rheological behavior in polyelectrolyte systems. The entanglement dynamics of salt-free aqueous solutions of poly(sodium styrenesulfonate) was investigated using conventional bulk shear rheometry and diffusing wave spectroscopy microrheometry. Our scaling analysis of the entanglement concentration, plateau modulus, and relaxation time revealed a clear crossover from polyelectrolyte-like to neutral polymer-like behavior at a critical monomer concentration cD ~ 0.3 M and a critical degree of polymerization N* ~ 6000. We also found that the polymer concentration and molecular weight dependence of the tested entanglement parameters showed good agreement with the Dobrynin model.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 11","pages":"1215-1225"},"PeriodicalIF":2.7,"publicationDate":"2025-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01079-9.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145436557","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}
Ring-opening alternating copolymerization (ROAC) of cyclic anhydrides and epoxides is a promising approach for the well-controlled synthesis of polyesters with versatile structures. ROAC typically yields amorphous polyesters owing to challenges in controlling the main-chain stereochemistry, whereas most applied polyesters are crystalline. Isobutylene oxide (IBO), a highly symmetric epoxide, can overcome this issue, thus facilitating the synthesis of crystalline polyesters via ROAC. However, low reactivity and potential side reactions remain major obstacles to achieving an IBO-based ROAC in a controlled manner. In this study, we successfully developed a well-controlled ROAC of cyclic anhydrides and IBO using environmentally benign organobase catalysts. Using t-BuP2 as a catalyst, the ROAC of phthalic anhydride (PA) and IBO proceeds smoothly, yielding crystalline P(PA-alt-IBO) with narrow molecular weight distribution (Đ ≤ 1.1). This method was extended to other cyclic anhydrides and initiators, enabling the synthesis of polyesters with diverse structures. Additionally, this ROAC system was applied to the synthesis of copolymers, including statistical copolymer of P(PA-alt-IBO) and P(PA-alt-butylene oxide), as well as block copolymer comprising P(PA-alt-IBO) and poly(trimethylene carbonate). This study not only expands the scope of epoxides in ROAC but also provides a straightforward and precise strategy for synthesizing crystalline polyesters and further macromolecular designs. A well-controlled ring-opening alternating copolymerization (ROAC) of cyclic anhydrides and isobutylene oxide (IBO) using organobase catalysts was developed. Using t-BuP2 as a catalyst, the ROAC of phthalic anhydride (PA) and IBO proceeds smoothly, yielding crystalline P(PA-alt-IBO) with narrow molecular weight distribution (Đ ≤ 1.1). This method was extended to other cyclic anhydrides and initiators. Additionally, this ROAC system was applied to the synthesis of copolymers, including statistical copolymer and block copolymer. This study provides a straightforward and precise strategy for synthesizing crystalline polyesters and further macromolecular designs.
{"title":"Ring-opening alternating copolymerization of cyclic anhydrides and isobutylene oxide using organobase catalysts","authors":"Moeno Sugiyama, Ryota Suzuki, Hiroto Ayakawa, Tianle Gao, Feng Li, Takuya Yamamoto, Takuya Isono, Toshifumi Satoh","doi":"10.1038/s41428-025-01087-9","DOIUrl":"10.1038/s41428-025-01087-9","url":null,"abstract":"Ring-opening alternating copolymerization (ROAC) of cyclic anhydrides and epoxides is a promising approach for the well-controlled synthesis of polyesters with versatile structures. ROAC typically yields amorphous polyesters owing to challenges in controlling the main-chain stereochemistry, whereas most applied polyesters are crystalline. Isobutylene oxide (IBO), a highly symmetric epoxide, can overcome this issue, thus facilitating the synthesis of crystalline polyesters via ROAC. However, low reactivity and potential side reactions remain major obstacles to achieving an IBO-based ROAC in a controlled manner. In this study, we successfully developed a well-controlled ROAC of cyclic anhydrides and IBO using environmentally benign organobase catalysts. Using t-BuP2 as a catalyst, the ROAC of phthalic anhydride (PA) and IBO proceeds smoothly, yielding crystalline P(PA-alt-IBO) with narrow molecular weight distribution (Đ ≤ 1.1). This method was extended to other cyclic anhydrides and initiators, enabling the synthesis of polyesters with diverse structures. Additionally, this ROAC system was applied to the synthesis of copolymers, including statistical copolymer of P(PA-alt-IBO) and P(PA-alt-butylene oxide), as well as block copolymer comprising P(PA-alt-IBO) and poly(trimethylene carbonate). This study not only expands the scope of epoxides in ROAC but also provides a straightforward and precise strategy for synthesizing crystalline polyesters and further macromolecular designs. A well-controlled ring-opening alternating copolymerization (ROAC) of cyclic anhydrides and isobutylene oxide (IBO) using organobase catalysts was developed. Using t-BuP2 as a catalyst, the ROAC of phthalic anhydride (PA) and IBO proceeds smoothly, yielding crystalline P(PA-alt-IBO) with narrow molecular weight distribution (Đ ≤ 1.1). This method was extended to other cyclic anhydrides and initiators. Additionally, this ROAC system was applied to the synthesis of copolymers, including statistical copolymer and block copolymer. This study provides a straightforward and precise strategy for synthesizing crystalline polyesters and further macromolecular designs.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 11","pages":"1153-1163"},"PeriodicalIF":2.7,"publicationDate":"2025-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01087-9.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145436550","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}
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