Palladium (Pd) recovery from high-level liquid waste (HLLW) is essential both for meeting ever-growing industrial demands and for immobilizing radioactive waste through vitrification. However, developing robust and highly selective Pd adsorbents that can operate in strong acids remains a significant challenge. Herein, we report a novel cysteine-tailored 2D polyaramid (2DPA-Cys) that exhibits superior selectivity, high adsorption capacity, and remarkable reusability for Pd2+ in HNO₃ solutions. The abundant cysteine groups in 2DPA-Cys provide binding sites for selective Pd adsorption, whereas the 2D polyaramid core ensures chemical stability and allows peripheral functionalization. Adsorption studies using linear pseudo-second-order and Langmuir isotherm models indicate uniform single-layer chemisorption, with a maximum adsorption capacity of approximately 0.65 mmol/g in 0.5 M HNO₃. X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) analyses revealed that the strong and highly selective adsorption of Pd2+ by 2DPA-Cys is attributable to the formation of S-Pd-O coordinate bonds. This work highlights a design strategy that leverages 2DPA as a low-cost, acid-stable platform rich in coupling sites, demonstrating its potential for efficient Pd recovery in acidic environments and suggesting broader applications in nuclear waste management. A novel cysteine-tailored 2D polyaramid (2DPA-Cys) was synthesized and exhibits superior selectivity, high adsorption capacity, and remarkable reusability for Pd2+ in HNO₃. The abundant cysteine groups provide binding sites for selective Pd adsorption, whereas the 2DPA core ensures chemical stability and peripheral functionalization. Adsorption studies of 2DPA-Cys indicated a maximum adsorption capacity of 0.65 mmol/g in 0.5 M HNO₃. XPS analysis and DFT calculations confirmed the crucial role of the thiol from cysteine and the synergistic effect of the amide from 2DPA in efficient and selective binding of Pd2+.
从高放废液（HLLW）中回收钯（Pd）对于满足日益增长的工业需求和通过玻璃化固定放射性废物都是必不可少的。然而，开发可在强酸中运行的坚固且高选择性的Pd吸附剂仍然是一个重大挑战。在这里，我们报告了一种新的半胱氨酸定制的2D聚酰胺（2DPA-Cys），它在HNO₃溶液中对Pd2+具有卓越的选择性、高吸附能力和显著的可重复使用性。2DPA-Cys中丰富的半胱氨酸基团为选择性吸附Pd提供了结合位点，而2D聚酰胺核心确保了化学稳定性并允许外围功能化。利用线性拟二阶和Langmuir等温线模型进行的吸附研究表明，在0.5 M HNO₃中，其最大吸附容量约为0.65 mmol/g。x射线光电子能谱（XPS）和密度泛函理论（DFT）分析表明，2DPA-Cys对Pd2+的强选择性吸附是由于形成了S-Pd-O配位键。这项工作强调了一种设计策略，利用2DPA作为一种低成本、酸稳定的平台，富含偶联位点，展示了其在酸性环境中有效回收Pd的潜力，并建议在核废料管理中更广泛的应用。合成了一种新型的半胱氨酸定制2D聚酰胺（2DPA-Cys），它对HNO₃中Pd2+具有优异的选择性、高的吸附能力和显著的可重复使用性。丰富的半胱氨酸基团为选择性吸附Pd提供了结合位点，而2DPA核心确保了化学稳定性和外围功能化。吸附研究表明，2DPA-Cys在0.5 M HNO₃中的最大吸附量为0.65 mmol/g。XPS分析和DFT计算证实了来自半胱氨酸的硫醇和来自2DPA的酰胺在有效和选择性结合Pd2+中的协同作用的关键作用。
{"title":"Acid-stable, cysteine-tailored two-dimensional polyaramid for selective palladium recovery","authors":"Zhengqiao Yin, Feifan Zheng, Hao Wu, Xiaoli Gong, Xinyi Wang, Yuwen Zeng","doi":"10.1038/s41428-025-01074-0","DOIUrl":"10.1038/s41428-025-01074-0","url":null,"abstract":"Palladium (Pd) recovery from high-level liquid waste (HLLW) is essential both for meeting ever-growing industrial demands and for immobilizing radioactive waste through vitrification. However, developing robust and highly selective Pd adsorbents that can operate in strong acids remains a significant challenge. Herein, we report a novel cysteine-tailored 2D polyaramid (2DPA-Cys) that exhibits superior selectivity, high adsorption capacity, and remarkable reusability for Pd2+ in HNO₃ solutions. The abundant cysteine groups in 2DPA-Cys provide binding sites for selective Pd adsorption, whereas the 2D polyaramid core ensures chemical stability and allows peripheral functionalization. Adsorption studies using linear pseudo-second-order and Langmuir isotherm models indicate uniform single-layer chemisorption, with a maximum adsorption capacity of approximately 0.65 mmol/g in 0.5 M HNO₃. X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) analyses revealed that the strong and highly selective adsorption of Pd2+ by 2DPA-Cys is attributable to the formation of S-Pd-O coordinate bonds. This work highlights a design strategy that leverages 2DPA as a low-cost, acid-stable platform rich in coupling sites, demonstrating its potential for efficient Pd recovery in acidic environments and suggesting broader applications in nuclear waste management. A novel cysteine-tailored 2D polyaramid (2DPA-Cys) was synthesized and exhibits superior selectivity, high adsorption capacity, and remarkable reusability for Pd2+ in HNO₃. The abundant cysteine groups provide binding sites for selective Pd adsorption, whereas the 2DPA core ensures chemical stability and peripheral functionalization. Adsorption studies of 2DPA-Cys indicated a maximum adsorption capacity of 0.65 mmol/g in 0.5 M HNO₃. XPS analysis and DFT calculations confirmed the crucial role of the thiol from cysteine and the synergistic effect of the amide from 2DPA in efficient and selective binding of Pd2+.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 11","pages":"1279-1285"},"PeriodicalIF":2.7,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01074-0.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145436539","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 : 2025-07-29DOI: 10.1038/s41428-025-01072-2
Fumihiko Tanaka, Jun Watanabe, Tatsuya Nakatani, Toru Ishikawa
This technical review introduces a groundbreaking strategy for improving carbon fiber performance through advanced microstructure control, overcoming the limitations of size effects. We pioneered the use of micromechanics to design microstructures that significantly improve carbon fiber performance. We subsequently developed innovative methods to control these fibers to achieve the desired microstructure. A key part of our research was the use of the Frontier Softmaterial Beamline (BL03XU beamline) at SPring-8, which allowed us to analyze structural variations within single fibers at the macroscopic, microscopic, and mesoscale levels. This approach led to the development of ultrastrong carbon fibers with a tensile strength improvement of approximately 10%, from 7 GPa to 8 GPa and a similar increase in compressive strength, all without altering the fiber diameter. These advances underscore the critical role of precise control of chemical reactions and continuous technological progress in enhancing the properties of carbon fibers. Our insights significantly contribute to potential applications of carbon fibers in various industries, particularly in the aerospace and energy sectors, where high-strength and lightweight materials are essential. We present a revolutionary approach to enhance carbon fiber performance through advanced microstructure design and control, addressing limitations of size effects. Utilizing micromechanics, we engineered optimized microstructures and developed innovative techniques for their precise manipulation. Key to our success was the use of synchrotron radiation facilities for X-ray structural analysis, enabling hierarchical examination of single fibers. This led to ultrastrong carbon fibers with a 10% increase in tensile strength (7 GPa to 8 GPa). Our findings hold transformative potential for aerospace and energy applications requiring high-strength, lightweight materials.
{"title":"Ultrastrong carbon fibers achieved through nanoscale tailoring","authors":"Fumihiko Tanaka, Jun Watanabe, Tatsuya Nakatani, Toru Ishikawa","doi":"10.1038/s41428-025-01072-2","DOIUrl":"10.1038/s41428-025-01072-2","url":null,"abstract":"This technical review introduces a groundbreaking strategy for improving carbon fiber performance through advanced microstructure control, overcoming the limitations of size effects. We pioneered the use of micromechanics to design microstructures that significantly improve carbon fiber performance. We subsequently developed innovative methods to control these fibers to achieve the desired microstructure. A key part of our research was the use of the Frontier Softmaterial Beamline (BL03XU beamline) at SPring-8, which allowed us to analyze structural variations within single fibers at the macroscopic, microscopic, and mesoscale levels. This approach led to the development of ultrastrong carbon fibers with a tensile strength improvement of approximately 10%, from 7 GPa to 8 GPa and a similar increase in compressive strength, all without altering the fiber diameter. These advances underscore the critical role of precise control of chemical reactions and continuous technological progress in enhancing the properties of carbon fibers. Our insights significantly contribute to potential applications of carbon fibers in various industries, particularly in the aerospace and energy sectors, where high-strength and lightweight materials are essential. We present a revolutionary approach to enhance carbon fiber performance through advanced microstructure design and control, addressing limitations of size effects. Utilizing micromechanics, we engineered optimized microstructures and developed innovative techniques for their precise manipulation. Key to our success was the use of synchrotron radiation facilities for X-ray structural analysis, enabling hierarchical examination of single fibers. This led to ultrastrong carbon fibers with a 10% increase in tensile strength (7 GPa to 8 GPa). Our findings hold transformative potential for aerospace and energy applications requiring high-strength, lightweight materials.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 12","pages":"1331-1337"},"PeriodicalIF":2.7,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145666280","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 : 2025-07-29DOI: 10.1038/s41428-025-01075-z
Satoshi Nakamura
Harnessing the plasmonic properties of gold nanorods (AuNRs) requires proper control of their arrangement and assembly. However, although the assembly of AuNRs into ordered structures has been achieved, active control over them remains challenging. The author and colleagues have developed methods to control the arrangement and assembly of AuNRs based on complex formation via electrostatic interactions with DNA, a polymer with unique properties, structure and excellent functionality. By adjusting the electrostatic interactions, the author and colleagues have achieved not only the ordered arrangement and assembly of AuNRs but also their active control. The author and colleagues have also successfully demonstrated the use of AuNR–DNA complex formation for analytical applications. This Focus Review presents our work on the arrangement and assembly of AuNRs by DNA. Harnessing the plasmonic properties of gold nanorods (AuNRs) requires proper control of their arrangement and assembly. However, although the assembly of AuNRs into ordered structures has been achieved, active control over them remains challenging. The author and colleagues have developed methods to control the arrangement and assembly of AuNRs based on complex formation via electrostatic interactions with DNA, a polymer with unique properties, structure and excellent functionality. This Focus Review presents our work on the arrangement and assembly of AuNRs by DNA.
{"title":"DNA-based arrangement and assembly of gold nanorods","authors":"Satoshi Nakamura","doi":"10.1038/s41428-025-01075-z","DOIUrl":"10.1038/s41428-025-01075-z","url":null,"abstract":"Harnessing the plasmonic properties of gold nanorods (AuNRs) requires proper control of their arrangement and assembly. However, although the assembly of AuNRs into ordered structures has been achieved, active control over them remains challenging. The author and colleagues have developed methods to control the arrangement and assembly of AuNRs based on complex formation via electrostatic interactions with DNA, a polymer with unique properties, structure and excellent functionality. By adjusting the electrostatic interactions, the author and colleagues have achieved not only the ordered arrangement and assembly of AuNRs but also their active control. The author and colleagues have also successfully demonstrated the use of AuNR–DNA complex formation for analytical applications. This Focus Review presents our work on the arrangement and assembly of AuNRs by DNA. Harnessing the plasmonic properties of gold nanorods (AuNRs) requires proper control of their arrangement and assembly. However, although the assembly of AuNRs into ordered structures has been achieved, active control over them remains challenging. The author and colleagues have developed methods to control the arrangement and assembly of AuNRs based on complex formation via electrostatic interactions with DNA, a polymer with unique properties, structure and excellent functionality. This Focus Review presents our work on the arrangement and assembly of AuNRs by DNA.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 12","pages":"1323-1330"},"PeriodicalIF":2.7,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01075-z.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145666269","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 : 2025-07-23DOI: 10.1038/s41428-025-01071-3
Thuong Thi Nghiem, Ba Lam Nguyen, Minh Tho Le, Van Hai Pham, Seiichi Kawahara
Self-healing (S-H) vulcanized natural rubber (V-NR) with multiple S-H factors was prepared via a magnesium oxide–zinc oxide (MgO–ZnO) coactivator. V-NR was prepared with the MgO–ZnO coactivator or ZnO alone and with N-tert-butyl-2-benzothiazyl sulfenamide (TBBS) or tetramethylthiuram disulfide (TMTD) as the accelerator. The most effective vulcanizing formulation incorporating the MgO–ZnO coactivator for S-H V-NR was subsequently applied to prepare S-H vulcanized epoxidized natural rubber (V-ENR). The curing characteristics of V-NR and V-ENR were analyzed, and their self-healability was assessed based on stress and strain recovery after the S-H process. The composition of the sulfur crosslink junctions was examined via Raman spectroscopy. The results revealed that the MgO‒ZnO coactivator facilitated disulfide and polysulfide bond formation, thereby enhancing self-healability through disulfide and/or polysulfide metathesis. Furthermore, the incorporation of the MgO‒ZnO coactivator to prepare V-ENR introduced multiple S-H factors, including the reformation of disulfide and polysulfide bonds and thermoreversible hydrogen bonding. Consequently, V-ENRs with multiple S-H factors exhibited superior self-healability compared with V-NRs prepared using the same vulcanizing formulation. Self-healing (S-H) vulcanized natural rubber (V-NR) and epoxidized natural rubber (V-ENR) were prepared using a magnesium oxide-zinc oxide (MgO-ZnO) coactivator. Compared to ZnO alone, the MgO-ZnO system enhanced disulfide and polysulfide bond formation, boosting self-healability through metathesis. Various accelerators, including N-tert-butyl-2-benzothiazyl sulfenamide (TBBS) and tetramethylthiuram disulfide (TMTD), were tested, and the optimal formulation was applied to V-ENR. The curing behavior and healing performance of V-NR and V-ENR were evaluated. V-ENR with MgO-ZnO showed superior healing due to multiple S-H factors, including disulfide and polysulfide bond reformation and thermoreversible hydrogen bonding.
{"title":"Preparation of self-healing vulcanized natural rubber with multiple self-healing factors by using a MgO‒ZnO coactivator","authors":"Thuong Thi Nghiem, Ba Lam Nguyen, Minh Tho Le, Van Hai Pham, Seiichi Kawahara","doi":"10.1038/s41428-025-01071-3","DOIUrl":"10.1038/s41428-025-01071-3","url":null,"abstract":"Self-healing (S-H) vulcanized natural rubber (V-NR) with multiple S-H factors was prepared via a magnesium oxide–zinc oxide (MgO–ZnO) coactivator. V-NR was prepared with the MgO–ZnO coactivator or ZnO alone and with N-tert-butyl-2-benzothiazyl sulfenamide (TBBS) or tetramethylthiuram disulfide (TMTD) as the accelerator. The most effective vulcanizing formulation incorporating the MgO–ZnO coactivator for S-H V-NR was subsequently applied to prepare S-H vulcanized epoxidized natural rubber (V-ENR). The curing characteristics of V-NR and V-ENR were analyzed, and their self-healability was assessed based on stress and strain recovery after the S-H process. The composition of the sulfur crosslink junctions was examined via Raman spectroscopy. The results revealed that the MgO‒ZnO coactivator facilitated disulfide and polysulfide bond formation, thereby enhancing self-healability through disulfide and/or polysulfide metathesis. Furthermore, the incorporation of the MgO‒ZnO coactivator to prepare V-ENR introduced multiple S-H factors, including the reformation of disulfide and polysulfide bonds and thermoreversible hydrogen bonding. Consequently, V-ENRs with multiple S-H factors exhibited superior self-healability compared with V-NRs prepared using the same vulcanizing formulation. Self-healing (S-H) vulcanized natural rubber (V-NR) and epoxidized natural rubber (V-ENR) were prepared using a magnesium oxide-zinc oxide (MgO-ZnO) coactivator. Compared to ZnO alone, the MgO-ZnO system enhanced disulfide and polysulfide bond formation, boosting self-healability through metathesis. Various accelerators, including N-tert-butyl-2-benzothiazyl sulfenamide (TBBS) and tetramethylthiuram disulfide (TMTD), were tested, and the optimal formulation was applied to V-ENR. The curing behavior and healing performance of V-NR and V-ENR were evaluated. V-ENR with MgO-ZnO showed superior healing due to multiple S-H factors, including disulfide and polysulfide bond reformation and thermoreversible hydrogen bonding.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"58 1","pages":"79-94"},"PeriodicalIF":2.7,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145896021","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 : 2025-07-09DOI: 10.1038/s41428-025-01051-7
Yu-I Hsu
Petroleum-based plastics are lightweight and durable and exhibit excellent formability. However, the increase in global plastics production, coupled with the economic development of emerging countries, and the resulting marine pollution caused by plastic waste have become serious problems in recent years. Polysaccharides, such as starch and cellulose, are the most abundant biopolymers in nature and are particularly promising plastic alternatives owing to their renewability, sustainability, and biodegradability. However, owing to their lack of water resistance and adequate mechanical properties, large-scale application of polysaccharide films in single-use plastics is limited because water resistance is preferred in many daily scenarios. Further research is required to optimize bioplastics to make them economically and practically feasible. In this report, we focus on stimuli-responsive materials that form or dissociate cross-linked structures in response to slight changes in external stimuli or the environment. We developed starch-based films with different disintegration/dissolution rates in freshwater and seawater as environmentally friendly materials. Modified starch was mixed with oxidized cellulose or a water-soluble polymer to prepare a transparent, homogeneous film. After the introduction of hydrogen bonds, the starch complex film was stable in freshwater; however, in seawater, the hydrogen bond crosslinks dissociated, causing the film to dissolve rapidly. This technology balances degradability in marine environments with water resistance in everyday environments, providing an alternative means of reducing marine plastic pollution, and it is expected to be applied in a variety of industrial sectors. In this study, we developed starch-based films with tunable disintegration and dissolution rates in freshwater and seawater. The modified starch was mixed with oxidized cellulose or a water-soluble polymer to produce transparent, homogeneous films. Hydrogen bonding stabilized the films in freshwater, while in seawater, the hydrogen bond crosslinks dissociated, causing the film to dissolve rapidly. This technology offers a strategic balance between water resistance in everyday environments and controlled disintegration in marine conditions, presenting a sustainable alternative to petrochemical plastics with potential applications across various industrial sectors.
{"title":"Development of functional degradable materials by precise crosslinking design of biobased polymers","authors":"Yu-I Hsu","doi":"10.1038/s41428-025-01051-7","DOIUrl":"10.1038/s41428-025-01051-7","url":null,"abstract":"Petroleum-based plastics are lightweight and durable and exhibit excellent formability. However, the increase in global plastics production, coupled with the economic development of emerging countries, and the resulting marine pollution caused by plastic waste have become serious problems in recent years. Polysaccharides, such as starch and cellulose, are the most abundant biopolymers in nature and are particularly promising plastic alternatives owing to their renewability, sustainability, and biodegradability. However, owing to their lack of water resistance and adequate mechanical properties, large-scale application of polysaccharide films in single-use plastics is limited because water resistance is preferred in many daily scenarios. Further research is required to optimize bioplastics to make them economically and practically feasible. In this report, we focus on stimuli-responsive materials that form or dissociate cross-linked structures in response to slight changes in external stimuli or the environment. We developed starch-based films with different disintegration/dissolution rates in freshwater and seawater as environmentally friendly materials. Modified starch was mixed with oxidized cellulose or a water-soluble polymer to prepare a transparent, homogeneous film. After the introduction of hydrogen bonds, the starch complex film was stable in freshwater; however, in seawater, the hydrogen bond crosslinks dissociated, causing the film to dissolve rapidly. This technology balances degradability in marine environments with water resistance in everyday environments, providing an alternative means of reducing marine plastic pollution, and it is expected to be applied in a variety of industrial sectors. In this study, we developed starch-based films with tunable disintegration and dissolution rates in freshwater and seawater. The modified starch was mixed with oxidized cellulose or a water-soluble polymer to produce transparent, homogeneous films. Hydrogen bonding stabilized the films in freshwater, while in seawater, the hydrogen bond crosslinks dissociated, causing the film to dissolve rapidly. This technology offers a strategic balance between water resistance in everyday environments and controlled disintegration in marine conditions, presenting a sustainable alternative to petrochemical plastics with potential applications across various industrial sectors.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 10","pages":"1095-1105"},"PeriodicalIF":2.7,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01051-7.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145228245","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}
Responsive materials have significant application value because of their ability to actively adjust their structure or properties in response to external stimuli. Poly(N-isopropylacrylamide) (PNIPAM) is widely used to form micelles, particularly for drug delivery, because its lower critical solution temperature (LCST) is close to body temperature. However, the preparation of micelles based on PNIPAM block copolymers often involves complex processes, which limit their broader application. Here, we employed polymerization-induced self-assembly (PISA) combined with in situ crosslinking to synthesize stabilized thermoresponsive micelles, such as poly(glycerol methacrylate)-b-poly(N-isopropylacrylamide)-B (PGMAx-b-PNIPAMy-B), which are spherical micelles with a thermoresponsive core of PNIPAM and a crosslinked shell of PGMA formed by sodium tetraborate decahydrate. The micelles exhibited rapid and reversible self-assembly and collapsed at 31 °C, enabling temperature regulation through light transmittance, which makes them suitable for smart window applications. Furthermore, these micelles demonstrated excellent friction-reducing and wear-resistant properties at various temperatures (25–36 °C) and under various loads (20–70 N), indicating their adaptive lubrication as additives. This work presents the facile fabrication of thermoresponsive micelles and expands the application of PISA technology in the tribological field. Responsive materials have significant application value because of their ability to actively adjust their structure or properties in response to external stimuli. We employed polymerization-induced self-assembly combined with in situ crosslinking to synthesize stabilized thermoresponsive micelles, such as poly(glycerol methacrylate)-b-poly(N-isopropylacrylamide)-B, which exhibited rapid and reversible self-assembly. Furthermore, these micelles demonstrated excellent friction-reducing and wear-resistant properties showcasing their adaptive lubrication as additives. This work presents the facile fabrication of thermoresponsive micelles and expands the application of PISA technology in the tribological field.
{"title":"Polymerization-induced self-assembly of thermoresponsive micelles and their lubrication adaptivity","authors":"Linjie Yang, Hanfeng Liu, Pengrui Cao, Junhui Gong, Xinrui Zhang, Tingmei Wang, Liming Tao, Xianqiang Pei, Qihua Wang, Jianqiang Zhang, Yaoming Zhang","doi":"10.1038/s41428-025-01057-1","DOIUrl":"10.1038/s41428-025-01057-1","url":null,"abstract":"Responsive materials have significant application value because of their ability to actively adjust their structure or properties in response to external stimuli. Poly(N-isopropylacrylamide) (PNIPAM) is widely used to form micelles, particularly for drug delivery, because its lower critical solution temperature (LCST) is close to body temperature. However, the preparation of micelles based on PNIPAM block copolymers often involves complex processes, which limit their broader application. Here, we employed polymerization-induced self-assembly (PISA) combined with in situ crosslinking to synthesize stabilized thermoresponsive micelles, such as poly(glycerol methacrylate)-b-poly(N-isopropylacrylamide)-B (PGMAx-b-PNIPAMy-B), which are spherical micelles with a thermoresponsive core of PNIPAM and a crosslinked shell of PGMA formed by sodium tetraborate decahydrate. The micelles exhibited rapid and reversible self-assembly and collapsed at 31 °C, enabling temperature regulation through light transmittance, which makes them suitable for smart window applications. Furthermore, these micelles demonstrated excellent friction-reducing and wear-resistant properties at various temperatures (25–36 °C) and under various loads (20–70 N), indicating their adaptive lubrication as additives. This work presents the facile fabrication of thermoresponsive micelles and expands the application of PISA technology in the tribological field. Responsive materials have significant application value because of their ability to actively adjust their structure or properties in response to external stimuli. We employed polymerization-induced self-assembly combined with in situ crosslinking to synthesize stabilized thermoresponsive micelles, such as poly(glycerol methacrylate)-b-poly(N-isopropylacrylamide)-B, which exhibited rapid and reversible self-assembly. Furthermore, these micelles demonstrated excellent friction-reducing and wear-resistant properties showcasing their adaptive lubrication as additives. This work presents the facile fabrication of thermoresponsive micelles and expands the application of PISA technology in the tribological field.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 10","pages":"1115-1125"},"PeriodicalIF":2.7,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145228248","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 : 2025-06-18DOI: 10.1038/s41428-025-01069-x
Kazuki Fukushima
Polymers and plastics pose environmental challenges, including marine pollution from waste and CO2 emissions from incineration. Recycling and upcycling are crucial strategies for conserving petroleum resources and reducing waste discharge. Additionally, developing sustainable polymers is essential for achieving a circular economy. Polymer degradation is a key process in both recycling and sustainable polymer development. This review examines the degradation of condensation polymers, such as polyesters and polycarbonates, when organic catalysts are used to enhance transesterification. Organic bases exhibit high catalytic efficiency in polymer degradation, whereas others facilitate the controlled polymerization of substituted cyclic esters and carbonates. Notably, 1,5,7-triazabicyclo[4.4.0]dec-7-ene has exceptional efficiency in degrading various condensation polymers, including aliphatic polycarbonates and liquid-crystalline wholly aromatic polyesters, via a dual hydrogen-bonding activation mechanism. The functionalization of aliphatic polycarbonates via side-chain modifications is a promising approach for producing functionalized degradable polymers, supported by efficient monomer synthesis and established ring-opening polymerization (ROP) techniques using organic catalysts. Precise polymer synthesis enhances mechanical and thermal properties by incorporating rigid moieties while enabling degradation control. These advancements contribute to the development of sustainable materials within a future circular economy. This paper reviews the degradation of polyesters and polycarbonates, including degradable aliphatic polymers. Organic catalysts enable efficient degradation and recycling of these condensation polymers, promoting a circular economy and reduction of waste and CO2 emissions. Although super engineering plastics are difficult to recycle, recent studies show organocatalysts can facilitate their depolymerization and monomer recovery. Advances in monomer synthesis and controlled ring-opening polymerization allow for functional, sustainable, and degradable polymers. Moreover, side-chain engineering in aliphatic polymers enables controlled degradation. Future work should emphasize greener synthesis and comprehensive analysis of degradation impacts.
{"title":"Degradation technologies for condensation polymers mediated by organic catalysts","authors":"Kazuki Fukushima","doi":"10.1038/s41428-025-01069-x","DOIUrl":"10.1038/s41428-025-01069-x","url":null,"abstract":"Polymers and plastics pose environmental challenges, including marine pollution from waste and CO2 emissions from incineration. Recycling and upcycling are crucial strategies for conserving petroleum resources and reducing waste discharge. Additionally, developing sustainable polymers is essential for achieving a circular economy. Polymer degradation is a key process in both recycling and sustainable polymer development. This review examines the degradation of condensation polymers, such as polyesters and polycarbonates, when organic catalysts are used to enhance transesterification. Organic bases exhibit high catalytic efficiency in polymer degradation, whereas others facilitate the controlled polymerization of substituted cyclic esters and carbonates. Notably, 1,5,7-triazabicyclo[4.4.0]dec-7-ene has exceptional efficiency in degrading various condensation polymers, including aliphatic polycarbonates and liquid-crystalline wholly aromatic polyesters, via a dual hydrogen-bonding activation mechanism. The functionalization of aliphatic polycarbonates via side-chain modifications is a promising approach for producing functionalized degradable polymers, supported by efficient monomer synthesis and established ring-opening polymerization (ROP) techniques using organic catalysts. Precise polymer synthesis enhances mechanical and thermal properties by incorporating rigid moieties while enabling degradation control. These advancements contribute to the development of sustainable materials within a future circular economy. This paper reviews the degradation of polyesters and polycarbonates, including degradable aliphatic polymers. Organic catalysts enable efficient degradation and recycling of these condensation polymers, promoting a circular economy and reduction of waste and CO2 emissions. Although super engineering plastics are difficult to recycle, recent studies show organocatalysts can facilitate their depolymerization and monomer recovery. Advances in monomer synthesis and controlled ring-opening polymerization allow for functional, sustainable, and degradable polymers. Moreover, side-chain engineering in aliphatic polymers enables controlled degradation. Future work should emphasize greener synthesis and comprehensive analysis of degradation impacts.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 10","pages":"1083-1094"},"PeriodicalIF":2.7,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01069-x.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145228246","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 designed and synthesized a filler comprising a polyoctahedral oligomeric silsesquioxane (POSS) core and perfluoroalkyl side chains. We found that by blending POSS fillers into a fluorinated polymer, the refractive indices of fluorinated polymer films can be efficiently lowered. The perfluoroalkyl side chains increase the compatibility with fluorinated polymers, and the dendrimer-like structure of POSS creates a large space in the material. The degree of packing was quantitatively evaluated by using the packing coefficient (kp), which was decomposed into two components: the fluorinated polymer (kp,1) and the POSS (kp,2). Owing to the small packing coefficient of the POSS component (kp,2 = 0.430–0.513), the refractive index (n) of the composite material decreased to n = 1.379 from that of the pristine fluorinated polymer (n = 1.424, kp,1 = 0.68–0.76). This study represents a milestone for further reducing the refractive indices of various fluorinated polymers currently in practical use. Fluorinated polymer composite materials of PVDF-HFP and a perfluoroalkylated POSS (F7POSS) filler were manufactured. The refractive indices of the resulting composite films decreased as the content of the POSS filler increased, and the thermal stability remained sufficient. The degree of packing was quantitatively evaluated by using the packing coefficient from the Lorentz–Lorenz equation.
{"title":"Fabrication of fluorinated polymer composite materials with a perfluoroalkylated POSS filler to reduce the refractive index","authors":"Tatsuaki Kunimitsu, Keisuke Shibahara, Masayuki Gon, Kazuo Tanaka","doi":"10.1038/s41428-025-01067-z","DOIUrl":"10.1038/s41428-025-01067-z","url":null,"abstract":"In this study, we designed and synthesized a filler comprising a polyoctahedral oligomeric silsesquioxane (POSS) core and perfluoroalkyl side chains. We found that by blending POSS fillers into a fluorinated polymer, the refractive indices of fluorinated polymer films can be efficiently lowered. The perfluoroalkyl side chains increase the compatibility with fluorinated polymers, and the dendrimer-like structure of POSS creates a large space in the material. The degree of packing was quantitatively evaluated by using the packing coefficient (kp), which was decomposed into two components: the fluorinated polymer (kp,1) and the POSS (kp,2). Owing to the small packing coefficient of the POSS component (kp,2 = 0.430–0.513), the refractive index (n) of the composite material decreased to n = 1.379 from that of the pristine fluorinated polymer (n = 1.424, kp,1 = 0.68–0.76). This study represents a milestone for further reducing the refractive indices of various fluorinated polymers currently in practical use. Fluorinated polymer composite materials of PVDF-HFP and a perfluoroalkylated POSS (F7POSS) filler were manufactured. The refractive indices of the resulting composite films decreased as the content of the POSS filler increased, and the thermal stability remained sufficient. The degree of packing was quantitatively evaluated by using the packing coefficient from the Lorentz–Lorenz equation.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 10","pages":"1107-1114"},"PeriodicalIF":2.7,"publicationDate":"2025-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01067-z.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145228244","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 : 2025-06-12DOI: 10.1038/s41428-025-01064-2
Hideo Ohkita
Polymer solar cells, which include a blend of electron-donating conjugated polymers and electron-accepting molecules in the photovoltaic layer, have been widely studied as next-generation solar cells. To improve photocurrent generation, it is necessary to harvest as many photons as possible in solar light, which distributes over a wide wavelength including the ultraviolet, visible, and near-infrared (near-IR) regions. However, covering such a wide solar spectrum by using binary blend polymer solar cells is inherently difficult because most organic materials (e.g., conjugated polymers) have a narrow absorption bandwidth (less than 200 nm). Ternary blend polymer solar cells can overcome this limitation by combining near-IR light-harvesting materials with the electron-donor conjugated polymer and the electron-acceptor molecule. In this review, recent progress in the development of polymer solar cells is briefly overviewed, followed by a detailed description of ternary blend polymer solar cells. Ternary blend polymer solar cells incorporating near-IR materials are among the most promising approaches for effectively improving photovoltaic performance because they can extend the light-harvesting wavelength range and simultaneously improve charge transport. Here, we briefly review the progress in polymer solar cells and describe our recent studies on ternary blend polymer solar cells incorporating near-IR dye molecules. Of particular importance is the interfacial engineering for the placement of near-IR dye molecules at the donor/acceptor interface in ternary blend polymer solar cells.
{"title":"Interface engineering for ternary blend polymer solar cells based on spectroscopic and device analyses","authors":"Hideo Ohkita","doi":"10.1038/s41428-025-01064-2","DOIUrl":"10.1038/s41428-025-01064-2","url":null,"abstract":"Polymer solar cells, which include a blend of electron-donating conjugated polymers and electron-accepting molecules in the photovoltaic layer, have been widely studied as next-generation solar cells. To improve photocurrent generation, it is necessary to harvest as many photons as possible in solar light, which distributes over a wide wavelength including the ultraviolet, visible, and near-infrared (near-IR) regions. However, covering such a wide solar spectrum by using binary blend polymer solar cells is inherently difficult because most organic materials (e.g., conjugated polymers) have a narrow absorption bandwidth (less than 200 nm). Ternary blend polymer solar cells can overcome this limitation by combining near-IR light-harvesting materials with the electron-donor conjugated polymer and the electron-acceptor molecule. In this review, recent progress in the development of polymer solar cells is briefly overviewed, followed by a detailed description of ternary blend polymer solar cells. Ternary blend polymer solar cells incorporating near-IR materials are among the most promising approaches for effectively improving photovoltaic performance because they can extend the light-harvesting wavelength range and simultaneously improve charge transport. Here, we briefly review the progress in polymer solar cells and describe our recent studies on ternary blend polymer solar cells incorporating near-IR dye molecules. Of particular importance is the interfacial engineering for the placement of near-IR dye molecules at the donor/acceptor interface in ternary blend polymer solar cells.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 10","pages":"1067-1081"},"PeriodicalIF":2.7,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01064-2.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145228249","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 behavior of water molecules significantly influences the effectiveness of protein stabilizers and biomaterials. Although the polymerization of low-molecular-weight molecules enhances their functionality, the hydration states and water dynamics around polymers and small molecules are typically examined separately. Therefore, the effect of polymerization on water dynamics at the molecular level remains unclear. By density functional tight-binding molecular dynamics (DFTB-MD) simulations of five zwitterionic solute solutions, (trimethylamine N-oxide) (TMAO), the N-[3-(dimethylamino)propyl]acrylamide N-oxide (DMAO) monomer, poly(N-[3-(dimethylamino)propyl]acrylamide N-oxide) (PDMAO), the 2-methacryloyloxyethyl phosphorylcholine (MPC) monomer, and poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC), the effects of polymerization on water dynamics were investigated. DMAO and MPC polymerization (to PDMAO and PMPC, respectively) promote the slow and rapid rotation of water molecules, respectively. In PDMAO, water molecules are trapped between side chains due to the formation of hydrogen bonds between water and PDMAO, resulting in slow water dynamics, whereas in PMPC, a reduction in the solvent-accessible surface area due to polymerization disrupts the hydrogen-bond network among the water molecules, resulting in acceleration of the rotational dynamics of water molecules. The hydration amount determined using differential scanning calorimetry (DSC) and terahertz time-domain spectroscopy (THz-TDS) is consistent with the MD simulation results, which provide molecular-level insights that advance the current understanding of water dynamics in small-molecule polymerization for potential functional enhancement. Caption: A different effect of polymerization on water dynamics: water molecules trapped by the side chains exhibit slow dynamics, whereas water dynamics is accelerated without the trap.
{"title":"Effect of zwitterionic monomer polymerization on water dynamics: a molecular dynamics simulation study supported by differential scanning calorimetry and terahertz spectroscopy","authors":"Md Abu Saleh, Yuji Higuchi, Shohei Shiomoto, Takahisa Anada, Mafumi Hishida, Masaru Tanaka","doi":"10.1038/s41428-025-01066-0","DOIUrl":"10.1038/s41428-025-01066-0","url":null,"abstract":"The behavior of water molecules significantly influences the effectiveness of protein stabilizers and biomaterials. Although the polymerization of low-molecular-weight molecules enhances their functionality, the hydration states and water dynamics around polymers and small molecules are typically examined separately. Therefore, the effect of polymerization on water dynamics at the molecular level remains unclear. By density functional tight-binding molecular dynamics (DFTB-MD) simulations of five zwitterionic solute solutions, (trimethylamine N-oxide) (TMAO), the N-[3-(dimethylamino)propyl]acrylamide N-oxide (DMAO) monomer, poly(N-[3-(dimethylamino)propyl]acrylamide N-oxide) (PDMAO), the 2-methacryloyloxyethyl phosphorylcholine (MPC) monomer, and poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC), the effects of polymerization on water dynamics were investigated. DMAO and MPC polymerization (to PDMAO and PMPC, respectively) promote the slow and rapid rotation of water molecules, respectively. In PDMAO, water molecules are trapped between side chains due to the formation of hydrogen bonds between water and PDMAO, resulting in slow water dynamics, whereas in PMPC, a reduction in the solvent-accessible surface area due to polymerization disrupts the hydrogen-bond network among the water molecules, resulting in acceleration of the rotational dynamics of water molecules. The hydration amount determined using differential scanning calorimetry (DSC) and terahertz time-domain spectroscopy (THz-TDS) is consistent with the MD simulation results, which provide molecular-level insights that advance the current understanding of water dynamics in small-molecule polymerization for potential functional enhancement. Caption: A different effect of polymerization on water dynamics: water molecules trapped by the side chains exhibit slow dynamics, whereas water dynamics is accelerated without the trap.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 10","pages":"1127-1139"},"PeriodicalIF":2.7,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01066-0.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145228250","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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