Pub Date : 2025-10-01DOI: 10.1038/s41428-025-01103-y
Hina Onozaki, Huynh Ngoc Dan Phuong, Sana Maruoka, Shingo Tamesue
Interest in environmental problems is increasing worldwide. Among these issues, microplastics—microscaled plastics formed from plastic waste—are emerging as a serious threat. Various animals in the ocean and other environments are affected by microplastics. In this work, we develop a decomposable and recyclable polymeric material using polystyrene with trithiocarbonate substituents in its chemical structure to remove plastic waste and address the environmental problems associated with plastics. This polymeric material can be decomposed by reaction with allylamine at room temperature and crumbles 96 h after allylamine is poured on it. Moreover, the decomposed polymer is recyclable via a thiol-ene reaction with UV irradiation (λ = 365 nm, 6 h). A decomposable and recyclable polymer consisting of polystyrene and trithiocarbonates was synthesized. The synthesized polymer decomposed by mixing with allylamine. The decomposition was due to the reaction between trithiocarbonate in the polymer and allylamine. The decomposition was evaluated by the indentation test and the spectroscopies (e.g., 1H NMR). Following the decomposition, the recycling of the decomposed polymer was conducted via a thiol-ene reaction by shining UV light (λ =365 nm). The resultant recycled polymer showed as high mechanical strength as the original polymer before decomposition.
{"title":"Design of a decomposable and recyclable polymeric material via oligo(trithiocarbonate) and its chemical reaction with allylamine","authors":"Hina Onozaki, Huynh Ngoc Dan Phuong, Sana Maruoka, Shingo Tamesue","doi":"10.1038/s41428-025-01103-y","DOIUrl":"10.1038/s41428-025-01103-y","url":null,"abstract":"Interest in environmental problems is increasing worldwide. Among these issues, microplastics—microscaled plastics formed from plastic waste—are emerging as a serious threat. Various animals in the ocean and other environments are affected by microplastics. In this work, we develop a decomposable and recyclable polymeric material using polystyrene with trithiocarbonate substituents in its chemical structure to remove plastic waste and address the environmental problems associated with plastics. This polymeric material can be decomposed by reaction with allylamine at room temperature and crumbles 96 h after allylamine is poured on it. Moreover, the decomposed polymer is recyclable via a thiol-ene reaction with UV irradiation (λ = 365 nm, 6 h). A decomposable and recyclable polymer consisting of polystyrene and trithiocarbonates was synthesized. The synthesized polymer decomposed by mixing with allylamine. The decomposition was due to the reaction between trithiocarbonate in the polymer and allylamine. The decomposition was evaluated by the indentation test and the spectroscopies (e.g., 1H NMR). Following the decomposition, the recycling of the decomposed polymer was conducted via a thiol-ene reaction by shining UV light (λ =365 nm). The resultant recycled polymer showed as high mechanical strength as the original polymer before decomposition.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"58 1","pages":"69-78"},"PeriodicalIF":2.7,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01103-y.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145896013","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 : 2025-09-26DOI: 10.1038/s41428-025-01105-w
Thuong Thi Nghiem, Ba Lam Nguyen, Minh Tho Le, Van Hai Pham, Seiichi Kawahara
{"title":"Correction: 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/s41428-025-01105-w","DOIUrl":"10.1038/s41428-025-01105-w","url":null,"abstract":"","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"58 1","pages":"101-101"},"PeriodicalIF":2.7,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01105-w.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145896017","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 : 2025-09-22DOI: 10.1038/s41428-025-01101-0
Yuuki Hata
Nanocelluloses, which are prepared from natural cellulose sources in a top-down manner through physical and/or chemical treatments, are broadening the scope of applications of sustainable biopolymers. These naturally derived nanocelluloses exhibit one-dimensional nanomorphologies, such as nanofibers and nanorods, which originate from the intrinsic nanostructures formed by cellulose molecules in plants and other cellulose-producing organisms. Recent studies have developed artificial nanocelluloses that are constructed in vitro at the molecular level via the self-assembly of low-molecular-weight (LMW) cellulose. These artificial nanocelluloses feature unique nanostructures, including rectangular nanosheets, square nanosheets, distorted nanosheets, and helical nanorods. Nevertheless, most artificial nanocelluloses reported to date are particulates. We have developed two types of nanostructured macroscopic materials through the self-assembly of LMW cellulose: nanoribbon network hydrogels and nanospiked microfibrous materials. These novel nanostructured cellulose materials have shown great promise for distinctive applications of cellulose. This Focus Review summarizes our work along with related studies on nanostructured macroscopic materials constructed via the self-assembly of LMW cellulose. Artificial nanocelluloses are produced via the self-assembly of low-molecular-weight (LMW) cellulose in vitro and represent an emerging class of nanocelluloses developed over the past decade. Most artificial nanocelluloses reported to date are particulates. We have developed two types of nanostructured macroscopic materials through the self-assembly of LMW cellulose: nanoribbon network hydrogels and nanospiked microfibrous materials. This Focus Review summarizes our work along with related studies on these novel nanostructured cellulose materials.
{"title":"Self-assembly of low-molecular-weight cellulose into nanostructured macroscopic materials","authors":"Yuuki Hata","doi":"10.1038/s41428-025-01101-0","DOIUrl":"10.1038/s41428-025-01101-0","url":null,"abstract":"Nanocelluloses, which are prepared from natural cellulose sources in a top-down manner through physical and/or chemical treatments, are broadening the scope of applications of sustainable biopolymers. These naturally derived nanocelluloses exhibit one-dimensional nanomorphologies, such as nanofibers and nanorods, which originate from the intrinsic nanostructures formed by cellulose molecules in plants and other cellulose-producing organisms. Recent studies have developed artificial nanocelluloses that are constructed in vitro at the molecular level via the self-assembly of low-molecular-weight (LMW) cellulose. These artificial nanocelluloses feature unique nanostructures, including rectangular nanosheets, square nanosheets, distorted nanosheets, and helical nanorods. Nevertheless, most artificial nanocelluloses reported to date are particulates. We have developed two types of nanostructured macroscopic materials through the self-assembly of LMW cellulose: nanoribbon network hydrogels and nanospiked microfibrous materials. These novel nanostructured cellulose materials have shown great promise for distinctive applications of cellulose. This Focus Review summarizes our work along with related studies on nanostructured macroscopic materials constructed via the self-assembly of LMW cellulose. Artificial nanocelluloses are produced via the self-assembly of low-molecular-weight (LMW) cellulose in vitro and represent an emerging class of nanocelluloses developed over the past decade. Most artificial nanocelluloses reported to date are particulates. We have developed two types of nanostructured macroscopic materials through the self-assembly of LMW cellulose: nanoribbon network hydrogels and nanospiked microfibrous materials. This Focus Review summarizes our work along with related studies on these novel nanostructured cellulose materials.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"58 1","pages":"31-41"},"PeriodicalIF":2.7,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01101-0.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145896016","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 : 2025-09-18DOI: 10.1038/s41428-025-01098-6
Rena Tajima, Shintaro Nakagawa, Naoko Yoshie
Polymers incorporating hydrogen bonding (H-bonding) units have attracted significant attention for their ability to enhance mechanical properties, including elastic modulus, toughness, and stretchability, owing to the reversible nature of H-bonds. These interactions can act as apparent crosslinks under small strains and facilitate energy dissipation and network restoration under large strains or upon stress release. A critical aspect influencing the macroscopic behavior of such materials is the structural flexibility of the H-bonding motifs. This review categorizes H-bonds into two groups: “rigid” multiple H-bonds, often characterized by π-conjugated units and structural complementarity (e.g., UPy and nucleobases), which impart directionality and strong association, and “flexible” multiple H-bonds (e.g., aliphatic vicinal diols), which exhibit various bonding modes due to conformational freedom and the absence of strong π-conjugation. We discuss how these differences in structural flexibility profoundly affect the mechanoresponsive behavior of the polymers. This review is specifically focused on H-bonds within polymers without solvents, thereby elucidating the intrinsic effects of H-bond architecture on material properties, independent of solvent or small-molecule interactions. This review delineates a design strategy for mechanoresponsive polymers by categorizing hydrogen-bonding (H-bonding) motifs into “rigid” and “flexible” types. Rigid H-bonds, with strong directionality, provide high elasticity and strength. In contrast, flexible H-bonds, such as aliphatic diols, possess multiple, conformationally diverse binding modes. This flexibility allows for more efficient energy dissipation and network recovery under strain, leading to materials with superior dynamicity. We discuss the intrinsic effects of structural flexibility of H-bonding groups on mechanical properties, independent of solvent interactions.
{"title":"Multiple hydrogen bonds as tools to enhance the mechanical and mechanoresponsive properties of polymers","authors":"Rena Tajima, Shintaro Nakagawa, Naoko Yoshie","doi":"10.1038/s41428-025-01098-6","DOIUrl":"10.1038/s41428-025-01098-6","url":null,"abstract":"Polymers incorporating hydrogen bonding (H-bonding) units have attracted significant attention for their ability to enhance mechanical properties, including elastic modulus, toughness, and stretchability, owing to the reversible nature of H-bonds. These interactions can act as apparent crosslinks under small strains and facilitate energy dissipation and network restoration under large strains or upon stress release. A critical aspect influencing the macroscopic behavior of such materials is the structural flexibility of the H-bonding motifs. This review categorizes H-bonds into two groups: “rigid” multiple H-bonds, often characterized by π-conjugated units and structural complementarity (e.g., UPy and nucleobases), which impart directionality and strong association, and “flexible” multiple H-bonds (e.g., aliphatic vicinal diols), which exhibit various bonding modes due to conformational freedom and the absence of strong π-conjugation. We discuss how these differences in structural flexibility profoundly affect the mechanoresponsive behavior of the polymers. This review is specifically focused on H-bonds within polymers without solvents, thereby elucidating the intrinsic effects of H-bond architecture on material properties, independent of solvent or small-molecule interactions. This review delineates a design strategy for mechanoresponsive polymers by categorizing hydrogen-bonding (H-bonding) motifs into “rigid” and “flexible” types. Rigid H-bonds, with strong directionality, provide high elasticity and strength. In contrast, flexible H-bonds, such as aliphatic diols, possess multiple, conformationally diverse binding modes. This flexibility allows for more efficient energy dissipation and network recovery under strain, leading to materials with superior dynamicity. We discuss the intrinsic effects of structural flexibility of H-bonding groups on mechanical properties, independent of solvent interactions.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"58 1","pages":"1-13"},"PeriodicalIF":2.7,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01098-6.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145896023","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 : 2025-09-01DOI: 10.1038/s41428-025-01093-x
Nam Truong Hoai, Trang Ho Le Hanh, Hang Nguyen Thi Thu, Ngoc Nguyen Vo Hong, An Ngo Ngoc Bao, Minh Vu Tue, Trong Tran Huy, Thanh Do Kim, Huyen Doan Thi Hoa, Luyen Thi Tran, Hiroaki Yoshida, Hiroharu Ajiro, Thuy Tran Thi
In this study, a novel poly(vinyl alcohol) (PVA) membrane modified with L-glutamic acid was synthesized using poly(ethylene glycol) (PEG) as a porogen to increase the surface area and improve Cu(II) adsorption. The phase separation between PVA and PEG induced pore formation, extending from the surface into the interior. PEG also acted as a plasticizer, increasing polymer chain flexibility. The effects of the PEG content on the structural and physicochemical properties were analyzed via water absorption, FT-IR, TGA, XRD, and SEM. The results showed that the incorporation of PEG significantly influenced the material properties. Additionally, adsorption, desorption, kinetic, and isotherm studies were conducted to evaluate the adsorption process. The Cu(II) adsorption capacity increased from 31.8 mg/g to 51.1 mg/g with an initial Cu(II) concentration of 95.0 mg/L. The adsorption equilibrium followed the Freundlich isotherm model, suggesting a heterogeneous surface with various adsorption sites. Kinetic analysis revealed pseudo-second-order kinetics. Desorption studies revealed efficient Cu(II) release in 2 M HNO3 within 150 min, resulting in an 81.9% desorption efficiency. Thermal analysis revealed a lower degradation range (262 °C) compared to that of pure PVA (339 °C), which was attributed to the increased surface area. Additionally, the incorporation of PEG reduced the crystallinity of PVA-c-Glu/PEG. These findings highlight the potential of PEG-modified porous PVA for sustainable heavy metal removal in environmental applications. This study presented a noval material derived from poly(vinyl alcohol) (PVA), which was crosslinked with L-glutamic acid to improve the poor stability of PVA in water and modified with surface porosity introduced by poly(ethylene glycol) (PEG). The research primarily focused on elucidating the influence of PEG on the physicochemical properties of the material, which were governed by phase separation and hydrogen bonding interactions with PVA. The presence of porous structures significantly altered the material’s properties and enhanced its adsorption capacity toward copper(II) ions.
本研究以聚乙二醇（PEG）为破孔剂，合成了l -谷氨酸修饰的聚乙烯醇（PVA）膜，增加了膜的表面积，提高了膜对Cu（II）的吸附能力。PVA和PEG之间的相分离诱导了孔隙的形成，从表面延伸到内部。聚乙二醇还起到增塑剂的作用，增加聚合物链的柔韧性。通过吸水率、红外光谱（FT-IR）、热重分析仪（TGA）、x射线衍射（XRD）、扫描电镜（SEM）等分析了PEG含量对聚合物结构和理化性质的影响。结果表明，聚乙二醇的掺入对材料性能有显著影响。此外，还进行了吸附、解吸、动力学和等温线研究来评价吸附过程。当Cu（II）初始浓度为95.0 mg/L时，Cu（II）的吸附容量由31.8 mg/g提高到51.1 mg/g。吸附平衡遵循Freundlich等温线模型，表明其表面具有不同的吸附位点。动力学分析显示为伪二级动力学。解吸研究表明，在2 M HNO3中，150 min内Cu（II）有效释放，解吸效率为81.9%。热分析显示，与纯PVA（339°C）相比，其降解范围（262°C）较低，这归因于增加的表面积。此外，PEG的掺入降低了PVA-c-Glu/PEG的结晶度。这些发现突出了聚乙二醇改性多孔聚乙烯醇在环境应用中可持续去除重金属的潜力。本研究以聚乙烯醇（PVA）为原料，通过与l -谷氨酸交联，改善PVA在水中稳定性差的问题，并通过聚乙二醇（PEG）引入表面孔隙进行改性，制备了一种新型材料。研究主要集中在阐明PEG对材料的物理化学性质的影响，这些影响是由相分离和与PVA的氢键相互作用决定的。多孔结构的存在显著改变了材料的性能，增强了其对铜（II）离子的吸附能力。
{"title":"Investigation of the effects of poly(ethylene glycol) on the properties of a novel poly(vinyl alcohol) membrane modified with L-glutamic acid for copper removal","authors":"Nam Truong Hoai, Trang Ho Le Hanh, Hang Nguyen Thi Thu, Ngoc Nguyen Vo Hong, An Ngo Ngoc Bao, Minh Vu Tue, Trong Tran Huy, Thanh Do Kim, Huyen Doan Thi Hoa, Luyen Thi Tran, Hiroaki Yoshida, Hiroharu Ajiro, Thuy Tran Thi","doi":"10.1038/s41428-025-01093-x","DOIUrl":"10.1038/s41428-025-01093-x","url":null,"abstract":"In this study, a novel poly(vinyl alcohol) (PVA) membrane modified with L-glutamic acid was synthesized using poly(ethylene glycol) (PEG) as a porogen to increase the surface area and improve Cu(II) adsorption. The phase separation between PVA and PEG induced pore formation, extending from the surface into the interior. PEG also acted as a plasticizer, increasing polymer chain flexibility. The effects of the PEG content on the structural and physicochemical properties were analyzed via water absorption, FT-IR, TGA, XRD, and SEM. The results showed that the incorporation of PEG significantly influenced the material properties. Additionally, adsorption, desorption, kinetic, and isotherm studies were conducted to evaluate the adsorption process. The Cu(II) adsorption capacity increased from 31.8 mg/g to 51.1 mg/g with an initial Cu(II) concentration of 95.0 mg/L. The adsorption equilibrium followed the Freundlich isotherm model, suggesting a heterogeneous surface with various adsorption sites. Kinetic analysis revealed pseudo-second-order kinetics. Desorption studies revealed efficient Cu(II) release in 2 M HNO3 within 150 min, resulting in an 81.9% desorption efficiency. Thermal analysis revealed a lower degradation range (262 °C) compared to that of pure PVA (339 °C), which was attributed to the increased surface area. Additionally, the incorporation of PEG reduced the crystallinity of PVA-c-Glu/PEG. These findings highlight the potential of PEG-modified porous PVA for sustainable heavy metal removal in environmental applications. This study presented a noval material derived from poly(vinyl alcohol) (PVA), which was crosslinked with L-glutamic acid to improve the poor stability of PVA in water and modified with surface porosity introduced by poly(ethylene glycol) (PEG). The research primarily focused on elucidating the influence of PEG on the physicochemical properties of the material, which were governed by phase separation and hydrogen bonding interactions with PVA. The presence of porous structures significantly altered the material’s properties and enhanced its adsorption capacity toward copper(II) ions.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"58 1","pages":"53-67"},"PeriodicalIF":2.7,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145896015","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 : 2025-08-29DOI: 10.1038/s41428-025-01091-z
Rintaro Takahashi, Ayae Sugawara-Narutaki, Ken Terao
Time-resolved small-angle X-ray scattering (TR-SAXS) is an indispensable technique for directly monitoring in situ kinetic processes in soft matter, providing real-time structural information from nanometer to micrometer length scales. This Focus Review summarizes recent significant advances in understanding the self-assembly kinetics of block copolymers in solution, primarily revealed through TR-SAXS. The review is structured into three key sections, each addressing distinct driving forces and mechanisms. First, we discuss the formation and transformation of micelles, predominantly driven by non-covalent interactions like van der Waals forces and hydrophobic interactions, leading to the spontaneous association of amphiphilic block copolymers in selective solvents. Next, we cover polyelectrolyte complex micelles and vesicles, where self-assembly is initiated by electrostatic interactions, as mixing oppositely charged block polyelectrolytes in aqueous media forms complex coacervate structures. Finally, we present polymerization-induced self-assembly (PISA), a unique approach involving the in situ formation and evolution of block copolymer nanostructures as a monomer is polymerized from a pre-existing polymer chain, simultaneously achieving block copolymer synthesis and self-assembly. Through these examples, we highlight the power of TR-SAXS in elucidating the intricate kinetic pathways and underlying mechanisms governing block copolymer self-assembly. Time-resolved small-angle X-ray scattering (TR-SAXS) is crucial for real-time monitoring of soft matter kinetics, offering nanometer-to-micrometer structural insights and revealing complex kinetic pathways and mechanisms. This review highlights its power in understanding block copolymer self-assembly kinetics in solution, covering micelle formation driven by non-covalent interactions, polyelectrolyte complex micelles via electrostatic interactions, and polymerization-induced self-assembly (PISA).
{"title":"A viewpoint on block copolymer self-assembly revealed by time-resolved small-angle X-ray scattering","authors":"Rintaro Takahashi, Ayae Sugawara-Narutaki, Ken Terao","doi":"10.1038/s41428-025-01091-z","DOIUrl":"10.1038/s41428-025-01091-z","url":null,"abstract":"Time-resolved small-angle X-ray scattering (TR-SAXS) is an indispensable technique for directly monitoring in situ kinetic processes in soft matter, providing real-time structural information from nanometer to micrometer length scales. This Focus Review summarizes recent significant advances in understanding the self-assembly kinetics of block copolymers in solution, primarily revealed through TR-SAXS. The review is structured into three key sections, each addressing distinct driving forces and mechanisms. First, we discuss the formation and transformation of micelles, predominantly driven by non-covalent interactions like van der Waals forces and hydrophobic interactions, leading to the spontaneous association of amphiphilic block copolymers in selective solvents. Next, we cover polyelectrolyte complex micelles and vesicles, where self-assembly is initiated by electrostatic interactions, as mixing oppositely charged block polyelectrolytes in aqueous media forms complex coacervate structures. Finally, we present polymerization-induced self-assembly (PISA), a unique approach involving the in situ formation and evolution of block copolymer nanostructures as a monomer is polymerized from a pre-existing polymer chain, simultaneously achieving block copolymer synthesis and self-assembly. Through these examples, we highlight the power of TR-SAXS in elucidating the intricate kinetic pathways and underlying mechanisms governing block copolymer self-assembly. Time-resolved small-angle X-ray scattering (TR-SAXS) is crucial for real-time monitoring of soft matter kinetics, offering nanometer-to-micrometer structural insights and revealing complex kinetic pathways and mechanisms. This review highlights its power in understanding block copolymer self-assembly kinetics in solution, covering micelle formation driven by non-covalent interactions, polyelectrolyte complex micelles via electrostatic interactions, and polymerization-induced self-assembly (PISA).","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"58 1","pages":"15-22"},"PeriodicalIF":2.7,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01091-z.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145896018","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-08-29DOI: 10.1038/s41428-025-01092-y
Masaki Nakahata
The selective capture of heavy metal ions is a persistent challenge in environmental remediation owing to the chemical similarities among metal ions and the need for high affinity, selectivity, and capacity. Biological systems have evolved efficient mechanisms to regulate metal ions, utilizing proteins such as phytochelatin, metallothionein, and lanmodulin. These biomacromolecules achieve affinity, selectivity, and capacity for metal ions at biologically relevant levels through well-organized structural motifs, inspiring the design of synthetic polymers with biomimetic functions. This focus review provides an overview of research on heavy metal-binding proteins and explores how these proteins inspired researchers to develop bioinspired and biointegrated materials. First, key structural and thermodynamic features of heavy metal-binding proteins and their roles in metal detoxification and homeostasis are discussed. Then, recent advancements in emerging materials that mimic these biological functions using synthetic peptides, polymers, and peptoids are highlighted. Finally, we review integrated systems that directly incorporate biological components with synthetic polymers to create advanced heavy metal adsorbents. Together, these approaches illustrate how bioinspired and biosynthetic integration strategies are driving innovations in heavy metal ion capture technologies. Continued interdisciplinary research promises to deliver next-generation materials with improved efficiency, specificity, and environmental compatibility for real-world applications. The selective capture of heavy metal ions is a major challenge due to the need for materials with high affinity, selectivity, and capacity. Nature uses proteins to manage metal ions via specific structural motifs. This focus review summarizes recent advances in bioinspired and biosynthetic integrated strategies for the capture of heavy metal ions. The topics discussed include (1) the structural and thermodynamic features of metal-binding proteins, (2) synthetic polymers that mimic the biological functions of proteins, and (3) hybrid materials that integrate biological (macro)molecules with synthetic polymers.
{"title":"Bioinspired and biosynthetic integrated polymeric materials for the selective capture of heavy metal ions","authors":"Masaki Nakahata","doi":"10.1038/s41428-025-01092-y","DOIUrl":"10.1038/s41428-025-01092-y","url":null,"abstract":"The selective capture of heavy metal ions is a persistent challenge in environmental remediation owing to the chemical similarities among metal ions and the need for high affinity, selectivity, and capacity. Biological systems have evolved efficient mechanisms to regulate metal ions, utilizing proteins such as phytochelatin, metallothionein, and lanmodulin. These biomacromolecules achieve affinity, selectivity, and capacity for metal ions at biologically relevant levels through well-organized structural motifs, inspiring the design of synthetic polymers with biomimetic functions. This focus review provides an overview of research on heavy metal-binding proteins and explores how these proteins inspired researchers to develop bioinspired and biointegrated materials. First, key structural and thermodynamic features of heavy metal-binding proteins and their roles in metal detoxification and homeostasis are discussed. Then, recent advancements in emerging materials that mimic these biological functions using synthetic peptides, polymers, and peptoids are highlighted. Finally, we review integrated systems that directly incorporate biological components with synthetic polymers to create advanced heavy metal adsorbents. Together, these approaches illustrate how bioinspired and biosynthetic integration strategies are driving innovations in heavy metal ion capture technologies. Continued interdisciplinary research promises to deliver next-generation materials with improved efficiency, specificity, and environmental compatibility for real-world applications. The selective capture of heavy metal ions is a major challenge due to the need for materials with high affinity, selectivity, and capacity. Nature uses proteins to manage metal ions via specific structural motifs. This focus review summarizes recent advances in bioinspired and biosynthetic integrated strategies for the capture of heavy metal ions. The topics discussed include (1) the structural and thermodynamic features of metal-binding proteins, (2) synthetic polymers that mimic the biological functions of proteins, and (3) hybrid materials that integrate biological (macro)molecules with synthetic polymers.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"58 1","pages":"23-30"},"PeriodicalIF":2.7,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01092-y.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145896019","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-08-29DOI: 10.1038/s41428-025-01090-0
Miona Iwai, Shin-ichi Matsuoka
The introduction of bulky and rigid polycyclic hydrocarbons into the polymer side chains increased the glass transition temperature (Tg), thereby broadening the application range of the polymer. We synthesized and polymerized new acrylate and methacrylate monomers bearing a norbornadiene dimer, exo-exo-4-pentacyclo[8.2.1.15,8.02,9.03,7]tetradecanyl acrylate (1) and its methacrylate analog (2). The polymerizations of 1 and 2 using Lewis pair catalysts comprising B(C6F5)3/PPh3 and methylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide) (MAD)/PCy3, respectively, proceeded with full conversion. The Tg values of poly1 and poly2 were approximately 120 °C and 200 °C, respectively. Considering the Tg and tacticity of poly2 obtained via radical polymerization (Tg = 135 °C; rr triad = 63%), the significantly higher Tg value (Tg = 206 °C) can be reasonably assumed to be due to the high syndiotacticity (rr = 87%), which is likely induced by the steric repulsion between the bulky MAD at the propagating terminal and the penultimate norbornadiene dimer moiety. New acrylate and methacrylate monomers (1 and 2) incorporating a bulky and rigid norbornadiene dimer were synthesized and polymerized using borane- and aluminum-based Lewis pair catalysts. The resulting polymers exhibited high glass transition temperatures (Tg). Notably, poly2 exhibited high syndiotacticity (rr = 87%), attributed to steric hindrance of the bulky MAD-coordinated chain end, resulting in a Tg of 206 °C. These findings indicate that incorporating sterically demanding side chains and enhancing syndiatacticity through Lewis pair polymerization can lead to the development of thermally stable (meth)acrylic polymers.
{"title":"Synthesis of high glass transition temperature (meth)acrylic polymers bearing norbornadiene dimer via Lewis pair polymerization","authors":"Miona Iwai, Shin-ichi Matsuoka","doi":"10.1038/s41428-025-01090-0","DOIUrl":"10.1038/s41428-025-01090-0","url":null,"abstract":"The introduction of bulky and rigid polycyclic hydrocarbons into the polymer side chains increased the glass transition temperature (Tg), thereby broadening the application range of the polymer. We synthesized and polymerized new acrylate and methacrylate monomers bearing a norbornadiene dimer, exo-exo-4-pentacyclo[8.2.1.15,8.02,9.03,7]tetradecanyl acrylate (1) and its methacrylate analog (2). The polymerizations of 1 and 2 using Lewis pair catalysts comprising B(C6F5)3/PPh3 and methylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide) (MAD)/PCy3, respectively, proceeded with full conversion. The Tg values of poly1 and poly2 were approximately 120 °C and 200 °C, respectively. Considering the Tg and tacticity of poly2 obtained via radical polymerization (Tg = 135 °C; rr triad = 63%), the significantly higher Tg value (Tg = 206 °C) can be reasonably assumed to be due to the high syndiotacticity (rr = 87%), which is likely induced by the steric repulsion between the bulky MAD at the propagating terminal and the penultimate norbornadiene dimer moiety. New acrylate and methacrylate monomers (1 and 2) incorporating a bulky and rigid norbornadiene dimer were synthesized and polymerized using borane- and aluminum-based Lewis pair catalysts. The resulting polymers exhibited high glass transition temperatures (Tg). Notably, poly2 exhibited high syndiotacticity (rr = 87%), attributed to steric hindrance of the bulky MAD-coordinated chain end, resulting in a Tg of 206 °C. These findings indicate that incorporating sterically demanding side chains and enhancing syndiatacticity through Lewis pair polymerization can lead to the development of thermally stable (meth)acrylic polymers.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"58 1","pages":"95-100"},"PeriodicalIF":2.7,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01090-0.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145896020","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-08-27DOI: 10.1038/s41428-025-01099-5
Jun Araki
Carboxy groups on cellulose nanowhiskers (CNWs) were quantified using two dyes in four states (original and purified forms of both methylene blue (MB) and toluidine blue O (TBO)). Only purified TBO yielded satisfactory accuracy. Unpurified TBO resulted in overestimation, attributed to impurities (typically inorganic salts), whereas both unpurified and purified MB led to underestimation, for reasons that remain unknown. Carboxy groups on cellulose nanowhiskers (CNWs) were quantified using two dyes in four states (original and purified methylene blue (MB) and toluidine blue O (TBO)). Only purified TBO yielded satisfactory accuracy. Unpurified TBO resulted in overestimation, attributed to impurities (typically inorganic salts), whereas unpurified and purified MB led to underestimation, the reasons for which are still unknown.
{"title":"Usability of different purified/unpurified cationic dyes for the quantitative determination of the anionic surface charge of cellulose nanowhiskers","authors":"Jun Araki","doi":"10.1038/s41428-025-01099-5","DOIUrl":"10.1038/s41428-025-01099-5","url":null,"abstract":"Carboxy groups on cellulose nanowhiskers (CNWs) were quantified using two dyes in four states (original and purified forms of both methylene blue (MB) and toluidine blue O (TBO)). Only purified TBO yielded satisfactory accuracy. Unpurified TBO resulted in overestimation, attributed to impurities (typically inorganic salts), whereas both unpurified and purified MB led to underestimation, for reasons that remain unknown. Carboxy groups on cellulose nanowhiskers (CNWs) were quantified using two dyes in four states (original and purified methylene blue (MB) and toluidine blue O (TBO)). Only purified TBO yielded satisfactory accuracy. Unpurified TBO resulted in overestimation, attributed to impurities (typically inorganic salts), whereas unpurified and purified MB led to underestimation, the reasons for which are still unknown.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 12","pages":"1421-1424"},"PeriodicalIF":2.7,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145666279","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 : 2025-08-26DOI: 10.1038/s41428-025-01083-z
De Nguyen, Kenji Kinashi, Yukihiro Nishikawa, Wataru Sakai, Naoto Tsutsumi
Cellulosic aerogels and sponges, multifunctional materials, are typically fabricated from cellulose nanocrystals (CNCs) and nanofibrils (CNFs). The zero-dimensional (0D) structures of CNCs and one-dimensional (1D) structures of CNFs exhibit loose point-to-point and line-to-line interactions among their constituent building blocks. Consequently, fabricating functional and mechanically stable aerogels and sponges from these 0D and 1D building blocks typically requires chemical crosslinking—a process that complicates fabrication and adds to the structural mass. In contrast, cellulose acetate sponges constructed from nanofilms via cryo-templating exhibit high porosity (>99%), low density (≤10 kg m−3), and a stable, continuous structure that does not require crosslinking while possessing mechanical properties comparable to those of crosslinked CNF sponges. These nanofilm-based sponges exhibit cell structures with a gradient thickness and increased apparent elasticity, which scales exponentially with relative density, characterized by a coefficient of 2.04 and an exponent of 2.48. Furthermore, they exhibit viscoelastic behavior, which is attributed to the bending of cell structures and the delamination and slippage of uncrosslinked nanofilms. This viscoelastic behavior can be altered by tailoring the pore size and pore distribution, thereby retarding stress relaxation and enhancing resilience. Cellulose acetate sponges were fabricated by cryo-templating, without chemical crosslinking, from cellulose acetate nanofilms produced using a nonsolvent-induced phase separation (NIPS)-jet spinning technique. X-ray computed tomography (X-CT) revealed their open-cell, continuous microstructure. The sponges exhibited resilience, stability, and mechanical tunability via microstructural tailoring. Their viscoelasticity was attributed to the bending of the cell structure and the delamination and slippage of the uncrosslinked nanofilms.
纤维素气凝胶和海绵是多功能材料，通常由纤维素纳米晶体（CNCs）和纳米原纤维（CNFs）制成。CNFs的零维（0D）结构和一维（1D）结构在其组成单元之间表现出松散的点对点和线对线相互作用。因此，从这些0D和1D构建块中制造功能和机械稳定的气凝胶和海绵通常需要化学交联，这一过程使制造变得复杂，并增加了结构质量。相比之下，由纳米膜通过低温模板构建的醋酸纤维素海绵具有高孔隙率（>99%），低密度（≤10 kg m - 3）和稳定，连续的结构，不需要交联，同时具有与交联CNF海绵相当的机械性能。纳米膜海绵具有梯度厚度的细胞结构，表观弹性随相对密度呈指数级增长，其系数为2.04，指数为2.48。此外，它们表现出粘弹性行为，这是由于细胞结构的弯曲和非交联纳米膜的分层和滑移。这种粘弹性行为可以通过调整孔隙大小和孔隙分布来改变，从而延缓应力松弛并增强弹性。以非溶剂诱导相分离（NIPS）喷射纺丝技术制备的醋酸纤维素纳米膜为原料，采用低温模板法制备醋酸纤维素海绵，无需化学交联。x射线计算机断层扫描（X-CT）显示其开孔，连续的微观结构。通过微观结构剪裁，海绵表现出弹性、稳定性和机械可调性。它们的粘弹性归因于细胞结构的弯曲和非交联纳米膜的分层和滑移。
{"title":"Mechanically tunable nanofilm-based cellulose acetate sponges via crosslinker-free cryo-templating","authors":"De Nguyen, Kenji Kinashi, Yukihiro Nishikawa, Wataru Sakai, Naoto Tsutsumi","doi":"10.1038/s41428-025-01083-z","DOIUrl":"10.1038/s41428-025-01083-z","url":null,"abstract":"Cellulosic aerogels and sponges, multifunctional materials, are typically fabricated from cellulose nanocrystals (CNCs) and nanofibrils (CNFs). The zero-dimensional (0D) structures of CNCs and one-dimensional (1D) structures of CNFs exhibit loose point-to-point and line-to-line interactions among their constituent building blocks. Consequently, fabricating functional and mechanically stable aerogels and sponges from these 0D and 1D building blocks typically requires chemical crosslinking—a process that complicates fabrication and adds to the structural mass. In contrast, cellulose acetate sponges constructed from nanofilms via cryo-templating exhibit high porosity (>99%), low density (≤10 kg m−3), and a stable, continuous structure that does not require crosslinking while possessing mechanical properties comparable to those of crosslinked CNF sponges. These nanofilm-based sponges exhibit cell structures with a gradient thickness and increased apparent elasticity, which scales exponentially with relative density, characterized by a coefficient of 2.04 and an exponent of 2.48. Furthermore, they exhibit viscoelastic behavior, which is attributed to the bending of cell structures and the delamination and slippage of uncrosslinked nanofilms. This viscoelastic behavior can be altered by tailoring the pore size and pore distribution, thereby retarding stress relaxation and enhancing resilience. Cellulose acetate sponges were fabricated by cryo-templating, without chemical crosslinking, from cellulose acetate nanofilms produced using a nonsolvent-induced phase separation (NIPS)-jet spinning technique. X-ray computed tomography (X-CT) revealed their open-cell, continuous microstructure. The sponges exhibited resilience, stability, and mechanical tunability via microstructural tailoring. Their viscoelasticity was attributed to the bending of the cell structure and the delamination and slippage of the uncrosslinked nanofilms.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 12","pages":"1409-1420"},"PeriodicalIF":2.7,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145666272","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}
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