Pub Date : 2025-04-11DOI: 10.1038/s41428-024-00995-6
Yoshitaka Koseki
This review focuses on the development of carrier-free nano-prodrugs as an innovative approach to cancer therapy. We discuss the design strategies, synthesis methods, and characteristics of nano-prodrugs responsive to various stimuli, including enzymes, reactive oxygen species (ROS), and glutathione (GSH). This paper highlights recent advances in the development of a new class of stimulus-responsive nano-prodrugs without the use of carriers, thereby addressing the challenges faced by conventional nanocarrier-based drug delivery systems. The key aspects covered include (1) the design and synthesis of esterase-activated nano-prodrugs based on the anticancer agent SN-38, demonstrating the importance of substituent hydrophobicity for controlling hydrolysis resistance and drug release profiles; (2) the development of ROS-activated nano-prodrugs using camptothecin combined with trimethyl lock groups, demonstrating a novel molecular design principle for drugs with tertiary alcohol moieties; and (3) the GSH-responsive dimeric prodrugs of SN-38 linked by disulfide bonds, demonstrating enhanced antitumor effects and reduced side effects in vivo. These carrier-free nano-prodrugs exhibit high drug-loading capacity, excellent stimulus responsiveness, and improved therapeutic efficacy with reduced side effects. Finally, we discuss future research directions, including the optimization of nanoprodrug designs for enhanced cancer therapy. Carrier-free nano-prodrugs (NPDs) were developed for selective drug release in cancer cells using stimulus-responsive systems: esterases, reactive oxygen species (ROS), and glutathione (GSH). Esterase-activated NPDs showed hydrophobicity-dependent drug release through SN-38 modification. ROS-responsive NPDs with trimethyl lock groups demonstrated selective activation by intracellular H2O2. GSH-responsive dimeric SN-38 prodrugs exhibited enhanced antitumor effects with reduced side effects. These NPDs achieved high drug loading and excellent stimulus responsiveness without using carriers, providing a promising platform for safer and more effective cancer therapy.
{"title":"Carrier-free nano-prodrugs for enhanced cancer therapy: stimuli-responsive design and applications","authors":"Yoshitaka Koseki","doi":"10.1038/s41428-024-00995-6","DOIUrl":"10.1038/s41428-024-00995-6","url":null,"abstract":"This review focuses on the development of carrier-free nano-prodrugs as an innovative approach to cancer therapy. We discuss the design strategies, synthesis methods, and characteristics of nano-prodrugs responsive to various stimuli, including enzymes, reactive oxygen species (ROS), and glutathione (GSH). This paper highlights recent advances in the development of a new class of stimulus-responsive nano-prodrugs without the use of carriers, thereby addressing the challenges faced by conventional nanocarrier-based drug delivery systems. The key aspects covered include (1) the design and synthesis of esterase-activated nano-prodrugs based on the anticancer agent SN-38, demonstrating the importance of substituent hydrophobicity for controlling hydrolysis resistance and drug release profiles; (2) the development of ROS-activated nano-prodrugs using camptothecin combined with trimethyl lock groups, demonstrating a novel molecular design principle for drugs with tertiary alcohol moieties; and (3) the GSH-responsive dimeric prodrugs of SN-38 linked by disulfide bonds, demonstrating enhanced antitumor effects and reduced side effects in vivo. These carrier-free nano-prodrugs exhibit high drug-loading capacity, excellent stimulus responsiveness, and improved therapeutic efficacy with reduced side effects. Finally, we discuss future research directions, including the optimization of nanoprodrug designs for enhanced cancer therapy. Carrier-free nano-prodrugs (NPDs) were developed for selective drug release in cancer cells using stimulus-responsive systems: esterases, reactive oxygen species (ROS), and glutathione (GSH). Esterase-activated NPDs showed hydrophobicity-dependent drug release through SN-38 modification. ROS-responsive NPDs with trimethyl lock groups demonstrated selective activation by intracellular H2O2. GSH-responsive dimeric SN-38 prodrugs exhibited enhanced antitumor effects with reduced side effects. These NPDs achieved high drug loading and excellent stimulus responsiveness without using carriers, providing a promising platform for safer and more effective cancer therapy.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 7","pages":"699-710"},"PeriodicalIF":2.3,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144574315","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}
{"title":"Special issue: Molecular picture of heterogeneity in polymer networks: from thermosetting polymers to elastomers and gels","authors":"Keiji Tanaka, Kenji Urayama, Tasuku Nakajima, Takeshi Serizawa","doi":"10.1038/s41428-025-01014-y","DOIUrl":"10.1038/s41428-025-01014-y","url":null,"abstract":"","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 4","pages":"341-342"},"PeriodicalIF":2.3,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-025-01014-y.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143787372","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 : 2025-03-28DOI: 10.1038/s41428-025-01029-5
Haruki Konta, Katsuya Maeyama
Three types of polyketones with different numbers of 3,5-(C4F9)2C6H3 groups at both ends were successfully synthesized. The resulting polyketones are soluble in typical organic solvents such as THF, CHCl3, and NMP. These materials exhibit good thermal stability above 519 °C (Td10) and high glass transition temperatures (Tg) above 221 °C. Furthermore, these polyketones have excellent water/oil repellency. Notably, the polyketone with ten C4F9 groups at each polymer end has a lower surface tension than PTFE (Polytetrafluoroethylene). XPS (X-ray Photoelectron Spectroscopy) measurements revealed that the increase in the water/oil repellency of the polyketones was due to the localization of terminal C4F9 groups on the film surface. Three types of polyketones with different numbers of 3,5-(C4F9)2C6H3 groups at both ends were successfully synthesized. The resulting polyketones are soluble in typical organic solvents such as THF, CHCl3, and NMP. They exhibit good thermal stability above 519 °C (Td10) and high glass transition temperature (Tg) above 221 oC. Furthermore, these polyketones also have excellent water/oil repellency.
{"title":"Development of water/oil repellent and heat-resistant aromatic poly(ether ketone)s bearing 3,5-(C4F9)2C6H3 groups at both ends","authors":"Haruki Konta, Katsuya Maeyama","doi":"10.1038/s41428-025-01029-5","DOIUrl":"10.1038/s41428-025-01029-5","url":null,"abstract":"Three types of polyketones with different numbers of 3,5-(C4F9)2C6H3 groups at both ends were successfully synthesized. The resulting polyketones are soluble in typical organic solvents such as THF, CHCl3, and NMP. These materials exhibit good thermal stability above 519 °C (Td10) and high glass transition temperatures (Tg) above 221 °C. Furthermore, these polyketones have excellent water/oil repellency. Notably, the polyketone with ten C4F9 groups at each polymer end has a lower surface tension than PTFE (Polytetrafluoroethylene). XPS (X-ray Photoelectron Spectroscopy) measurements revealed that the increase in the water/oil repellency of the polyketones was due to the localization of terminal C4F9 groups on the film surface. Three types of polyketones with different numbers of 3,5-(C4F9)2C6H3 groups at both ends were successfully synthesized. The resulting polyketones are soluble in typical organic solvents such as THF, CHCl3, and NMP. They exhibit good thermal stability above 519 °C (Td10) and high glass transition temperature (Tg) above 221 oC. Furthermore, these polyketones also have excellent water/oil repellency.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 7","pages":"745-759"},"PeriodicalIF":2.3,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-025-01029-5.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144574316","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}
Biomass plastics with biodegradability and suitable mechanical performance are needed to replace persistent synthetic plastics derived from fossil fuels. Lignocellulosic agricultural wastes, such as sugarcane bagasse, are promising renewable resources that offer better thermal processability when their abundant hydroxy (OH) groups are substituted with acyl groups, particularly those with longer chain lengths. However, excessive chemical modification can impair the inherent biodegradability of lignocellulose and weaken the resulting plastics. In this study, the acyl group was optimized to a decanoyl (De, C=10) group, which was the most effective in lowering the melt flow temperature of the fully substituted bagasse monoester to improve thermal moldability. The bagasse decanoate (BagDe) series were synthesized using different amounts of vinyl decanoate (VDe) ranging from 3 to 0.4 molar equivalents to the total OH content of bagasse, and their thermal/mechanical properties and degradability in soil were examined. BagDe synthesized with more than 0.6 equivalents of VDe could be hot-press molded, while the increased residual OH content improved the water uptake, degradation rate, and tensile strength. These findings indicate the potential applications of lignocellulose-based biodegradable plastics, such as agricultural mulch films.
{"title":"Degradation behavior in soil and mechanical properties of bagasse monoesters with different acyl chain lengths and residual hydroxy contents","authors":"Shiori Suzuki, Shogo Ishikura, Shoichi Ikebata, Naoki Wada, Kenji Takahashi","doi":"10.1038/s41428-025-01031-x","DOIUrl":"10.1038/s41428-025-01031-x","url":null,"abstract":"Biomass plastics with biodegradability and suitable mechanical performance are needed to replace persistent synthetic plastics derived from fossil fuels. Lignocellulosic agricultural wastes, such as sugarcane bagasse, are promising renewable resources that offer better thermal processability when their abundant hydroxy (OH) groups are substituted with acyl groups, particularly those with longer chain lengths. However, excessive chemical modification can impair the inherent biodegradability of lignocellulose and weaken the resulting plastics. In this study, the acyl group was optimized to a decanoyl (De, C=10) group, which was the most effective in lowering the melt flow temperature of the fully substituted bagasse monoester to improve thermal moldability. The bagasse decanoate (BagDe) series were synthesized using different amounts of vinyl decanoate (VDe) ranging from 3 to 0.4 molar equivalents to the total OH content of bagasse, and their thermal/mechanical properties and degradability in soil were examined. BagDe synthesized with more than 0.6 equivalents of VDe could be hot-press molded, while the increased residual OH content improved the water uptake, degradation rate, and tensile strength. These findings indicate the potential applications of lignocellulose-based biodegradable plastics, such as agricultural mulch films.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 7","pages":"761-769"},"PeriodicalIF":2.3,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-025-01031-x.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144574320","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 : 2025-03-21DOI: 10.1038/s41428-025-01028-6
Ayae Sugawara-Narutaki
The soluble precursors of elastin protein and elastin-like polypeptides (ELPs) are polymers that typically undergo liquid‒liquid phase separation to form coacervates. In addition to their fundamental importance in biology, the dynamic nature of coacervates makes them attractive platforms as innovative materials in bioengineering and nanomedicine. This focus review presents the latest research on the requirements of elastin-like polypeptide sequences for phase separation and the dynamics of coacervates. Research attempting to control the phase-transition behavior of ELPs in living cells is also presented. In addition, a molecular design strategy for ELPs to obtain anisotropic nanofibers by coacervation, their functionalization for biomaterial applications, and the unique viscoelastic properties of hydrogels composed of nanofibers are discussed. These research trends indicate that the molecular design of ELPs enables control of the dynamics and morphology of coacervates. This fundamental knowledge will be useful for the dynamic functional design of drug delivery systems and scaffolds for regenerative medicine. Elastin-like polypeptides (ELPs) typically undergo liquid‒liquid phase separation to form coacervates. This focus review presents a molecular design strategy for novel ELPs to obtain self-assembled nanofibers via coacervation. In this molecular design, various functional motifs can be presented on the nanofiber surface, allowing cell-selective growth and differentiation control. In addition, unique viscoelastic properties of hydrogels composed of the nanofibers are discussed. These nanofibers and hydrogels could serve as platforms for small-diameter artificial blood vessels and scaffold materials for regenerative medicine.
{"title":"Self-assembled nanofibers and hydrogels of double-hydrophobic elastin-like polypeptides formed via coacervation","authors":"Ayae Sugawara-Narutaki","doi":"10.1038/s41428-025-01028-6","DOIUrl":"10.1038/s41428-025-01028-6","url":null,"abstract":"The soluble precursors of elastin protein and elastin-like polypeptides (ELPs) are polymers that typically undergo liquid‒liquid phase separation to form coacervates. In addition to their fundamental importance in biology, the dynamic nature of coacervates makes them attractive platforms as innovative materials in bioengineering and nanomedicine. This focus review presents the latest research on the requirements of elastin-like polypeptide sequences for phase separation and the dynamics of coacervates. Research attempting to control the phase-transition behavior of ELPs in living cells is also presented. In addition, a molecular design strategy for ELPs to obtain anisotropic nanofibers by coacervation, their functionalization for biomaterial applications, and the unique viscoelastic properties of hydrogels composed of nanofibers are discussed. These research trends indicate that the molecular design of ELPs enables control of the dynamics and morphology of coacervates. This fundamental knowledge will be useful for the dynamic functional design of drug delivery systems and scaffolds for regenerative medicine. Elastin-like polypeptides (ELPs) typically undergo liquid‒liquid phase separation to form coacervates. This focus review presents a molecular design strategy for novel ELPs to obtain self-assembled nanofibers via coacervation. In this molecular design, various functional motifs can be presented on the nanofiber surface, allowing cell-selective growth and differentiation control. In addition, unique viscoelastic properties of hydrogels composed of the nanofibers are discussed. These nanofibers and hydrogels could serve as platforms for small-diameter artificial blood vessels and scaffold materials for regenerative medicine.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 8","pages":"863-871"},"PeriodicalIF":2.7,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-025-01028-6.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144774164","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}
Polyrotaxane (PR) exhibits unique mechanical properties due to the ability of its cyclic molecules to move or slide along the axial chain. Thus, to design advanced polymer-based composite materials and organic devices, it is crucial to better understand the aggregation states at the surface and substrate interface in polymer films containing PR. Here, we report the depth profile of PR along the direction normal to the interface when it is mixed with polystyrene (PS). Neutron reflectivity and X-ray photoelectron spectroscopy revealed that PS and PR segregated at the surface and substrate interface, respectively, and that the extent of segregation depended on the length of PS. The surface enrichment of PS is driven by both energy and entropy, whereas the enrichment of PR at the substrate interface is energy driven. To design and fabricate advanced polymer-based multilayer devices and composite materials, it is crucial to gain a better understanding of the aggregation states at the surface and at interfaces with solid materials in polymer films. Here, we report the depth profile of polyrotaxane (PR) when mixed with polystyrene (PS), analyzed using X-ray photoelectron spectroscopy and neutron reflectivity. Our findings indicate that PS and PR segregated at the surface and the substrate interface, respectively, with the extent of segregation depending on the length of the PS chains.
{"title":"Surface and interfacial aggregation states in thin films of a polystyrene/polyrotaxane blend","authors":"Miki Taguchi, Noboru Miyata, Tsukasa Miyazaki, Hiroyuki Aoki, Satoru Ozawa, Ryuichi Hasegawa, Yuma Morimitsu, Daisuke Kawaguchi, Satoru Yamamoto, Keiji Tanaka","doi":"10.1038/s41428-025-01030-y","DOIUrl":"10.1038/s41428-025-01030-y","url":null,"abstract":"Polyrotaxane (PR) exhibits unique mechanical properties due to the ability of its cyclic molecules to move or slide along the axial chain. Thus, to design advanced polymer-based composite materials and organic devices, it is crucial to better understand the aggregation states at the surface and substrate interface in polymer films containing PR. Here, we report the depth profile of PR along the direction normal to the interface when it is mixed with polystyrene (PS). Neutron reflectivity and X-ray photoelectron spectroscopy revealed that PS and PR segregated at the surface and substrate interface, respectively, and that the extent of segregation depended on the length of PS. The surface enrichment of PS is driven by both energy and entropy, whereas the enrichment of PR at the substrate interface is energy driven. To design and fabricate advanced polymer-based multilayer devices and composite materials, it is crucial to gain a better understanding of the aggregation states at the surface and at interfaces with solid materials in polymer films. Here, we report the depth profile of polyrotaxane (PR) when mixed with polystyrene (PS), analyzed using X-ray photoelectron spectroscopy and neutron reflectivity. Our findings indicate that PS and PR segregated at the surface and the substrate interface, respectively, with the extent of segregation depending on the length of the PS chains.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 7","pages":"737-743"},"PeriodicalIF":2.3,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-025-01030-y.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144574321","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}
Surfactant-free coupling polymerization of pyrrole (Py) and its derivatives, namely, N-methylpyrrole (MPy) and N-ethylpyrrole (EPy), was conducted using solid Fe(NO3)3 in the presence of an aqueous medium, resulting in aqueous dispersions of polymer particles. Dynamic light scattering studies revealed the production of colloidally stable polymer nanoparticles with diameters of 153–206 nm, 262–294 nm and 273–278 nm in aqueous media for the Py, MPy and EPy systems, respectively. The particle sizes of poly(N-methylpyrrole) (PMPy) and poly(N-ethylpyrrole) (PEPy) were larger than those of polypyrrole (PPy), which could be due to the greater hydrophobicity of MPy and EPy than Py. The particles could achieve colloidal stability through an electrostatic stabilization mechanism, as the polymerization process introduces cationic charges to the polymers via doping. Larger amounts of hydroxy and carbonyl groups were introduced into PMPy and PEPy because of the easier overoxidation of MPy and EPy due to their lower redox potentials than that of Py. Furthermore, the resulting particles could adsorb on oil‒water interfaces and work as effective Pickering-type emulsifiers. Suspension polymerization of vinyl monomer-in-water Pickering emulsions stabilized with PPy and PMPy nanoparticles resulted in the production of nanoparticle-coated polymer microparticles with diameters of 25 μm and 154 μm, respectively. “Polypyrrole, poly(N-methylpyrrole) and poly(N-ethylpyrrole) nanoparticles with surfactant-free clean surfaces were successfully synthesized via a vapor-phase coupling polymerization protocol. The particles could achieve colloidal stability through an electrostatic stabilization mechanism, as the polymerization process introduces cationic charges to the polymers via doping. The particles could adsorb on oil‒water interfaces and work as effective Pickering-type emulsifiers. Suspension polymerization of vinyl monomer-in-water Pickering emulsions stabilized with the nanoparticles resulted in the production of nanoparticle-coated polymer microparticles.”
{"title":"Synthesis of polypyrrole and its derivative nanoparticles via a surfactant-free coupling polymerization protocol","authors":"Yuya Atsuta, Kazusa Takeuchi, Tomoki Sakuma, Koji Mitamura, Seiji Watase, Yuan Song, Tomoyasu Hirai, Yoshinobu Nakamura, Yuya Oaki, Syuji Fujii","doi":"10.1038/s41428-025-01026-8","DOIUrl":"10.1038/s41428-025-01026-8","url":null,"abstract":"Surfactant-free coupling polymerization of pyrrole (Py) and its derivatives, namely, N-methylpyrrole (MPy) and N-ethylpyrrole (EPy), was conducted using solid Fe(NO3)3 in the presence of an aqueous medium, resulting in aqueous dispersions of polymer particles. Dynamic light scattering studies revealed the production of colloidally stable polymer nanoparticles with diameters of 153–206 nm, 262–294 nm and 273–278 nm in aqueous media for the Py, MPy and EPy systems, respectively. The particle sizes of poly(N-methylpyrrole) (PMPy) and poly(N-ethylpyrrole) (PEPy) were larger than those of polypyrrole (PPy), which could be due to the greater hydrophobicity of MPy and EPy than Py. The particles could achieve colloidal stability through an electrostatic stabilization mechanism, as the polymerization process introduces cationic charges to the polymers via doping. Larger amounts of hydroxy and carbonyl groups were introduced into PMPy and PEPy because of the easier overoxidation of MPy and EPy due to their lower redox potentials than that of Py. Furthermore, the resulting particles could adsorb on oil‒water interfaces and work as effective Pickering-type emulsifiers. Suspension polymerization of vinyl monomer-in-water Pickering emulsions stabilized with PPy and PMPy nanoparticles resulted in the production of nanoparticle-coated polymer microparticles with diameters of 25 μm and 154 μm, respectively. “Polypyrrole, poly(N-methylpyrrole) and poly(N-ethylpyrrole) nanoparticles with surfactant-free clean surfaces were successfully synthesized via a vapor-phase coupling polymerization protocol. The particles could achieve colloidal stability through an electrostatic stabilization mechanism, as the polymerization process introduces cationic charges to the polymers via doping. The particles could adsorb on oil‒water interfaces and work as effective Pickering-type emulsifiers. Suspension polymerization of vinyl monomer-in-water Pickering emulsions stabilized with the nanoparticles resulted in the production of nanoparticle-coated polymer microparticles.”","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 7","pages":"723-735"},"PeriodicalIF":2.3,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144574318","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 : 2025-03-04DOI: 10.1038/s41428-025-01024-w
Jianghao Wang, Shuyan Yu, Congju Li
The ongoing surge in portable and smart device technology drives the need for materials that are both flexible and conductive. Owing to their high surface area and stability, carbon nanofibers (CNFs) are ideal for these applications. Electrospinning is a superior method for producing uniform CNFs with adjustable sizes, allowing for precise property control. The focus of this concise review is on enhancing the stress distribution and flexibility of electrospun CNFs, and the importance of optimizing pre-oxidation and carbonization to improve crystallinity and performance is emphasized. Physical stretching techniques and the addition of nanoparticles to create heterogeneous phases within the carbon matrix are discussed as the methods used to increase the mechanical properties of CNFs and develop porous structures. Additionally, the broad applications of flexible CNFs are outlined, and insights into current research and future prospects are provided, with an emphasis on the significance of CNFs in flexible material development. This review highlights key strategies to enhance the flexibility of carbon nanofibers (CNFs) and their applications. The preparation strategies encompass pore creation, nanoparticle doping, reaction process regulation, and tension stretching. These approaches are designed to refine the reaction process and bolster the physical characteristics of CNFs. The applications extend across supercapacitors to lithium-ion batteries, underscoring the versatile potential of flexible CNFs.
{"title":"Preparation and application of flexible carbon nanofiber membranes via electrospinning: from stress dispersion to multifunctionality","authors":"Jianghao Wang, Shuyan Yu, Congju Li","doi":"10.1038/s41428-025-01024-w","DOIUrl":"10.1038/s41428-025-01024-w","url":null,"abstract":"The ongoing surge in portable and smart device technology drives the need for materials that are both flexible and conductive. Owing to their high surface area and stability, carbon nanofibers (CNFs) are ideal for these applications. Electrospinning is a superior method for producing uniform CNFs with adjustable sizes, allowing for precise property control. The focus of this concise review is on enhancing the stress distribution and flexibility of electrospun CNFs, and the importance of optimizing pre-oxidation and carbonization to improve crystallinity and performance is emphasized. Physical stretching techniques and the addition of nanoparticles to create heterogeneous phases within the carbon matrix are discussed as the methods used to increase the mechanical properties of CNFs and develop porous structures. Additionally, the broad applications of flexible CNFs are outlined, and insights into current research and future prospects are provided, with an emphasis on the significance of CNFs in flexible material development. This review highlights key strategies to enhance the flexibility of carbon nanofibers (CNFs) and their applications. The preparation strategies encompass pore creation, nanoparticle doping, reaction process regulation, and tension stretching. These approaches are designed to refine the reaction process and bolster the physical characteristics of CNFs. The applications extend across supercapacitors to lithium-ion batteries, underscoring the versatile potential of flexible CNFs.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 6","pages":"605-622"},"PeriodicalIF":2.3,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144214283","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}
In this study, a highly viscoelastic, deformable, and adhesive hydrogel was synthesized by crosslinking a 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer hydrogel with a chemical crosslinker [N,N′-methylenebisacrylamide (MB)] using a cationic initiator, 2,2′-azobis-[2-(1,3-dimethyl-4,5-dihydro-1H-imidazol-3-ium-2-yl)]propane triflate (ADIP). The adhesive PMPC gel was tolerant to peeling during adhesion, and the adhesion energy of the hydrogel increased as the contact time with the adhesion target increased. Furthermore, the mechanism underlying the synthesis of deformable and adhesive hydrogels was determined by analyzing the polymerization behavior. The polymer synthesized with ADIP had a lower molecular weight than that synthesized with a conventional redox-type initiator, ammonium persulfate/N,N,N′,N′-tetramethylethylenediamine. Moreover, an analysis of the reactivity of various monomers and crosslinkers indicated low reactivity of the acrylamide-type crosslinker MB to methacrylate-type monomers; on this basis, the appropriate combination of monomers and crosslinkers for generating the target hydrogel was determined. The cytocompatibility of the prepared PMPC hydrogel was also confirmed. Thus, this study provides guidelines for the rational design of highly deformable, adhesive hydrogels with cytocompatibility. In this study, a deformable and adhesive biocompatible hydrogel composed of 2-methacryloyloxyethyl phosphorylcholine (MPC) with a chemical crosslinker [N,N′-methylenebisacrylamide] was synthesized using a cationic radical initiator, 2,2′-azobis-[2-(1,3-dimethyl- 4,5-dihydro-1H-imidazol-3-ium-2-yl)]propane triflate (ADIP). The adhesive PMPC gel was tolerant to peeling during adhesion. Furthermore, the formation mechanism underlying the synthesis of deformable and adhesive hydrogels was determined by analyzing the polymerization behavior. The polymer synthesized with ADIP had a lower molecular weight than that synthesized with a conventional redox-type initiator, ammonium persulfate/N,N,N′,N′-tetamethylethylenediamine. Moreover, the appropriate combination of monomers and crosslinkers required to generate the target hydrogel was determined
{"title":"Development of deformable and adhesive biocompatible polymer hydrogels by a simple one-pot method using ADIP as a cationic radical initiator","authors":"Tsukuru Masuda, Yui Saegusa, Toshikazu Tsuji, Madoka Takai","doi":"10.1038/s41428-025-01025-9","DOIUrl":"10.1038/s41428-025-01025-9","url":null,"abstract":"In this study, a highly viscoelastic, deformable, and adhesive hydrogel was synthesized by crosslinking a 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer hydrogel with a chemical crosslinker [N,N′-methylenebisacrylamide (MB)] using a cationic initiator, 2,2′-azobis-[2-(1,3-dimethyl-4,5-dihydro-1H-imidazol-3-ium-2-yl)]propane triflate (ADIP). The adhesive PMPC gel was tolerant to peeling during adhesion, and the adhesion energy of the hydrogel increased as the contact time with the adhesion target increased. Furthermore, the mechanism underlying the synthesis of deformable and adhesive hydrogels was determined by analyzing the polymerization behavior. The polymer synthesized with ADIP had a lower molecular weight than that synthesized with a conventional redox-type initiator, ammonium persulfate/N,N,N′,N′-tetramethylethylenediamine. Moreover, an analysis of the reactivity of various monomers and crosslinkers indicated low reactivity of the acrylamide-type crosslinker MB to methacrylate-type monomers; on this basis, the appropriate combination of monomers and crosslinkers for generating the target hydrogel was determined. The cytocompatibility of the prepared PMPC hydrogel was also confirmed. Thus, this study provides guidelines for the rational design of highly deformable, adhesive hydrogels with cytocompatibility. In this study, a deformable and adhesive biocompatible hydrogel composed of 2-methacryloyloxyethyl phosphorylcholine (MPC) with a chemical crosslinker [N,N′-methylenebisacrylamide] was synthesized using a cationic radical initiator, 2,2′-azobis-[2-(1,3-dimethyl- 4,5-dihydro-1H-imidazol-3-ium-2-yl)]propane triflate (ADIP). The adhesive PMPC gel was tolerant to peeling during adhesion. Furthermore, the formation mechanism underlying the synthesis of deformable and adhesive hydrogels was determined by analyzing the polymerization behavior. The polymer synthesized with ADIP had a lower molecular weight than that synthesized with a conventional redox-type initiator, ammonium persulfate/N,N,N′,N′-tetamethylethylenediamine. Moreover, the appropriate combination of monomers and crosslinkers required to generate the target hydrogel was determined","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 11","pages":"1257-1268"},"PeriodicalIF":2.7,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01025-9.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145436510","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 : 2025-02-26DOI: 10.1038/s41428-025-01016-w
Chenyue He, Takuya Matsumoto, Takashi Nishino
In this study, the stress transfer behaviors of poly(L-lactic acid) (PLLA)/hydroxyapatite (HAp) composites during tensile tests were investigated by in situ synchrotron X-ray diffraction. When tensile stress was applied to the composite, a diffraction peak assigned to the (211) plane of HAp shifted to a lower angle, and the stress was transferred through the interface between the PLLA matrix and HAp fillers. The stress distributed to the HAp fillers was several times greater than the applied stress. The dependence of the stress transfer on the fraction ratio of the HAp filler to the filler size was attained. Furthermore, the correlation between the macroscopic mechanical properties and stress transfer behaviors of the composites during tensile deformation and fracture was revealed using in situ X-ray diffraction measurements with synchrotron radiation. At the yielding points, interfacial failure between PLLA and HAp was determined. In situ X-ray diffraction measurements were shown to be reliable and provided a practical analysis method to obtain an understanding of the dynamic process of the mechanical deformation of composites. In this study, the stress transfer behaviors of poly(L-lactic acid) (PLLA)/hydroxyapatite (HAp) composites during tensile tests were investigated by in situ synchrotron X-ray diffraction. The effects of HAp fillers and their size on the stress transfer behaviors were discussed. Furthermore, the correlation between the macroscopic mechanical properties and stress transfer behaviors of the composites during tensile deformation and fracture was revealed. At the yielding points, interfacial failure between PLLA and HAp was determined.
{"title":"Stress transfer analyses of poly(L-lactic acid)/hydroxyapatite composites by synchrotron radiation","authors":"Chenyue He, Takuya Matsumoto, Takashi Nishino","doi":"10.1038/s41428-025-01016-w","DOIUrl":"10.1038/s41428-025-01016-w","url":null,"abstract":"In this study, the stress transfer behaviors of poly(L-lactic acid) (PLLA)/hydroxyapatite (HAp) composites during tensile tests were investigated by in situ synchrotron X-ray diffraction. When tensile stress was applied to the composite, a diffraction peak assigned to the (211) plane of HAp shifted to a lower angle, and the stress was transferred through the interface between the PLLA matrix and HAp fillers. The stress distributed to the HAp fillers was several times greater than the applied stress. The dependence of the stress transfer on the fraction ratio of the HAp filler to the filler size was attained. Furthermore, the correlation between the macroscopic mechanical properties and stress transfer behaviors of the composites during tensile deformation and fracture was revealed using in situ X-ray diffraction measurements with synchrotron radiation. At the yielding points, interfacial failure between PLLA and HAp was determined. In situ X-ray diffraction measurements were shown to be reliable and provided a practical analysis method to obtain an understanding of the dynamic process of the mechanical deformation of composites. In this study, the stress transfer behaviors of poly(L-lactic acid) (PLLA)/hydroxyapatite (HAp) composites during tensile tests were investigated by in situ synchrotron X-ray diffraction. The effects of HAp fillers and their size on the stress transfer behaviors were discussed. Furthermore, the correlation between the macroscopic mechanical properties and stress transfer behaviors of the composites during tensile deformation and fracture was revealed. At the yielding points, interfacial failure between PLLA and HAp was determined.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 6","pages":"653-664"},"PeriodicalIF":2.3,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144214240","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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