{"title":"聚n -异丙基丙烯酰胺接枝聚合物侧链结构相关的热响应行为","authors":"Fujin Duan, Gege Liu, Jinqian Zhang, Xin Zhao, Qingqing Wang, Youliang Zhao","doi":"10.1021/acs.macromol.4c02611","DOIUrl":null,"url":null,"abstract":"The variations of side-chain architecture can significantly affect the thermoresponsive behaviors of graft polymers. This study is aimed at designing linear graft polymers with linear or cyclic pendants (LGPLs/LGPCs) to elucidate the distinct thermostability of polymer solutions. Three pairs of poly(<i>N</i>-isopropylacrylamide) (PNIPAM)-bearing graft polymers with a weight-average graft number (<i>N</i><sub>g</sub>) up to 16 are synthesized by the combination of the ring-first method, fractionation, and topology transformation. The chain architecture and graft number can affect the thermostability and thermosensitivity of polymer aqueous solutions, in which thermo-induced maximal variations of transmittance, light scattering intensity, and fluorescence intensity ratio related to amide–water hydrogen bonding drastically decrease with the incorporation of cyclic pendants and an increase of <i>N</i><sub>g</sub>. LGPLs with pronounced chain entanglement can self-assemble into thermostable lamellae, while other polymer assemblies are subjected to thermo-induced sphere-to-vesicle or vesicle-to-lamella transitions. This research affords a promising method to construct graft polymers with variable architectural parameters to achieve topology-dependent thermoresponsive behaviors.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"234 1","pages":""},"PeriodicalIF":5.2000,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Side-Chain Architecture-Dependent Thermoresponsive Behaviors of Graft Polymers with Poly(N-isopropylacrylamide) Pendants\",\"authors\":\"Fujin Duan, Gege Liu, Jinqian Zhang, Xin Zhao, Qingqing Wang, Youliang Zhao\",\"doi\":\"10.1021/acs.macromol.4c02611\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The variations of side-chain architecture can significantly affect the thermoresponsive behaviors of graft polymers. This study is aimed at designing linear graft polymers with linear or cyclic pendants (LGPLs/LGPCs) to elucidate the distinct thermostability of polymer solutions. Three pairs of poly(<i>N</i>-isopropylacrylamide) (PNIPAM)-bearing graft polymers with a weight-average graft number (<i>N</i><sub>g</sub>) up to 16 are synthesized by the combination of the ring-first method, fractionation, and topology transformation. The chain architecture and graft number can affect the thermostability and thermosensitivity of polymer aqueous solutions, in which thermo-induced maximal variations of transmittance, light scattering intensity, and fluorescence intensity ratio related to amide–water hydrogen bonding drastically decrease with the incorporation of cyclic pendants and an increase of <i>N</i><sub>g</sub>. LGPLs with pronounced chain entanglement can self-assemble into thermostable lamellae, while other polymer assemblies are subjected to thermo-induced sphere-to-vesicle or vesicle-to-lamella transitions. This research affords a promising method to construct graft polymers with variable architectural parameters to achieve topology-dependent thermoresponsive behaviors.\",\"PeriodicalId\":51,\"journal\":{\"name\":\"Macromolecules\",\"volume\":\"234 1\",\"pages\":\"\"},\"PeriodicalIF\":5.2000,\"publicationDate\":\"2025-01-30\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Macromolecules\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.macromol.4c02611\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Macromolecules","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.macromol.4c02611","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Side-Chain Architecture-Dependent Thermoresponsive Behaviors of Graft Polymers with Poly(N-isopropylacrylamide) Pendants
The variations of side-chain architecture can significantly affect the thermoresponsive behaviors of graft polymers. This study is aimed at designing linear graft polymers with linear or cyclic pendants (LGPLs/LGPCs) to elucidate the distinct thermostability of polymer solutions. Three pairs of poly(N-isopropylacrylamide) (PNIPAM)-bearing graft polymers with a weight-average graft number (Ng) up to 16 are synthesized by the combination of the ring-first method, fractionation, and topology transformation. The chain architecture and graft number can affect the thermostability and thermosensitivity of polymer aqueous solutions, in which thermo-induced maximal variations of transmittance, light scattering intensity, and fluorescence intensity ratio related to amide–water hydrogen bonding drastically decrease with the incorporation of cyclic pendants and an increase of Ng. LGPLs with pronounced chain entanglement can self-assemble into thermostable lamellae, while other polymer assemblies are subjected to thermo-induced sphere-to-vesicle or vesicle-to-lamella transitions. This research affords a promising method to construct graft polymers with variable architectural parameters to achieve topology-dependent thermoresponsive behaviors.
期刊介绍：
Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.
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