Counteranion effect on the RAFT polymerization of methacrylate-g-pentaarginine and its UCST-type thermoresponsive behavior

IF 6.3 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal Pub Date : 2025-08-12 DOI:10.1016/j.eurpolymj.2025.114202

Amélie Augé , Tetiana Dorosh , Ayoub Rachdi , Quentin Bievelot , Alain Chaumont , Fouzia Boulmedais , Delphine Chan-Seng

{"title":"Counteranion effect on the RAFT polymerization of methacrylate-g-pentaarginine and its UCST-type thermoresponsive behavior","authors":"Amélie Augé , Tetiana Dorosh , Ayoub Rachdi , Quentin Bievelot , Alain Chaumont , Fouzia Boulmedais , Delphine Chan-Seng","doi":"10.1016/j.eurpolymj.2025.114202","DOIUrl":null,"url":null,"abstract":"<div><div>Poly(methacrylate-<em>g</em>-pentaarginine) prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization exhibits an upper critical solution temperature (UCST) behavior with a sharp transition in pure water that can be affected by the presence of salts. In this work after optimizing the conditions for the synthesis of methacylate-<em>g</em>-pentaarginine (MA–hR5) and its RAFT polymerization, the effect of kosmotropic anions on the polymerization and the thermoresponsive behavior of these polymers in aqueous solutions was investigated experimentally and computationally. The use of chloride, phosphate, and sulfate anions lowered the phase transition temperature, while citrate ones increased it. The latter phenomenon was attributed to the ability of citrate anions to form bridges with the guanidinium groups present on the polymers according the protonation state of the citrate anions.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"238 ","pages":"Article 114202"},"PeriodicalIF":6.3000,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"European Polymer Journal","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0014305725004902","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}

引用次数: 0

Abstract

Poly(methacrylate-g-pentaarginine) prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization exhibits an upper critical solution temperature (UCST) behavior with a sharp transition in pure water that can be affected by the presence of salts. In this work after optimizing the conditions for the synthesis of methacylate-g-pentaarginine (MA–hR5) and its RAFT polymerization, the effect of kosmotropic anions on the polymerization and the thermoresponsive behavior of these polymers in aqueous solutions was investigated experimentally and computationally. The use of chloride, phosphate, and sulfate anions lowered the phase transition temperature, while citrate ones increased it. The latter phenomenon was attributed to the ability of citrate anions to form bridges with the guanidinium groups present on the polymers according the protonation state of the citrate anions.

Abstract Image

查看原文本刊更多论文

反阴离子对甲基丙烯酸酯-戊精氨酸RAFT聚合及其ucst型热响应行为的影响

通过可逆加成-破碎链转移（RAFT）聚合制备的聚甲基丙烯酸酯-g-五精氨酸在纯水中表现出较高的临界溶液温度（UCST）行为，并伴有急剧转变，这可能受到盐的存在的影响。本文在优化了甲基乙酸-g-五精氨酸（MA-hR5）的合成条件及其RAFT聚合的基础上，通过实验和计算研究了异向阴离子对聚合的影响以及聚合物在水溶液中的热响应行为。氯化物、磷酸盐和硫酸盐阴离子的使用降低了相变温度，柠檬酸盐阴离子的使用提高了相变温度。后一种现象归因于柠檬酸阴离子能够根据柠檬酸阴离子的质子化状态与聚合物上的胍基形成桥接。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

European Polymer Journal 化学-高分子科学

CiteScore

9.90

自引率

10.00%

发文量

691

审稿时长

23 days

期刊介绍： European Polymer Journal is dedicated to publishing work on fundamental and applied polymer chemistry and macromolecular materials. The journal covers all aspects of polymer synthesis, including polymerization mechanisms and chemical functional transformations, with a focus on novel polymers and the relationships between molecular structure and polymer properties. In addition, we welcome submissions on bio-based or renewable polymers, stimuli-responsive systems and polymer bio-hybrids. European Polymer Journal also publishes research on the biomedical application of polymers, including drug delivery and regenerative medicine. The main scope is covered but not limited to the following core research areas: Polymer synthesis and functionalization • Novel synthetic routes for polymerization, functional modification, controlled/living polymerization and precision polymers. Stimuli-responsive polymers • Including shape memory and self-healing polymers. Supramolecular polymers and self-assembly • Molecular recognition and higher order polymer structures. Renewable and sustainable polymers • Bio-based, biodegradable and anti-microbial polymers and polymeric bio-nanocomposites. Polymers at interfaces and surfaces • Chemistry and engineering of surfaces with biological relevance, including patterning, antifouling polymers and polymers for membrane applications. Biomedical applications and nanomedicine • Polymers for regenerative medicine, drug delivery molecular release and gene therapy The scope of European Polymer Journal no longer includes Polymer Physics.