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聚(甲基丙烯酸 2-(二甲基氨基)乙酯-co-(聚乙二醇)甲基丙烯酸酯)无规共聚物及其改性衍生物的刺激响应性自组装

Stimuli-Responsive Self-Assembly of Poly(2-(Dimethylamino)ethyl Methacrylate-co-(oligo ethylene glycol)methacrylate) Random Copolymers and Their Modified Derivatives.

作者信息

Vardaxi Antiopi, Pispas Stergios

机构信息

Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vassileos Constantinou Avenue, 11635 Athens, Greece.

Department of Chemistry, National and Kapodistrian University of Athens (NKUA), 15784 Athens, Greece.

出版信息

Polymers (Basel). 2023 Mar 19;15(6):1519. doi: 10.3390/polym15061519.

DOI:10.3390/polym15061519
PMID:36987299
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10059824/
Abstract

In this work, the synthesis and the stimuli-responsive self-assembly behavior of novel double-hydrophilic poly(2-(dimethylamino)ethyl methacrylate-co-(oligo ethylene glycol)methacrylate) random copolymers and their chemically modified derivatives are presented. The synthesis of P(DMAEMA-co-OEGMA) copolymers of different DMAEMA mass compositions was successfully conducted through RAFT polymerization, further followed by the hydrophilic/hydrophobic quaternization with methyl iodide (CHI), 1-iodohexane (CHI), and 1-iodododecane (CHI). The tertiary and quaternary amines are randomly arranged within the DMAEMA segment, responding thus to pH, temperature, and salt alterations in aqueous solutions. Light scattering techniques elucidated the intramolecular self-folding and intermolecular self-assembly of polymer chains of P(DMAEMA-co-OEGMA) copolymers upon exposure to different pHs and temperatures. Q(P(DMAEMA-co-OEGMA)) cationic polyelectrolytes demonstrated moderate response to pH, temperature, and ionic strength as a result of the permanent hydrophilic/hydrophobic profile, closely connected with the attached alkyl chains and the quaternization degree. Moreover, fluorescence spectroscopy measurements confirmed the internal micropolarity and the picture of the aggregate inner structure.

摘要

在本工作中,介绍了新型双亲水聚(甲基丙烯酸2-(二甲氨基)乙酯-共-(低聚乙二醇)甲基丙烯酸酯)无规共聚物及其化学修饰衍生物的合成和刺激响应性自组装行为。通过可逆加成-断裂链转移(RAFT)聚合成功合成了不同DMAEMA质量组成的P(DMAEMA-共-OEGMA)共聚物,随后用甲基碘(CHI)、1-碘己烷(CHI)和1-碘十二烷(CHI)进行亲水/疏水季铵化。叔胺和季铵盐在DMAEMA链段中随机排列,因此对水溶液中的pH、温度和盐变化有响应。光散射技术阐明了P(DMAEMA-共-OEGMA)共聚物的聚合物链在暴露于不同pH值和温度时的分子内自折叠和分子间自组装。由于与连接的烷基链和季铵化程度密切相关的永久亲水/疏水特性,Q(P(DMAEMA-共-OEGMA))阳离子聚电解质对pH、温度和离子强度表现出适度的响应。此外,荧光光谱测量证实了内部微极性和聚集体内部结构的情况。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/38c0/10059824/e9f5ddb58423/polymers-15-01519-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/38c0/10059824/d0cbdefc1c15/polymers-15-01519-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/38c0/10059824/0dfe63b9eeb5/polymers-15-01519-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/38c0/10059824/ba4527915180/polymers-15-01519-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/38c0/10059824/2d2b0d456e0d/polymers-15-01519-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/38c0/10059824/cf64f49f6262/polymers-15-01519-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/38c0/10059824/d84ab13de26a/polymers-15-01519-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/38c0/10059824/ff4fc6dac870/polymers-15-01519-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/38c0/10059824/e9f5ddb58423/polymers-15-01519-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/38c0/10059824/d0cbdefc1c15/polymers-15-01519-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/38c0/10059824/0dfe63b9eeb5/polymers-15-01519-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/38c0/10059824/ba4527915180/polymers-15-01519-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/38c0/10059824/2d2b0d456e0d/polymers-15-01519-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/38c0/10059824/cf64f49f6262/polymers-15-01519-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/38c0/10059824/d84ab13de26a/polymers-15-01519-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/38c0/10059824/ff4fc6dac870/polymers-15-01519-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/38c0/10059824/e9f5ddb58423/polymers-15-01519-g007.jpg

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