Degradable and Comb-Like PEG-Based Copolymers by Nitroxide-Mediated Radical Ring-Opening Polymerization
Degradable and Comb-Like PEG-Based Copolymers by Nitroxide-Mediated Radical Ring-Opening Polymerization
复制标题
DOI：
10.1021/bm401157g
复制
发表时间：
2013-10-01
影响因子：
6.2
通讯作者：
Nicolas, Julien
中科院分区：
文献类型：
--
作者：
Delplace, Vianney;Tardy, Antoine;Nicolas, Julien
以2-亚甲基-1，3-二氧杂环庚烷（MDO）、5，6-苯并-2-亚甲基-1，3-二氧杂环庚烷（BMDO）和2-亚甲基-4-苯基-1，3-二氧杂环戊烷（MPDL）为原料，分别与低聚（乙二醇）甲基醚甲基丙烯酸酯和少量丙烯腈（或苯乙烯）在90 ° C下通过氮氧介导的自由基开环聚合，作为制备用于生物医学应用的可降解PEG基共聚物的方便方法。MPDL是最好的候选者，能够实现高单体转化率，并合成主链中酯基数量可调的明确的基于PEG的共聚物，导致几乎完全的水解降解（5% KOH水溶液，环境温度）。在三种不同的细胞系（即，成纤维细胞、内皮细胞和巨噬细胞），代表了通过NMP技术设计用于PEG化和生物缀合的可降解前体的有前景的方法。
Three cyclic ketene acetals, 2-methylene-1,3-dioxepane (MDO), 5,6-benzo-2-methylene-1,3-dioxepane (BMDO), and 2-methylene-4-phenyl-1,3-dioxolane (MPDL), have been copolymerized with oligo(ethylene glycol) methyl ether methacrylate and a small amount of acrylonitrile (or styrene) at 90 degrees C by nitroxidemediated radical ring-opening polymerization, as a convenient way to prepare degradable PEG-based copolymers for biomedical applications. MPDL was the best candidate, enabling high monomer conversions to be reached and well-defined PEG-based copolymers with adjustable amount of ester groups in the main chain to be synthesized, leading to nearly complete hydrolytic degradation (5% KOH aqueous solution, ambient temperature). The noncytotoxicity of the obtained copolymers was shown on three different cell lines (i.e., fibroblasts, endothelial cells and macrophages), representing a promising approach for the design of degradable precursors for PEGylation and bioconjugation via the NMP technique.