Synthesis and characterization of amphiphilic poly(ε-caprolactone)-b-polyphosphoester diblock copolymers bearing multifunctional pendant groups
Synthesis and characterization of amphiphilic poly(ε-caprolactone)-b-polyphosphoester diblock copolymers bearing multifunctional pendant groups
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DOI：
10.1016/j.polymer.2012.05.013
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发表时间：
2012-06-21
期刊：
影响因子：
4.6
通讯作者：
Ni, Peihong
中科院分区：
文献类型：
--
作者：
Shao, Haiyan;Zhang, Mingzu;Ni, Peihong
采用开环聚合法合成了一系列不同嵌段长度的聚（ε-己内酯）-嵌段-聚[2-（2-氧代-1，3，2-二氧杂磷酰氧基）丙烯酸乙酯]（PCL-b-POPEA）母体嵌段共聚酯，并将四种硫醇通过Michael加成反应进行后聚合改性，得到了具有不同官能度（如，羟基、羧基、胺和氨基酸）。用红外光谱、核磁共振谱和凝胶渗透色谱对嵌段共聚物的结构进行了表征。利用荧光探针技术、透射电镜（TEM）和高性能粒度仪（HPPS）研究了PCL-b-POPEA的自组装行为。体外细胞毒性试验表明，该嵌段共聚物具有良好的生物相容性。使用阿霉素（DOX）作为模型药物的初始体外药物装载和释放研究表明，与没有酶的系统相比，在磷酸二酯酶I存在下更快地释放。此外，发现载DOX纳米粒对KB细胞增殖的抑制作用比游离DOX更强。因此，ROP和Michael型加成反应的结合提供了获得各种类型的多功能和可生物降解材料的一般途径。(C)2012爱思唯尔有限公司保留所有权利。
A series of parent block copolyesters poly(epsilon-caprolactone)-block-poly[2-(2-oxo-1, 3, 2-dioxaphospholoyloxy)ethyl acrylate] (PCL-b-POPEA) with different block lengths have been synthesized by ring-opening polymerization (ROP) and four kinds of mercaptans were then used in the post-polymerization modification via Michael-type addition reaction, resulting in several block copolyesters with various functionalities (e.g., hydroxyl, carboxyl, amine, and amino acid) in their pendant groups. The chemical structures of these block copolymers were characterized by FT-IR, NMR spectroscopy and GPC analysis. The self-assembly behaviors of PCL-b-POPEA have been studied by fluorescence probe technique, transmission electron microscopy (TEM) and high-performance particle size (HPPS) instrument. In vitro cytotoxicity test indicated that the block copolymers possess good biocompatibility. Initial in vitro drug loading and release studies using Doxorubicin (DOX) as a model drug demonstrated a faster release in the presence of phosphodiesterase I as compared to the system without enzyme. Moreover, it was found that DOX-loaded nanoparticles displayed higher inhibition to KB cell proliferation in comparison with free DOX. Therefore, the combination of ROP and Michael-type addition reaction provides a general access to various types of multifunctional and biodegradable materials. (C) 2012 Elsevier Ltd. All rights reserved.