Synthesis of Poly(N-vinylpyrrolidone)-Based Polymer Bottlebrushes by ATRPA and RAFT Polymerization: Toward Drug Delivery Application
Synthesis of Poly(N-vinylpyrrolidone)-Based Polymer Bottlebrushes by ATRPA and RAFT Polymerization: Toward Drug Delivery Application
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DOI：
10.3390/polym11061079
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发表时间：
2019-06-01
期刊：
影响因子：
5
通讯作者：
Huang, Chih-Feng
中科院分区：
文献类型：
--
作者：
Huang, Yi-Shen;Chen, Jem-Kun;Huang, Chih-Feng
本文利用原子转移自由基加成聚合（ATRPA）合成了一种特殊功能的聚酯。对2-溴-2-苯乙酸4-乙烯基苄基酯（VBBPA）进行了ATRPA，成功地合成了主链沿着含苄基溴的线型聚（VBBPA）（PVBBPA）聚酯。然而，为了获得一种新型的两亲性聚合物瓶刷，PVBBPA与N-乙烯基吡咯烷酮（NVP）的侧向ATRP扩链遇到了定量二聚化的问题。通过有效地将溴代物替换为黄原酸酯部分，我们观察到伪线性一级可逆加成-断裂链转移（RAFT）聚合，从而获得新型聚（4-乙烯基苄基-2-苯乙酸酯）-g-聚（NVP）（PVBPA-g-PNVP）两亲性聚合物瓶刷。通过荧光光谱、动态光散射（DLS）和扫描电子显微镜（SEM）表征了两亲聚合物瓶刷的临界胶束浓度（CMC）和粒径（CMC < 0.5 mg/mL;粒径=约0.5 nm）。100 nm）。对于药物递送应用，我们使用尼罗红的模型药物在不同pH环境（3、5和7）下检查释放曲线。最终，证明了聚合物瓶刷胶束的低细胞毒性和Madin-Darby犬肾上皮细胞（MDCK）的良好细胞摄取。
Atom transfer radical polyaddition (ATRPA) was utilized herein to synthesize a specific functional polyester. We conducted ATRPA of 4-vinylbenzyl 2-bromo-2-phenylacetate (VBBPA) inimer and successfully obtained a linear type poly(VBBPA) (PVBBPA) polyester with benzylic bromides along the backbone. To obtain a novel amphiphilic polymer bottlebrush, however, the lateral ATRP chain extension of PVBBPA with N-vinyl pyrrolidone (NVP) met the problem of quantitative dimerization. By replacing the bromides to xanthate moieties efficiently, we thus observed a pseudo linear first order reversible addition-fragmentation chain transfer (RAFT) polymerization to obtain novel poly(4-vinylbenzyl-2-phenylacetate)-g-poly(NVP) (PVBPA-g-PNVP) amphiphilic polymer bottlebrushes. The critical micelle concentration (CMC) and particle size of the amphiphilic polymer bottlebrushes were characterized by fluorescence spectroscopy, dynamic light scattering (DLS), and scanning electron microscopy (SEM) (CMCs < 0.5 mg/mL; particle sizes = ca. 100 nm). Toward drug delivery application, we examined release profiles using a model drug of Nile red at different pH environments (3, 5, and 7). Eventually, low cytotoxicity and well cell uptake of the Madin-Darby Canine Kidney Epithelial (MDCK) for the polymer bottlebrush micelles were demonstrated.