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第 36 卷第 7 期 精 细 化 工 Vol.36, No.7
201 9 年 7 月 FINE CHEMICALS July 2019

功能材料
温度响应的酶催化核交联胶束

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方 倩，彭志平
（南昌大学 材料科学与工程学院，江西 南昌 330031）

摘要：以聚 4-乙酰氧基苯乙烯 P(4-ASt)和 N-异丙基丙烯酰胺（NIPAm）为单体，通过可逆加成-断裂链转移聚合
（RAFT）合成了结构明确窄相对分子质量分布（M w /M n =1.28）的两嵌段共聚物 P(4-ASt-b-NIPAm)。通过水合肼
将 P(4-ASt-b-NIPAm)中的 P(4-ASt)嵌段上的乙酰基团选择性水解后得到聚（4-乙烯基苯酚-b-N-异丙基丙烯酰胺）
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两嵌段共聚物 P(4-VPh-b-NIPAm)。采用 HNMR、FTIR 和 GPC 对 P(4-VPh-b-NIPAm)结构进行了表征，利用荧
光光谱、透光率法和 DLS 研究了其水溶液的聚集行为和温度响应性。结果表明，P(4-VPh-b-NIPAm)在水中可自
组装形成以 P（4-VPh）为核、PNIPAm 为壳的胶束，其临界胶束浓度（CMC）为 0.015 g/L，室温下平均粒径约
为 137 nm，低临界溶解温度（LCST）为 31.2 ℃。以辣根过氧化物酶（HRP）催化交联 P(4-VPh)核制备了平均
粒径约为 119 nm 的核交联胶束，TEM 显示干态核交联胶束为球形，粒径为 60~100 nm。核交联胶束水溶液具有
良好的热稳定性和温度响应性，其相转变温度为 32~36 ℃，LCST 约为 34.9 ℃，随温度升高平均粒径从 25 ℃
的 119 nm 减小至 37 ℃的 92.9 nm。
关键词：核交联胶束；酶催化交联；聚（4-乙烯基苯酚）；温度响应；两亲性嵌段共聚物
中图分类号：O631.3；TQ460.1 文献标识码：A 文章编号：1003-5214 (2019) 07-1326-08

Temperature-Responsive and Enzymatically Core-Crosslinked Micelles

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FANG Qian, PENG Zhi-ping
（School of Materials Science and Engineering, Nanchang University, Nanchang 330031, Jiangxi, China）

Abstract: Diblock copolymer P(4-ASt-b-NIPAm) with well-defined structure and narrow molecular-weight
distribution (M w/M n=1.28) was synthesized by reversible addition-fragmentation transfer (RAFT)
polymerization using poly(4-acetoxystyrene) P(4-ASt) and N-isopropylacrylamide (NIPAm) as monomers.
The acetyl groups in the chain of P(4-ASt-b-NIPAm) were selectively hydrolyzed by hydrazine hydrate to
obtain diblock copolymer P(4-VPh-b-NIPAm). Copolymer P(4-VPh-b-NIPAm) was characterized by
1 HNMR, FTIR and GPC. The aggregation behavior and temperature response of P(4-VPh-b-NIPAm)
aqueous solution were studied by fluorescence spectrum, transmittance method and DLS. The results
showed that copolymer P(VPh-b-NIPAm) could self-assemble into micelles using P(4-VPh) as core and
PNIPAm as shell in aqueous solution and the critical micelle concentration (CMC) was 0.015 g/L. The
average particle size was about 137 nm at room temperature and the lower critical solution temperature
(LCST) was 31.2 ℃. Horseradish peroxidase (HRP) catalyzed cross-linking of P(4-VPh) core to prepare
core-crosslinked micelles with an average particle size of 119 nm. TEM showed that dry core-crosslinked
micelles were spherical with particle size of 60~100 nm. The aqueous solution of core-crosslinked micelles
had good stability and temperature response. Its phase transition temperature ranged from 32 ℃ to 36 ℃
and its LCST was about 34.9 ℃. The average diameter of core-crosslinked micelles decreased from
119 nm to 92.9 nm with increasing temperature from 25 ℃ to 37 ℃.
Key words: core-crosslinked micelles; enzymactically crosslinked; poly(4-vinyl phenol); temperature
response; amphiphilic block copolymer

收稿日期：2019-01-20; 定用日期：2019-03-12; DOI: 10.13550/j.jxhg.20190066
基金项目：国家自然科学基金（21664010）；江西省自然科学基金（20161BAB206121）；南昌大学研究生创新专项资金（CX2017003）
作者简介：方 倩（1993—），女，硕士生。联系人：彭志平（1977—），男，副教授，E-mail：zzpeng@ncu.edu.cn。