Yan Chuan, Yang Liqin, Mo Xiangquan, Chen Keying, Niu Weiya, Zhao Zhiju, Li Guanghua
Guangxi Key Laboratory of Petrochemical Resource Processing & Process Intensification Technology, School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, China.
Hebei Functional Polymer Materials R&D and Engineering Application Technology Innovation Center, College of Chemistry & Chemical Engineering, Xingtai University, Xingtai 050041, China.
Materials (Basel). 2021 Dec 21;15(1):2. doi: 10.3390/ma15010002.
Amphiphilic random copolymer poly(methacrylamido-azobenzene)--poly(2-hydroxyethylacrylate) (PMAAAB--PHEA) was synthesized via hydrolysis of poly(methacrylamido-azobenzene)--poly[2-((2'-tetrahydropyranyl)oxy)ethylacrylate] (PMAAAB--P(THP-HEA)), which was prepared by conventional radical polymerization. PMAAAB--PHEA micelles were then prepared via dialysis method against water with DMF as solvent. The structure, morphology, size, and low critical solution temperature (LCST) of PMAAAB--PHEA and its micelles were determined by H-NMR, GPC, TEM, and DLS. The thermo- and photo-responsive behaviors of the resulting polymer micelles were investigated with Nile red as a fluorescence probe. The results showed that PMAAAB--PHEA micelles were porous or bowl-shaped and its size was 135-150 nm, and its LCST was 55 °C when of the random copolymer was 0.5351; the hydrophobicity of the micellar core was changed reversibly under the irradiation of UV light and visible light without release of Nile red or disruption of micelles; the size and solubilization capacity of the micelles were dependent on temperature, and Nile red would migrate for many times between the water phase and the micelles, and finally increasingly accumulated during the repeated heating and cooling processes.
两亲性无规共聚物聚（甲基丙烯酰胺基偶氮苯）-聚（丙烯酸2-羟乙酯）（PMAAAB-PHEA）是通过聚（甲基丙烯酰胺基偶氮苯）-聚[2-（（2'-四氢吡喃基）氧基）丙烯酸乙酯]（PMAAAB-P（THP-HEA））水解合成的，后者通过常规自由基聚合制备。然后以N，N-二甲基甲酰胺（DMF）为溶剂，通过对水透析的方法制备了PMAAAB-PHEA胶束。通过氢核磁共振（H-NMR）、凝胶渗透色谱（GPC）、透射电子显微镜（TEM）和动态光散射（DLS）测定了PMAAAB-PHEA及其胶束的结构、形态、尺寸和低临界溶液温度（LCST）。以尼罗红为荧光探针，研究了所得聚合物胶束的热响应和光响应行为。结果表明，PMAAAB-PHEA胶束呈多孔或碗状，尺寸为135-150nm，当无规共聚物的摩尔分数为0.5351时，其LCST为55℃；在紫外光和可见光照射下，胶束核的疏水性可逆变化，尼罗红未释放，胶束也未破坏；胶束的尺寸和增溶能力取决于温度，尼罗红会在水相和胶束之间多次迁移，最终在反复加热和冷却过程中逐渐积累。
