水中阴离子型二嵌段共聚物的pH响应性分子内和分子间胶束形成

pH-Responsive Intra- and Inter-Molecularly Micelle Formation of Anionic Diblock Copolymer in Water.

作者信息

Mizusaki Masanobu, Shimada Yoshihiko, Morishima Yotaro, Yusa Shin-Ichi

机构信息

Department of Applied Chemistry, Graduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo 671-2280, Japan.

Faculty of Engineering, Fukui University of Technology, 6-3-1 Gakuen, Fukui 910-8505, Japan.

出版信息

Polymers (Basel). 2016 Feb 19;8(2):56. doi: 10.3390/polym8020056.

DOI:10.3390/polym8020056

PMID:30979151

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6432565/

Abstract

Poly(sodium2-(acrylamido)-2-methylpropanesulfonate)--poly(sodium11-(acrylamido)undecanoate) (PAMPS⁻PAaU) was synthesized via reversible addition-fragmentation chain transfer (RAFT)-controlled radical polymerization. The "living" polymerization of PAaU was evidenced by the fact that the molecular weight distribution was narrow (/ = 1.23). The pH-induced association behavior of PAMPS⁻PAaU in 0.1 M NaCl aqueous solutions as a function of solution pH was investigated by ¹H NMR spin-spin relaxation time, dynamic light scattering (DLS), static light scattering (SLS), and fluorescence probe techniques. These results indicated that PAMPS⁻PAaU formed polymer micelles in 0.1 M NaCl aqueous solutions at pH < 9. At pH = 8⁻9, the polymer formed the micelles intramolecularly due to hydrophobic self-association of the PAaU block within the single polymer chain. On the other hand, at pH < 8, micellization occurred intermolecularly to form polymer micelles comprising hydrophobic PAaU cores and hydrophilic PAMPS shells.

摘要

通过可逆加成-断裂链转移（RAFT）可控自由基聚合合成了聚（2-（丙烯酰胺基）-2-甲基丙磺酸钠）-聚（11-（丙烯酰胺基）十一酸钠）（PAMPS⁻PAaU）。PAaU的“活性”聚合通过分子量分布狭窄（/ = 1.23）这一事实得到证明。采用¹H NMR自旋-自旋弛豫时间、动态光散射（DLS）、静态光散射（SLS）和荧光探针技术研究了PAMPS⁻PAaU在0.1 M NaCl水溶液中作为溶液pH函数的pH诱导缔合行为。这些结果表明，PAMPS⁻PAaU在pH < 9的0.1 M NaCl水溶液中形成聚合物胶束。在pH = 8⁻9时，由于单个聚合物链内PAaU嵌段的疏水自缔合，聚合物在分子内形成胶束。另一方面，在pH < 8时，分子间发生胶束化，形成由疏水PAaU核和亲水PAMPS壳组成的聚合物胶束。