Kinetics of pH-induced formation and dissociation of polymeric vesicles assembled from a water-soluble zwitterionic diblock copolymer

Kinetics of pH-induced formation and dissociation of polymeric vesicles assembled from a water-soluble zwitterionic diblock copolymer
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由水溶性两性离子二嵌段共聚物组装而成的聚合物囊泡的 pH 诱导形成和解离的动力学

DOI:
10.1021/la801190z
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发表时间:
2008-09-16
期刊:
影响因子:
3.9
通讯作者:
Liu, Shiyong
Liu, Shiyong
中科院分区:
化学2区
文献类型:
--
作者:
Shen, Lei;Du, Jianzhong;Liu, Shiyong

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The kinetics of pH-induced formation and dissociation of vesicles self-assembled from a biocompatible zwitterionic diblock copolymer, poly (2-(methacryloyloxy)ethy I phosphorylcholine)-b-poly(2-(diisopropylamino)ethyl methacrylate) (PMPC-b-PDPA), was investigated in detail via a combination of stopped-flow light scattering and laser light scattering (LLS). Upon jumping from pH 2 to 10, stopped-flow light scattering reveals three distinct relaxation processes for the early stages of vesicle self-assembly (0-40 s). Kinetic sequences associated with the obtained three characteristic relaxation times have been tentatively proposed. Moreover, the kinetics of vesicle formation in the later stage (from 3 min onward) was investigated by dynamic LLS. It was found that both the intensity-averaged hydrodynamic radius, < R-h >, and the polydispersity, mu(2)/Gamma(2), decrease exponentially, yielding a characteristic relaxation time of similar to 350 s. To our knowledge, this is the first report on the kinetics of the unimer-to-vesicle transition of a stimulus-responsive diblock copolymer. The kinetics of vesicle dissociation for a pH jump from 12 to 2 was also investigated. The breakdown of polymeric vesicles is extremely fast and is independent of polymer concentration; it is complete within similar to 5 ms and is in marked contrast to the much slower rate of vesicle formation.