Controlling Vesicular Size via Topological Engineering of Amphiphilic Polymer in Polymerization-Induced Self-Assembly

Controlling Vesicular Size via Topological Engineering of Amphiphilic Polymer in Polymerization-Induced Self-Assembly
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通过聚合诱导自组装中两亲性聚合物的拓扑工程控制囊泡尺寸

DOI:
10.1021/acs.macromol.7b02039
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发表时间:
2017-12-26
期刊:
影响因子:
5.5
通讯作者:
Yuan, Jinying
Yuan, Jinying
中科院分区:
化学1区
文献类型:
--
作者:
Huo, Meng;Xu, Ziyang;Yuan, Jinying

文献摘要

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聚合物拓扑结构对聚合物组装体尺寸和形貌的影响研究较少。在此,我们报告了通过聚合诱导自组装(PISA)两亲共聚物的疏溶剂嵌段的拓扑工程制备具有可调尺寸的聚合体。两种具有不同分子几何形状的单体在不同投料比下进行可逆加成-破碎链转移(RAFT)分散共聚,可以很容易地调节疏溶剂嵌段的拓扑结构。作为一项概念验证研究,甲基丙烯酸苄酯(BzMA)和甲基丙烯酸硬脂酯(SMA)的RAFT分散共聚产生的聚合体大小从200到1500 nm不等,具体取决于BzMA/SMA的比例。除了囊泡外,通过改变BzMA/SMA的比例,还获得了具有复杂内部结构的组件,表明了该策略的鲁棒性。通过一系列粗粒度的分子模拟揭示了这一机制,并阐明了其机理。
The significance of polymer topology to the size and morphology of polymeric assemblies was less studied. Herein we report the preparation of polymersomes with tunable sizes via topological engineering of the solvophobic block of the amphiphilic copolymer in polymerization-induced self-assembly (PISA). The topology of the solvophobic block could be facilely regulated by reversible addition–fragmentation chain transfer (RAFT) dispersion copolymerization of two kinds of monomers with distinctive molecular geometries at variable feed ratios. As a proof-of-concept study, RAFT dispersion copolymerization of benzyl methacrylate (BzMA) and stearyl methacrylate (SMA) produced polymersomes with size ranging from 200 to 1500 nm depending on the ratio of BzMA/SMA. Besides vesicles, assemblies with complex internal structures were obtained by varying the ratio of BzMA/SMA, suggesting the robustness of this strategy. The mechanism was revealed by a series of coarse-grained molecular simulations, which elucidated the d...