writer：Ruijing Liang, Jiangping Xu, Weikun Li, Yonggui Liao, Ke Wang, Jichun You, Jintao Zhu, Wei Jiang
keywords：无机纳米粒子, 嵌段共聚物, 胶束聚集体, 氢键定向超分子组装, 定位, 金纳米粒子
source：期刊
specific source：Macromolecules, 2015, 48(1), 256-263
Issue time：2015年

摘要：无机纳米粒子（NPs）在聚合物基体中的定位对其杂化材料性能具有关键作用。本文采用简单而通用的氢键定向超分子组装（HBSA）策略，通过调控Au纳米粒子表面聚合物刷的选择性，实现Au NPs在聚苯乙烯-b-聚4-乙烯基吡啶（PS-b-P4VP）圆柱形胶束聚集体中从中心到界面的精确控制。PS-b-P4VP与正十五烷基苯酚（PDP）通过P4VP吡啶基与PDP羟基之间的氢键形成PS-b-P4VP(PDP)x梳-线团超分子；PS接枝Au NPs选择性分布在PS畴中，而PS/P4VP接枝Au NPs的二元混合物吸附在PS与P4VP(PDP)x畴之间的界面，这可能是由于Au NPs表面的PS和P4VP配体重新分布，形成两亲性类表面活性剂NPs。通过选择性解组装超分子，可获得Au NPs定位可控的孤立圆柱形胶束聚集体。研究还系统考察了超分子嵌段畴尺寸、超分子组成、Au NPs尺寸和体积分数对杂化胶束聚集体形貌及NP定位的影响。这些定位和负载效率可控的杂化胶束聚集体可拓展其在光学/电子器件、催化和药物递送系统中的应用。

Abstract：Localization of inorganic nanoparticles (NPs) into polymer matrix plays a crucial role in determining the performance of hybrid materials. A simple, yet versatile hydrogen bonding directed supramolecular assembly (HBSA) strategy is employed to control the localization of Au NPs from the center to the interface in polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) cylindrical micellar aggregates by tailoring the selectivity of polymer brushes on the surface of Au NPs. PS-b-P4VP(PDP)x comb-coil supramolecules are constructed by PS-b-P4VP and n-pentadecylphenol (PDP) via hydrogen bonding. PS-tethered Au NPs are selectively localized in the PS domain, while a binary mixture of PS- and P4VP-tethered Au NPs are adsorbed to the interface between PS and P4VP(PDP)x domains, presumably due to redistribution of PS and P4VP ligands on the Au NPs surface. Isolated cylindrical micellar aggregates with controlled localization of Au NPs are obtained by selective disassembly of the supramolecules. The effects of supramolecular block domain size, composition of the supramolecules, size of the Au NPs, and volume fraction of the Au NPs on the morphology and localization are carefully investigated. These hybrid micellar aggregates with controlled localization and loading efficiency of Au NPs may find more potential uses in optical/electronic devices, catalysis, and drug delivery systems.

论文链接：https://doi.org/10.1021/ma501835r