writer：Nan Yan, Yan Zhang, Yun He, Yutian Zhu, Wei Jiang
keywords：无机纳米粒子, 嵌段共聚物, 自组装支架, 熵贡献, 焓贡献, 受限共组装
source：期刊
specific source：Macromolecules, 2017, 50(17), 6771-6778
Issue time：2017年

摘要：精确控制功能纳米粒子（NPs）在聚合物支架上的空间位置和排列，不仅对创造新型纳米结构很重要，也对增强杂化纳米材料性能至关重要。本文提出一种通过调控熵贡献和焓贡献，在乳液液滴内嵌段共聚物（BCP）与金纳米粒子（AuNPs）受限共组装过程中，将AuNPs精确定位于BCP支架上的策略。根据该策略，AuNPs配体损失构象熵产生的熵效应以及AuNPs配体与油/水界面表面活性剂之间的焓吸引，促使固体AuNPs向BCP表面移动；而AuNPs配体与相应聚合物链之间的焓相互作用则引导AuNPs定位在合适位置。通过该策略，可任意控制AuNPs在BCP支架上的位置和排列，例如位于蛹状支架两端或沿片层边界、松果状或芽状支架基部、Janus状支架一个半球的头部、整个半球或两个不同半球之间的边界。该方法可为功能NPs在BCP支架上的精确定位提供通用途径。

Abstract：Precisely controlling the spatial location and alignment of functional nanoparticles (NPs) on polymeric scaffolds is of great importance to not only create novel nanostructures but also enhance the properties of hybrid nanomaterials. A strategy of tailoring the entropic and enthalpic contributions to precisely position gold nanoparticles (AuNPs) on block copolymer (BCP) scaffolds through the confined coassembly of BCPs and AuNPs within the emulsion droplet is demonstrated. The entropic effect arisen by the loss in conformational entropy and the enthalpic attraction between ligands on AuNPs and surfactants at the oil/water interface induce the solid AuNPs to move to the BCP surface, while the enthalpic interaction between the ligands on AuNPs and the corresponding polymer chains guides the AuNPs to position at the appropriate place. By this strategy, both the location and alignment of AuNPs on BCP scaffolds can be controlled at will, such as at the two terminals or along the lamellar boundary of the pupa-like scaffolds, or at the bases of pinecone-like or bud-like scaffolds, or at the head of one hemisphere, the entire hemisphere, or along the boundary between the two distinct hemispheres of the Janus-like scaffolds. This methodology can offer a universal route to achieve the precise positioning of functional NPs on the BCP scaffolds.

论文链接：https://doi.org/10.1021/acs.macromol.7b01076