State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200438, People's Republic of China.
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Science, Changchun 130022, People's Republic of China.
J Am Chem Soc. 2021 Apr 7;143(13):5060-5070. doi: 10.1021/jacs.1c00310. Epub 2021 Mar 26.
Patchy colloidal nanoparticles are important for a broad range of applications, especially as building blocks for complex and functional structural materials, but the controllable generation of chemical patches on as-synthesized nanoparticles remains a challenge. This article describes a robust strategy for the scalable synthesis of high-quality patchy nanoparticles in high yield and solid content. A simple thermal treatment of a mixture of gold nanoparticles and thiol-terminated block-random copolymers in selected solvents produced a variety of patchy nanoparticles with a controlled morphology and number of polymeric patches (e.g., beanlike patch, one patch, two patches, three patches, multiple patches, and open-configuration patch). We show in experiments and simulations that the dynamic detachment/attachment of copolymers and the exchange of copolymers between the nanoparticle surface and free micelles in the solution-which are dictated by the architecture of copolymers-govern the formation of polymeric patches. This work not only offers an effective approach to patchy nanoparticles but also provides new insights into the phase behaviors of copolymers on nanoscale surfaces.
具有不规则胶体纳米颗粒的物质在很多领域都有重要应用，尤其是作为复杂且多功能结构材料的构建模块。然而，如何在合成后的纳米颗粒上可控地生成化学补丁仍然是一个挑战。本文描述了一种在高固体含量和高产量下，可规模化制备高质量具有不规则胶体纳米颗粒的稳健策略。在选择的溶剂中，通过简单的热处理金纳米颗粒和巯基封端的嵌段无规共聚物的混合物，可得到具有可控形貌和聚合物补丁数量（例如，豆状补丁、一个补丁、两个补丁、三个补丁、多个补丁和开放式补丁）的各种不规则胶体纳米颗粒。我们通过实验和模拟表明，共聚物的动态脱落/附着以及纳米颗粒表面和溶液中游离胶束之间共聚物的交换（由共聚物的结构决定）决定了聚合物补丁的形成。这项工作不仅为制备具有不规则胶体纳米颗粒提供了有效途径，还为共聚物在纳米尺度表面的相行为提供了新的见解。
