Department of Chemistry, University of Toronto, 80 Saint George Street, Toronto, Ontario, M5S 3H6, Canada.
School of Chemistry, University of Bristol, Bristol, BS8 1TS, UK.
Macromol Rapid Commun. 2018 Feb;39(3). doi: 10.1002/marc.201700554. Epub 2017 Nov 16.
Chemical and topographic surface patterning of inorganic polymer-functionalized nanoparticles (NPs) and their self-assembly in nanostructures with controllable architectures enable the design of new NP-based materials. Capping of NPs with inorganic polymer ligands, such as metallopolymers, can lead to new synergetic properties of individual NPs or their assemblies, and enhance NP processing in functional materials. Here, for gold NPs functionalized with polyferrocenylsilane, two distinct triggers are used to induce attraction between the polymer ligands and achieve NP self-assembly or topographic surface patterning of individual polymer-capped NPs. Control of polymer-solvent interactions is achieved by either changing the solvent composition or by the electrooxidation of polyferrocenylsilane ligands. These results expand the range of polymer ligands used for NP assembly and patterning, and can be used to explore new self-assembly modalities. The utilization of electrochemical polymer oxidation stimuli at easily accessible potentials broadens the range of stimuli leading to NP self-assembly and patterning.
无机聚合物功能化纳米粒子 (NPs) 的化学和形貌表面图案化及其在具有可控结构的纳米结构中的自组装使新型基于 NP 的材料的设计成为可能。用无机聚合物配体(如金属聚合物)对 NPs 进行封端,可以导致单个 NPs 或其组装体的新协同性质,并增强 NP 在功能材料中的加工。在这里,对于用聚二茂铁硅烷功能化的金 NPs,使用两种不同的触发因素来诱导聚合物配体之间的吸引力,从而实现 NP 自组装或单个聚合物封端 NPs 的形貌表面图案化。通过改变溶剂组成或通过聚二茂铁硅烷配体的电化学氧化来控制聚合物-溶剂相互作用。这些结果扩展了用于 NP 组装和图案化的聚合物配体的范围,并可用于探索新的自组装方式。在易于接近的电势下利用电化学聚合物氧化刺激拓宽了导致 NP 自组装和图案化的刺激范围。