Multistimuli Responsive Nanocomposite Tectons for Pathway Dependent Self-Assembly and Acceleration of Covalent Bond Formation
Multistimuli Responsive Nanocomposite Tectons for Pathway Dependent Self-Assembly and Acceleration of Covalent Bond Formation
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DOI：
10.1021/jacs.9b06695
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发表时间：
2019-07
影响因子：
15
通讯作者：
Yuping Wang;Peter Santos;Joshua M Kubiak;Xinheng Guo;Margaret S. Lee;R. Macfarlane
中科院分区：
文献类型：
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作者：
Yuping Wang;Peter Santos;Joshua M Kubiak;Xinheng Guo;Margaret S. Lee;R. Macfarlane
纳米复合结构（nct）是最近发展起来的用于聚合物-纳米颗粒复合合成的构建块，由纳米颗粒核组成，这些纳米颗粒核被密集的单层聚合物链功能化，这些聚合物链终止于能够将nct连接成分层结构的超分子识别基团。原则上，使用分子结合来指导颗粒组装允许nct在设计上高度模块化，可以独立控制颗粒核心和聚合物刷的组成。然而，实现一系列组成和结构变化的NCT基材料的主要挑战是开发不同的超分子键相互作用来控制NCT组装，以及了解纳米颗粒支架周围多个超分子基团的组织如何影响它们的集体键相互作用。在这里，我们提出了一套合理设计的NCT系统，其中使用多种类型的超分子相互作用（氢键，金属络合和动态共价键形成）来调节NCT组装，作为多种外部刺激的函数，包括温度，小分子，pH和光。此外，在单个NCT系统中加入多个正交超分子化学物质，可以以途径依赖的方式决定组装的NCT的形态。最后，多刺激响应型nct能够通过组装后功能化修饰复合材料的性质，其中通过共价键连接的nct具有显著增强的稳定性，以快速有效的方式获得。因此，本文提出的设计为复合材料合成领域提供了重大进展，为合成具有复杂装配行为的分层有序复合材料建立了框架。
Nanocomposite tectons (NCTs) are a recently developed building block for polymer–nanoparticle composite synthesis, consisting of nanoparticle cores functionalized with dense monolayers of polymer chains that terminate in supramolecular recognition groups capable of linking NCTs into hierarchical structures. In principle, the use of molecular binding to guide particle assembly allows NCTs to be highly modular in design, with independent control over the composition of the particle core and polymer brush. However, a major challenge to realize an array of compositionally and structurally varied NCT-based materials is the development of different supramolecular bonding interactions to control NCT assembly, as well as an understanding of how the organization of multiple supramolecular groups around a nanoparticle scaffold affects their collective binding interactions. Here, we present a suite of rationally designed NCT systems, where multiple types of supramolecular interactions (hydrogen bonding, metal complexation, and dynamic covalent bond formation) are used to tune NCT assembly as a function of multiple external stimuli including temperature, small molecules, pH, and light. Furthermore, the incorporation of multiple orthogonal supramolecular chemistries in a single NCT system makes it possible to dictate the morphologies of the assembled NCTs in a pathway-dependent fashion. Finally, multistimuli responsive NCTs enable the modification of composite properties by postassembly functionalization, where NCTs linked by covalent bonds with significantly enhanced stability are obtained in a fast and efficient manner. The designs presented here therefore provide major advancement for the field of composite synthesis by establishing a framework for synthesizing hierarchically ordered composites capable of complicated assembly behaviors.