Department of Chemistry & Biochemistry, University of the Sciences , Philadelphia, Pennsylvania 19104, United States.
Cornell High Energy Synchrotron Source , Ithaca, New York 14853, United States.
ACS Appl Mater Interfaces. 2018 Feb 28;10(8):7459-7468. doi: 10.1021/acsami.7b18305. Epub 2018 Feb 15.
The concept of co-ordinated responsive arrays of surface-linked islands (polymer CORALs) is introduced. This study targets a responsive system capable of revealing or covering the substrate surface in response to environmental changes in a reversible way. A convenient method of fabrication of polymer CORALs is proposed. It is based on microphase separation that occurs in thin films of supramolecular assemblies of block copolymers with reactive blocks. Such blocks form nanometer-size domains that may serve as anchors for surface-linked polymer islands. Two characteristics of the islands are critically important for the switching function: high grafting density within the islands and small lateral separation that allows interactions between polymer chains grafted to the neighboring islands. This combination permits complete coverage of the substrate surface upon exposure to a good solvent (relaxed state). In a weak solvent, the chains collapse within the islands, thus revealing the substrate (compact state). The morphology of the CORALs in both states and some details of the switching process were studied with atomic force microscopy, grazing incidence small-angle scattering, and coarse-grained molecular dynamic simulations.
引入了协同响应表面连接岛的阵列(聚合物 CORAL)的概念。本研究的目标是一个响应系统,能够以可逆的方式响应环境变化,从而揭示或覆盖基底表面。提出了一种制造聚合物 CORAL 的方便方法。它基于超分子组装嵌段共聚物的薄膜中发生的微相分离,其中具有反应性的嵌段形成纳米级的域,可作为表面连接聚合物岛的锚。对于开关功能,岛的两个特征非常重要:岛内的高接枝密度和允许相邻岛屿上接枝的聚合物链相互作用的小的横向分离。这种组合允许在暴露于良溶剂时完全覆盖基底表面(松弛状态)。在弱溶剂中,链在岛内坍塌,从而暴露出基底(紧凑状态)。用原子力显微镜、掠入射小角散射和粗粒分子动力学模拟研究了两种状态下 CORAL 的形态和开关过程的一些细节。