Chen Nicolas, Davydovich Oleg, McConnell Caitlyn, Sidorenko Alexander, Moore Preston B
Department of Chemistry & Biochemistry, University of the Sciences in Philadelphia, Philadelphia, PA 19104, USA.
2720 Beckman Institute, 405 North Mathews Avenue, Urbana, IL 61801, USA.
Polymers (Basel). 2021 Aug 1;13(15):2570. doi: 10.3390/polym13152570.
COordinated Responsive Arrays of Surface-Linked polymer islands (CORALS) allow for the creation of molecular surfaces with novel and switchable properties. Critical components of CORALs are the uniformly distributed islands of densely grafted polymer chains (nanoislands) separated by regions of bare surface. The grafting footprint and separation distances of nanoislands are comparable to that of the constituent polymer chains themselves. Herein, we characterize the structural features of the nanoislands and semiflexible polymers within to better understand this critical constituent of CORALs. We observe different characteristics of grafted semiflexible polymers depending on the polymer island's size and distance from the center of the island. Specifically, the characteristics of the chains at the island periphery are similar to isolated tethered polymer chains (full flexible chains), while chains in the center of the island experience the neighbor effect such as chains in the classic polymer brush. Chains close to the edge of the islands exhibit unique structural features between these two regimes. These results can be used in the rational design of CORALs with specific interfacial characteristics and predictable responses to external stimuli. It is hoped that this the discussion of the different morphologies of the polymers as a function of distance from the edge of the polymer will find applications in a wide variety of systems.
表面连接聚合物岛的协同响应阵列（CORALS）能够创建具有新颖且可切换特性的分子表面。CORALS的关键组成部分是由裸露表面区域隔开的密集接枝聚合物链的均匀分布岛（纳米岛）。纳米岛的接枝覆盖范围和间隔距离与构成聚合物链本身的相当。在此，我们表征了纳米岛和其中的半柔性聚合物的结构特征，以更好地理解CORALS的这一关键组成部分。我们观察到接枝的半柔性聚合物具有不同的特性，这取决于聚合物岛的大小以及与岛中心的距离。具体而言，岛周边的链的特性类似于孤立的拴系聚合物链（完全柔性链），而岛中心的链则会经历类似于经典聚合物刷中链的邻域效应。靠近岛边缘的链在这两种状态之间呈现出独特的结构特征。这些结果可用于合理设计具有特定界面特性和对外部刺激有可预测响应的CORALS。希望关于聚合物不同形态随距聚合物边缘距离变化的讨论能在各种各样的系统中得到应用。
