Topology-Controlled Self-Assembly of Amphiphilic Block Copolymers

Contemporary synthetic chemistry approaches can be used to yield a range of distinct polymer topologies with precise control. The topology of a polymer strongly influences its self-assembly into complex nanostructures however a clear mechanistic understanding of the relationship between polymer topology and self-assembly has not yet been developed. In this manuscript, we utilize classical all-atom molecular dynamics simulations of three different topologies (two triblock linear polymers and one ring polymer) of poly(ethylene oxide) - poly(methyl acrylate) block copolymers to provide a mechanistic understanding of the influence of topology in micelle size and stability. We find that the topology affects the ability of the micelle to form a compact hydrophobic core, which directly affects its stability. Also, we apply unsupervised machine learning techniques to show that the topology of a polymer affects its ability to take a conformation in response to the local environment within the micelles. This work provides foundations for the rational design of polymer nanostructures based on their underlying topology.