Topology-Controlled Self-Assembly of Amphiphilic Block Copolymers

14 February 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


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.


Molecular dynamics simulations
polymer micelles
polymer topology
ring polymers

Supplementary materials

Supporting information
The Supporting Information contains (i) a detailed description of the analysis carried out for the various simulations, (ii) plots of the radius of gyration and eccentricity of the micelles as a function of time, (iii) the contacts between the EO monomers and the hydration of the EO monomers on the polymers within each micelle, (iv) the intrinsic density of the various components within the simulations for each micelle and (v) the outputs of the dimensionality reduction and clustering of the molecules within each micelle.


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