Effect of polymer topology on the self-assembly of micellesRaquel Lopez-Rios De Castro*, Robert M. Ziolek & Christian D. LorenzBiological Physics & Soft Matter Research Group, Department of Physics,King’s College London, London, UK WC2R 2LS

The structure of molecules has often been shown to play an important role in the function and properties of the materials that they form at various lengths and time scales. In polymer science, the choice of macromolecular structures historically has been linear and randomly branched. More recently, more controlled polymer topologies have been formulated because of the development of advanced synthetic techniques. As a result, there has been an increased interest in the role that topology plays in a variety of systems. While in all these investigations there are differences observed as a result of the changing topologies, very little is known as to how the molecular scale interactions of these polymers which have the same composition but just different topology result in these differences.

We have conducted molecular dynamics simulations in which we investigte how different polymer topologies: (linear diblock, linear triblock, branched and cyclic) of poly(methyl acrylate)-poly(ethylene oxide) block polymers affect their self-assembly, which ultimately results in physical differences in between these micelles. In doing so, we combine graph theory and machine learning (dimension reduction and clustering) techniques to gain a unique insight into the self-assembly process of these different topology polymer molecules. With this detailed description of the structure of these micelles, we have the foundations for topology-based rational design of self-assembled polymeric nanoparticles.