Kinetically-arrested single-polymer nanostructures from amphiphilic mikto-grafted bottlebrushes in solution: a simulation study

Abstract

Solution self-assembly of molecular bottlebrushes offers a rich platform to create complex functional organic nanostructures. Recently, it has become evident that kinetics, not just thermodynamics, plays an important role in defining the self-assembled structures that can be formed. In this work, we present results from extensive molecular dynamics simulations that explore the self-assembly behavior of mikto-grafted bottlebrushes when the solvent quality for one of the side blocks is changed by a rapid quench. We have performed a systematic study of the effect of different structural parameters and the degree of incompatibility between side chains on the final self-assembled nanostructures in the low concentration limit. We found that kinetically-trapped complex nanostructures are prevalent as the number of macromonomers increases. We performed a quantitative analysis of the self-assembled morphologies by computing the radius of gyration tensor and relative shape anisotropy as the different relevant parameters were varied. Our results are summarized in terms of non-equilibrium morphology diagrams.