Kinetically-Arrested Nanostructures from Amphiphilic Mikto-Grafted Molecular Brush Polymers in Solution

The solution self-assembly of heterografted molecular brush polymers offers a rich platform to create functional organic nanostructures. In recent years, it has become evident that kinetics, not just thermodynamics, plays an important role in defining the self-assembled structures that can be created. In this work, we present results from extensive molecular dynamics simulations that explore the self-assembly behavior of amphiphilic mikto-grafted brush polymers as 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 architectural parameters and the degree of incompatibility between side chains on the final self-assembled nanostructures. Our simulation results indicate that kinetically-trapped complex nanostructures are prevalent as the number of macromonomers increases. A quantitative analysis on the structure of the self-assembled morphologies was performed by computing the gyration tensor and relative shape anisotropy as the different relevant architectural parameters were varied. Our results are summarized in terms of non-equilibrium morphology diagrams.