Computational Study of Solution-Based Assemblies of Bottlebrush Block Copolymers

Solution self-assembly of molecular bottlebrushes offers a powerful platform to create functional nanostructures with potential applications in biomedical and electronic fields. Thermodynamics and kinetics play a crucial role in determining the possible nanostructures that can be formed. In this work, molecular simulations are used to explore the non-equilibrium self-assembly of amphiphilic diblock bottlebrush copolymers into nanoparticles, triggered by a rapid change in solvent quality. A structural comparison of these nonequilibrium nanoparticles with their equilibrium micelle counterparts is performed. Nanoparticles show lower aggregation numbers, more frustrated core packing, and reduced surface hydrophilicity compared to micelles. Additionally, hydrophobic solute encapsulation studies reveal that nanoparticles offer excellent efficiency and capacity, demonstrating their potential for drug delivery applications. Simulation results were corroborated by experimental measurements.