Computational and experimental study of solution-based assemblies of bottlebrush diblock copolymers

Amphiphilic bottlebrush block copolymers are promising materials due to their ability to self-assemble into complex structures with potential applications in biomedical and electronic fields. In this work, a combined experimental-simulation effort was performed to understand how the architectural motifs on the hydrophilic block, in a bottlebrush diblock copolymer, affect the solution self-assembly into core-corona nanoparticles triggered by rapid solvent-quality changes. Our results demonstrate that the architecture of the hydrophilic block can be used to control the self-assembly, morphology and internal structure of the nanoparticles. The length of sidechains, in particular, has a strong effect on those nanoparticle properties, reducing aggregation numbers and core sizes, whereas the overall nanoparticle size increases. Shape anisotropy is also affected: the core remains essentially spherical, whereas the whole nanoparticle becomes progressively less spherical as sidechain length increases. The findings reported here provide molecular insights towards the design of bottlebrush diblock copolymers for drug-delivery and other advanced applications.