Self-Assembly of Linear-Dendritic and Double Dendritic Block Copolymers: From Dendromicelles to Dendrimersomes

Nanostructures formed upon self-assembly of amphiphilic block copolymers with linear and dendronized blocks are promising as nanocarriers for targeted drug and gene delivery. We propose a theoretical framework to predict how dimensions and morphologies of such nanostructures as well as the number of potentially functionalized terminal groups exposed to surrounding media can be controlled by adjusting molecular architecture parameters of dendronized blocks (i.e., number of generations and branching functionality). We demonstrate that dendronization of the soluble block stabilizes spherical micelles with a dendritic corona, whereas block copolymers with dendritic insoluble blocks give rise to cylindrical wormlike micelles or polymersomes even if homologous linear-linear block copolymers assemble into spherical micelles. Spherical micelles with a dendronized corona combine smaller hydrodynamic dimensions with a larger number of terminal groups as compared to micelles formed by homologous linear diblock copolymers. Our findings provide guidelines for design of targetable vector systems in nanomedicine.