Amphiphilic Arborescent Copolymers and Microgels: From Unimolecular Micelles in a Selective Solvent to the Stable Monolayers of Variable Density and Nanostructure at a Liquid Interface.

Amphiphilic arborescent block copolymers of two generations (G2 and G3) and polymer microgels, obtained via cross-linking of diblock copolymers, were studied in a selective solvent and at liquid interface via dissipative particle dynamics (DPD) simulations. Depending on the primary structure, single arborescent macromolecules in selective solvent can have both core-corona and multicore structures. Self-assembly of the G2, G3, and microgels in the selective solvent is compared with equivalent linear diblock copolymers. The latter self-assemble into spherical micelles of large enough aggregation number. On the contrary, stability of unimolecular micelles is a feature of the arborescent copolymers and microgels, whereas their ability to aggregate is very low. Adsorption of the single molecules at liquid (oil-water) interface leads to their flattening and segregation of the amphiphilic blocks: hydrophilic and hydrophobic blocks are exposed toward water and oil, respectively. Depending on the character of interactions between monomer units, which can be controlled by temperature or solvent(s) quality, Janus, patchy, and nanosegregated structures can be formed within the macromolecules. Their self-assembly at the interface can lead to the formation of both loose and dense monolayers, which can be homogeneous and nanostructured. The pretty fast adsorption kinetics of G2 macromolecules make them efficient stabilizers of emulsions.