Synthesis and mechanistic insights of macromolecular assemblies from ABA triblock copolymer blends

Macromolecular assembly of block copolymers into numerous nanostructures resembles self-organization of proteins and cellular components found in nature. In order to mimic nature’s assemblies either to cure a disease or construct functional devices, the organization principles underpinning the emergence of complex shapes need to be understood. In the same vein, this study aimed at understanding morphology evolution in a triblock copolymer blend in aqueous solution. An ABA type amphiphilic triblock copolymer (polystyrene-b-polyethylene oxide-b-polystyrene, PS-b-PEO-b-PS) was synthesized at different compositions via atom transfer radical polymerization (ATRP) and self-assembly behavior of a binary mixture in aqueous solution was studied. Block copolymers that form worms and vesicles in its pristine state was shown to form complex morphologies such as fused rings, “jellyfish”, toroid vesicles, large compound vesicles and large lamellae after blending. The tendency of vesicle-forming block copolymer to form bilayers may be responsible for triggering complex morphologies when mixed with a worm or micelle-forming polymer. In other words, the interplay between curvature effects produced by two distinct polymers with different hydrophobic block lengths results in complex morphologies due to chain segregation within the nanostructure.