Hydrogen bonding induced vesicular morphologies in diblock copolymer complexes

It is well-known that the self-assembly of block copolymers either in water or in organic solvents can form a wide range of morphologies in nanometer dimensions depending on its chemical nature. In the present study, the complexation and aggregate morphologies in a model AB/AC diblock copolymer system consisting of polystyrene-block-poly(acrylic acid) (PS-b-PAA) and polystyrene-block-poly(ethylene oxide) (PS-b-PEO) in water were studied using transmission electron microscopy (TEM), small angle X-ray scattering (SAXS), and dynamic light scattering (DLS). By varying the relative amounts of the two block copolymers, a variety of bilayer aggregates were formed, including vesicles, multilamellar vesicles (MLVs), thick-walled vesicles (TWVs), interconnected compound vesicles (ICCVs), and irregular aggregates. The hydrophobic PS blocks were segregated as the cores while the hydrogen bonded PEO and PAA blocks formed the coronae of bilayer aggregates. We also investigate how the addition of PS-b-PEO into PS-b-PAA solutions influences the aggregate morphology of the resulting complexes. This work introduces a viable route to multicompartment vesicles in aqueous solutions. The formation of block copolymer vesicles in water is of particular interest because of their potential in various applications.