Preparation and pH triggered inversion of vesicles from poly(acrylic acid)-block-polystyrene-block-poly(4-vinyl pyridine)

The aggregate morphologies of the biamphiphilic triblock PAA(26)-b-PS890-b-P4VP(40) have been studied by TEM as a function of pH in DMF/THF/H2O mixtures. The outside surfaces of the aggregates were characterized by potential measurements. Starting at the apparent pH (pH*) of 1, and increasing gradually to pH*14, the aggregate morphologies of this triblock change progressively from vesicles (pH*1), to solid spherical or ellipsoidal aggregates (pH*3similar to11), and finally back to vesicles (pH*14). Vesicles prepared at pH(*)1 contain P4VP chains on the outside and PAA chains on the inside, while those prepared from the same triblock at pH*14 contain PAA outside and P4VP inside. The segregation is based on the difference in repulsive interactions within the PAA or P4VP corona under different pH conditions. At low pH, the curvature is stabilized through increased repulsive interactions between the P4VP chains on the outside relative to the less repulsive interactions between the PAA chains on the inside. At pH* 14, by contrast, the PAA is preferentially segregated to the outside and the P4VP to the inside because of the increased repulsive interaction between PAA chains and the decreased repulsive interaction between P4VP chains at high pH. Most importantly, vesicles with PAA on the outside can be inverted to P4VP on the outside by changing the pH while the vesicles have swollen cores and are under dynamic conditions. The conversion mechanism is suggested to involve a whole vesicle process because the CMC is far too low for single chain reassembly to be involved.