Versatile Diblock Polyampholytes Can Form Two Types of Charged and Internally Structured Core–Shell Particles by Complexation with Cationic or Anionic Surfactants

We used diblock poly(acrylic acid)-b-poly(2-dimethylamino ethyl methacrylate) (PAA-b-PDMAEMA) polyampholytes to prepare core-shell complexes with ionic surfactants. The dispersions have been characterized by means of small-angle X-ray scattering (SAXS), cryogenic transmission electron microscopy (Cryo-TEM), dynamic light-scattering, and zeta potential methods. Using cationic or anionic surfactants it is possible to produce particles with either positively or negatively charged shells, both having an internal liquid-crystalline core structure. For the different systems, different preparation protocols were found to be successful to produce stable and reproducible particles. The particle morphologies depend on the surfactant used. Complexes with the cationic surfactant hexadecyltrimethylammonium (CTA+) form oblate particles, while complexes with dodecyl sulfate (DS-) form cylindrical rods. In both complexes, the smallest dimension of the core does not exceed twice the block length of the core-forming polymer block. For the particles with CTA+, nonelectrostatic attractive interactions among the PDMAEMA chains in the shells seem to be present, affecting the particle shape. In both types of particles, the surfactant in the core forms rod-like aggregates, arranged in a two-dimensional hexagonal structure with the surfactant rods aligned with the axis of rotational symmetry in the particle. With charged polymer chains in the shell, the aggregates present a striking stability over time, displaying no change in particle size over the time scale investigated (10 months). Nevertheless, the aggregates are highly dynamic in nature, and their shapes and structures can be changed dramatically in dispersion, without intermediate precipitation, by changes in the composition of the medium. Specifically, a transition from aggregates with cationic surfactant to aggregates with anionic surfactant can be achieved.