Sequence of polyurethane ionomers determinative for core structure of surfactant–copolymer complexes

The core of micelles self‐assembled from amphiphiles is hydrophobic and contains little water, whereas complex coacervate core micelles co‐assembled from oppositely charged hydrophilic polymers have a hydrophilic core with a high water content. Co‐assembly of ionic surfactants with ionic‐neutral copolymers yields surfactant–copolymer complexes known to be capable of solubilizing both hydrophilic and hydrophobic cargo within the mixed core composed of a coacervate phase with polyelectrolyte‐decorated surfactant micelles. Here we formed such complexes from asymmetric (PUI‐A2) and symmetric (PUI‐S2), sequence‐controlled polyurethane ionomers and poly(N‐methyl‐2‐vinylpyridinium iodide)29‐b‐poly(ethylene oxide)204 copolymers. The complexes with PUI‐S2 were 1.3‐fold larger in mass and 1.8‐fold larger in radius of gyration than the PUI‐A2 complexes. Small‐angle X‐ray scattering revealed differences in the packing of the similarly sized PUI micelles within the core of the complexes. The PUI‐A2 micelles were arranged in a more ordered fashion and were spaced further apart from each other (10 nm vs. 6 nm) than the PUI‐S2 micelles. Hence, this work shows that the monomer sequence of amphiphiles can be varied to alter the internal structure of surfactant–copolymer complexes. Since the structure of the micellar core may affect both the cargo loading and release, our findings suggest that these properties may be tuned through control of the monomer sequence of the micellar constituents.