Solution behavior of rod-like polyelectrolyte-surfactant aggregates polymerized from wormlike micelles.

The behavior of a rod-like, water-soluble, polyelectrolyte-surfactant aggregate system (pC16TVB) in aqueous solution is characterized to determine the partitioning of surfactant in these systems and the impact on aggregate structure. These aggregates are generated by in situ polymerization of a cationic surfactant-hydrotrope wormlike micelle system. This system differs from most other polyelectrolyte-surfactant systems in that the monomer groups and the surfactant are present in ion pairs in the absence of added salts or counterions, so the stoichiometry (with respect to charge) is 1:1 for the system. Therefore, after polymerization the surfactant acts as the counterion for the polyelectrolyte chains as other counterions (salts) are not available. Despite being present in a 1:1 molar ratio, the aggregates are surprisingly stable in water (concentrations >600 mg/mL have been achieved). The conformation of the polyelectrolyte in the aggregate is analogous to the case of a polymer chain in tight confinement in a "tube" or cylindrical pore in which the pore walls are attractive--the tube is formed by the surfactant which is free to dissociate from the aggregates. A simple model for the structure and partitioning is presented and the ability to manipulate the aggregate structure is demonstrated.