Salt effect on microstructures in cationic gemini surfactant solutions as studied by dynamic light scattering

A cationic gemini surfactant, dodecanediyl-1,12-bis(dodecyldiethylammonium bromide) (C12C12C12(Et)), in aqueous solutions with varying NaBr concentration was studied by dynamic light scattering (DLS). As a comparison, its single-chained counterpart, dodecyl triethylammonium bromide (DTEAB), was also investigated under the same conditions. Similar to the case of a polyelectrolyte, C12C12C12(Et) underwent a typical ordinary-to-extraordinary (o-e) transition with decreasing salt concentration to zero. At higher salt concentration, a single relaxation mode, corresponding to the diffusion of regular micelles, was observed. While in the 'extraordinary regime, DLS detected two characteristic relaxation modes with the values of the diffusion coefficient being different by at least 2 orders. The fast mode was consistent with the polyion-small ion coupled-mode theories, as well as the direct polyion-polyion repulsion interactions. Because the slow mode disappeared at elevated salt concentrations and generated negligible scattered intensity, we attributed it to multimacroion domains.