Interactions and aggregations in aqueous and brine solutions of poly(diallydimethylammonium chloride)/sodium...

The interactions between the anionic surfactant sodium bis(2-ethylhexyl) sulfosuccinate (AOT) and the polycation poly(diallydimethylammonium chloride) (PDDAC), the aggregations of AOT and PDDAC-bound AOT in PDDAC/AOT aqueous solutions, and the influence of salt on the interactions and aggregations have been studied by isothermal titration calorimetry (ITC), dynamic light scattering (DLS), and negative staining transmission electron microscopy (TEM). The adsorptions of AOT onto PDDAC and the formations of PDDAC-bound AOT micelles, free AOT micelles, and AOT vesicles were examined, and the corresponding critical concentrations were determined. Combining calculations of thermodynamic parameters with the above three experimental techniques, it was shown that the micellization of free AOT is driven by entropy gain, while the adsorption of AOT onto PDDAC and the micellization of PDDAC-bound AOT are driven by both enthalpy and entropy. It was also found that addition of salt enhances the binding of AOT onto PDDAC through the ion exchange and favors the formations of PDDAC/AOT micelles, free AOT micelles, and free AOT vesicles but prevents the transition of PDDAC/AOT micelles to the vesicles. Thermodynamic analysis suggested that the adsorption of AOT onto PDDAC and the micellization of PDDAC/AOT in PDDAC/AOT brine solutions are different in mechanism compared with that in corresponding aqueous solutions.