Fine-tuning the nonequilibrium behavior of oppositely charged macromolecule/surfactant mixtures via the addition of nonionic amphiphiles.

The various commercial applications of oppositely charged polyelectrolytes (P) and ionic surfactants (S) with added nonionic amphiphiles initiated intensive research on the polyion/mixed surfactant interaction. A large group of earlier studies revealed that one of the major effects of the nonionic cosurfactants is the suppression of the associative phase separation of P/S systems. In contrast, recent studies indicated that in the dilute surfactant concentration range the added uncharged amphiphile enhances the precipitation concentration range. In order to rationalize these observations, the mixtures of poly(diallyldimethylammonium chloride) (PDADMAC), sodium dodecyl sulfate (SDS), and dodecyl maltoside (C12G2) are investigated using a variety of experimental methods. It is shown that the nonionic cosurfactant has two distinct and competing impacts on the mixed surfactant binding onto the polyions. The composition dependent variation of the chemical potentials of the amphiphiles determines which of these effects is the dominant one, explaining the seemingly diverse earlier observations and their interpretations. We also demonstrate that the nonionic amphiphile affects considerably the nonequilibrium features of polyion/ionic surfactant complexation. Namely, the presence of the uncharged surfactant can destabilize the colloidal dispersion of P/S nanoparticles formed in the two-phase composition range. However, at the same concentration range highly stable dispersions of polyion/mixed surfactant nanoparticles can be produced through the application of a new two-step solution preparation technique. This method is based on the order of addition effect of the two surfactants which can be utilized in future scientific and industrial applications.