Journal of Physical Chemistry B, Vol.121, No.17, 4466-4473, 2017
Precipitate-Coacervate Transformation in Polyelectrolyte-Mixed Micelle Systems
The polycation/anionic-nonionic mixed micelle, poly-(diallyldimethylammonium chloride)-sodium dodecyl sulfate/Triton X-100 (PDADMAC-SDS/TX100), is a model polyelectrolyte-colloid system in that the micellar mole fraction of SDS (Y) controls the micelle surface charge density, thus modulating the polyelectrolyte-colloid interaction. The exquisite temperature dependence of this system provides an important additional variable, controlling both liquid-liquid (L-L) and liquid-solid (L-S) phase separation, both of which are driven by the entropy of small ion release. In order to elucidate these transitions, we applied high-precision turbidimetry (+/- 0.1 %), isothermal titration calorimetry, and epifluorescence microscopy which demonstrates preservation of micelle structure under all conditions. The L-S region at large Y including precipitation displays a remarkable linear, inverse Y-dependence of the L-S transition temperature T-s. In sharp contrast, the critical temperature for L-L coacervation T-phi, shows nearly symmetrical effects of positive and negative deviations in Y from the point of soluble complex neutrality, which is controlled in solution by the micelle charge and the number of micelles bound per polymer chain n (Z(complex) = Z(polymer) + nZ(micelle)). In solid-like states, n no longer signifies the number of micelles bound per polymer chain, since the proximity of micelles inverts the hostguest relationship with each micelle binding multiple PE chains. This intimate binding goes hand-in-hand with the entropy of release of micelle-localized charge-compensating ions whose concentration depends on Y. These ions need not be released in L-L coacervation, but during L-S transition their displacement by PE accounts for the inverse dependence of T-s on micelle charge, Y.