The phase behavior and aggregate morphology of
mixtures of the oppositely charged surfactants cetyltrimethylammonium bromide (CTAB) and sodium octyl sulfate (SOS) are
explored with cryotransmission electron
microscopy, quasielastic light scattering, and surface tensiometry.
Differences in the lengths of the two
hydrophobic chains stabilize vesicles relative to other microstructures
(e.g., liquid crystalline and precipitate
phases), and vesicles form spontaneously over a wide range of
compositions in both CTAB-rich and SOS-rich solutions. Bilayer properties of the vesicles depend on the
ratio of CTAB to SOS, with CTAB-rich
bilayers stiffer than SOS-rich ones. We observe two modes of
microstructural transition between micelles
and vesicles. The first transition, between rodlike micelles and
vesicles, is first order, and so there is
macroscopic phase separation. This transition occurs in CTAB-rich
solutions and in SOS-rich solutions at
higher surfactant concentrations. In the second transition mode,
mixtures rich in SOS at low surfactant
concentrations exhibit no phase separation. Instead, small
micelles abruptly transform into vesicles over a
narrow range of surfactant concentration. Since the vesicles that
form in mixtures of oppositely charged
surfactants are equilibrium microstructures, the microstructural
evolution is related solely to the phase transition
and is thus under thermodynamic control. This differs from
experiments reported on the dissolution of
metastable vesicles, such as the detergent solubilization of biological
phospholipid membranes, which may
be controlled by kinetics. Despite these differences, we find that
the evolution in microstructure in our mixtures
of oppositely charged surfactants is analogous to that reported for
biological membrane solubilization.
Vesicles form spontaneously in a variety of aqueous mixtures of oppositely charged surfactants. Here we report the morphological transition from spherical micelles to vesicles observed in mixtures of dodecyltrimethylammonium chloride (DTAC) and sodium dodecylbenzenesulfonate (SDBS) as probed by the complementary techniques of quasielastic light scattering (QLS), NMR self-diffusion and relaxation measurements, and time-resolved fluorescence quenching (TRFQ) experiments. In these mixtures, there is limited growth of the micelles with changes in composition, and vesicles abruptly begin to form at a characteristic mixing ratio of the two surfactants. As the composition moves further into the vesicle region, the quantity of micelles decreases in proportion to the number of vesicles that form. Thus, in mixtures of DTAC and SDBS, the transition from micelles to vesicles is continuous. This is in contrast to the first-order phase transition exhibited by other aqueous mixtures of oppositely charged surfactants, in which micelles first grow into extended threadlike micelles and samples intermediate to the micellar and vesicle phases separate into two macroscopic phases.
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