The rheology of wormlike micelles ("worms") formed by surfactants in water often follows nonmonotonic trends as functions of composition. For example, a study by Raghavan et al. (Langmuir 2002, 18, 3797) on mixtures of the anionic surfactant sodium oleate (NaOA) and the cationic surfactant octyl trimethylammonium bromide (OTAB) reported a pronounced peak in the zero-shear viscosity eta0 as a function of NaOA/OTAB ratio at a constant surfactant concentration (3 wt %). In this work, we study the origins of rheological changes in the NaOA/OTAB system and the relations between the composition and structural characteristics using cryo-transmission electron microscopy (cryo-TEM). When either surfactant is in large excess, the dominating morphology is that of spherical micelles. As oppositely charged surfactant is added to the mixture, the spheres grow into linear worms and these continue to elongate as the viscosity peak (which occurs at a 70/30 NaOA/OTAB ratio) is approached from either end. At the viscosity peak, the sample shows numerous long worms as well as a small number of branched worms. Taken together, NaOA/OTAB rheology can be primarily understood on the basis of micellar growth, which is explained primarily by packing arguments. While the size of the hydrophobic micellar core continuously decreases as the short amphiphile OTAB is added at the expense of NaOA, screening of charges goes through a maximum, which contributes to the asymmetry of the viscosity curve. With regard to micellar branching, there is no significant difference in the density of branched worms on either side of the viscosity peak. Therefore, it appears that in contrast to the behavior of some surfactant/salt systems, branching does not have a significant influence on the rheology of this mixed catanionic surfactant system. Instead, our data clearly indicate that the origin of the viscosity peak is linked with micellar growth and micellar shortening.
The LCST phase-transition of aqueous PNIPA solutions in rising concentrations of the strong chaotropic salt KSCN was studied microcalorimetrically by DSC and apparently for the first time by ITC. An endothermic (entropy driven) binding of KSCN onto PNIPA was observed, explained by electrostatic perturbation of hydrophobic hydration by adsorbed ions. A good fit was found for the one-typeof-sites binding model, and the binding affinity increased with rising temperature from 15 to 20 °C but decreased at 25 °C. DSC measurements emphasized the lowering and broadening of the endothermic peak of PNIPA phase-transition with rising KSCN concentration, explained by reduced cooperativity of coil-toglobule collapse with increased heterogeneity along the polymer chain, caused by salt adsorption. A hysteresis was observed between heating and cooling DSC peaks, which decreased asymptotically with rising KSCN concentration, further supporting that binding occurs. This work provides new insights into the mechanisms of chaotropic salt effects on polymers and biopolymers in aqueous solutions.
The association behavior, critical micellization concentration (CMC), and enthalpy of demicellization (DeltaHdemic) of bovine beta-casein were studied, for the first time by isothermal titration calorimetry, in a pH 7.0 phosphate buffer with 0.1 ionic strength and in pure water. In the buffer solutions, the CMC decreased asymptotically from 0.15 to 0.006 mM as the temperature was raised from 16 to 45 degrees C. DeltaHdemic decreased with increasing temperature between 16 and 28 degrees C but increased from 28 to 45 degrees C. Thermodynamic analysis below 30 degrees C is consistent with the Kegeles shell model, which suggests a stepwise association process. At higher temperatures, this model exhibits limitations, and the micellization becomes much more cooperative. The CMC values in water, measured between 17 and 28 degrees C, decreased with increasing temperature and, expectedly, were higher than those found in the buffer solutions. beta-Casein micelles were visualized and characterized, for the first time in their hydrated state, using advanced digital-imaging cryogenic transmission electron microscopy. The images revealed small, oblate micelles, about approximately 13 nm in diameter. The micelles shape and dimensions remained nearly constant in the temperature range of 24-35 degrees C.
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