No abstract

The effects of pH and electrolyte concentration on protein-protein interactions in lysozyme and chymotrypsinogen solutions were investigated by static light scattering (SLS) and small-angle neutron scattering (SANS). Very good agreement between the values of the virial coefficients measured by SLS and SANS was obtained without use of adjustable parameters. At low electrolyte concentration, the virial coefficients depend strongly on pH and change from positive to negative as the pH increases. All coefficients at high salt concentration are slightly negative and depend weakly on pH. For lysozyme, the coefficients always decrease with increasing electrolyte concentration. However, for chymotrypsinogen there is a cross-over point around pH 5.2, above which the virial coefficients decrease with increasing ionic strength, indicating the presence of attractive electrostatic interactions. The data are in agreement with Derjaguin-Landau-Verwey-Overbeek (DLVO)-type modeling, accounting for the repulsive and attractive electrostatic, van der Waals, and excluded volume interactions of equivalent colloid spheres. This model, however, is unable to resolve the complex short-ranged orientational interactions. The results of protein precipitation and crystallization experiments are in qualitative correlation with the patterns of the virial coefficients and demonstrate that interaction mapping could help outline new crystallization regions.

Cationic surfactants having long (C22) mono-unsaturated tails were studied in aqueous solutions containing salt using steady and dynamic rheology. The surfactant erucyl bis(hydroxyethyl)methylammonium chloride self-assembles into giant wormlike micelles, giving rise to unusually strong viscoelasticity. Under ambient conditions, the viscosity enhancement due to surfactant exceeds a factor of 107. Some samples behave as gel-like solids at low temperatures and revert to the viscoelastic (Maxwellian) response only at higher temperatures. These samples display appreciable viscosities (>10 Pa·s) up to very high temperatures (ca. 90 °C). Salts with counterions that penetrate into the hydrophobic interior of the micelles, such as sodium salicylate, are much more efficient at promoting self-assembly than salts with nonbinding counterions, such as sodium chloride. Changing the surfactant headgroup to the more conventional trimethylammonium group reduces the viscosity at high temperatures.

Microstructured particles were synthesized by growing colloidal crystals in aqueous droplets suspended on fluorinated oil. The droplets template highly ordered and smooth particle assemblies, which diffract light and have remarkable structural stability. The method allows control of particle size and shape from spheres through ellipsoids to toroids by varying the droplet composition. Cocrystallization in colloidal mixtures yields anisotropic particles of organic and inorganic materials that can, for example, be oriented and turned over by magnetic fields. The results open the way to controllable formation of a wide variety of microstructures.

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.