Structure, diffusion, and permeability of protein-stabilized monodispersed oil in water emulsions and their gels: a self-diffusion NMR study.

Self-diffusion NMR is used to investigate monodispersed oil in water emulsions and the subsequent gel formed by removing the water through evaporation. The radius of the oil droplets in the emulsions is measured using a number of diffusion methods based on the measurement of the mean squared displacement of the oil, water, and tracer molecules. The results are consistent with the known size of the emulsions. Bragg-like reflections due to the restricted diffusion of the water around the oil droplets are observed due to the low polydispersity of the emulsions and the dense packing. The resulting data are fitted to a pore glass model to give the diameter of both the pools of interstitial water and the oil droplets. In the gel, information on the residual three-dimensional structure is obtained using the short time behavior of the effective diffusion coefficient to give the surface to volume ratio of the residual protein network structure. The values for the surface to volume ratio are found to be consistent with the expected increase of the surface area of monodisperse droplets forming a gel network. At long diffusion observation times, the permeability of the network structure is investigated by diffusion NMR to give a complete picture of the colloidal system considered.

Emulsion-templated fully reversible protein-in-oil gels.

We have developed a new method allowing us to transform low-viscous apolar fluids into elastic solids with a shear elastic modulus of the order of 10(3)-10(5) Pa. The elasticity of the elastic solid is provided by a percolating 3D network of proteins, which are originally adsorbed at the interface of an oil-in-water emulsion template. By cross-linking the protein films at the interface and upon removal of water, the template is driven into a structure resembling a dry foam where the protein interfaces constitute the walls of the foam and the air is replaced by oil confined within polyhedral, closely packed droplets. Depending on the density of the protein network, the final material consists of chemically unmodified oil in a proportion of 95 to 99.9%. The physical properties of the elastic solid obtained can be tuned by changing either the average diameter size of the emulsion template or the cross-linking process of the protein film. However, the original low-viscosity emulsion can be restored by simply rehydrating the solidified fluid. Therefore, the present procedure offers an appealing strategy to build up solid properties for hydrophobic liquids while preserving the low viscosity and ease of manufacturing.

Cross linking and rheological characterization of adsorbed protein layers at the oil-water interface.

The dilatational rheological properties of cross-linked protein layers adsorbed at the oil-water interface were investigated with help of a modified drop tensiometer allowing successive replacements of the external phase. This setup enables one to perform cross-linking reactions at the interface only, that is, without any contact between the cross-linking agent and protein molecules in solution, under continuous monitoring of the interfacial tension. The mechanical properties of the resulting interface were investigated with dilatational large strain experiments. Measured rheological properties were related to the expected stability of an emulsion against disproportionation by considering the ratio of the interfacial elasticity to the interfacial tension. In an attempt to increase this ratio to improve the resistance against disproportionation, experiments were performed with densified protein layers obtained via reduction of the droplet area prior to cross linking. To highlight the influence of the protein morphology on the dilatational rheological properties of the cross-linked adsorbed layers, experiments were performed with random coil (beta-casein) as well as globular (beta-lactoglobulin) proteins. Glutaraldehyde was used as a cross-linking agent. Experiments were performed at 55 degrees C and pH 7.0 in 20 mM imidazole buffer for later comparison with enzymatically cross-linked adsorbed protein layers. The present work demonstrated substantial qualitative and quantitative differences in the interfacial rheological properties of cross-linked random coil and globular proteins.

Polysaccharide-induced order-to-order transitions in lyotropic liquid crystals.

We report on the order-to-order transitions of lyotropic liquid crystals formed by self-assembled monogylcerides and water in the presence of polysaccharides of various molecular weights. The phase diagram of monoglyceride-water-polysaccharide systems, their morphology, and the topology of liquid crystalline structures were determined by combining optical cross-polarization, oscillatory shear rheometry, and small-angle X-ray scattering. The presence of hydrophilic mono-, oligo-, and polysaccharides in the water domains of liquid crystalline phases resulted in a general decrease of the cubic-to-hexagonal transition temperature. Provided that the sugar could fit within the water channels, the decrease was observed to be dependent on the polysaccharide concentration but independent of its molecular weight. For isotropic bicontinuous cubic phases, monomeric sugars such as glucose were reported to shrink the lattice parameter of the structure without inducing phase transitions. However, when a polymeric form of glucose was used, such as dextran, transitions from the gyroidal Ia3d cubic phase to double diamond Pn3m cubic phases were observed at well-defined molecular weights of polysaccharide. These results were interpreted in terms of size exclusions of polymer sugars by the water domains of the liquid crystal phases as well as the different topologies of water channels. Molecular dynamics simulations of polysaccharides in the water environment were performed to support these findings.

Shear rheology of lyotropic liquid crystals: a case study.

We have investigated the rheological properties of lyotropic liquid crystals (LCs) formed by self-assembled neutral lipids and water, their relationship with the topology of the structure, and their dependence on temperature and water content. The phase diagram of a representative monoglyceride-water system, determined by combining cross-polarized optical microscopy and small-angle X-ray scattering (SAXS), included four structures: lamellar, hexagonal, gyroid bicontinuous cubic (Ia3d), and double diamond bicontinuous cubic (Pn3m), as well as several regions of two-phase coexistence of some of the above structures. Rheology in the linear viscoelastic regime revealed a specific signature that was characteristic of the topology of each structure considered. The order-order transitions lamellar-to-cubic and cubic-to-hexagonal, as well as the order-disorder transitions from each LC to an isotropic fluid, were easily identified by following the development of the storage and loss moduli, G' and G'', respectively. The viscoelastic properties of both bicontinuous cubic phases were shown to be strongly frequency-dependent, following a pseudo-Maxwell behavior, with multiple relaxation times. Cubic-to-cubic transitions were nicely captured by scaling the longest relaxation time, tau, with either temperature or water volume fraction. Therefore, the set of the three main parameters used to establish the rheological behavior of the structure, that is, G', G'', and relaxation time, tau, constitutes a consistent ensemble to identify the structures of the liquid crystal. Finally, relaxation spectra, extracted for all liquid crystalline phases, allowed an additional possible identification criterion of the various structures considered.

Dynamic oscillatory behavior of a linear viscoelastic fluid bounded by an ideal linear viscoelastic membrane in torsional flow.

In rotational oscillatory rheological measurement techniques involving the plate-plate and cone-plate geometries, the interface between the measured liquid and the ambient atmosphere is sheared to the same extent as the liquid sample. In this paper, we look at the influence of a rheologically distinct lateral surface on the measured properties of the liquid and surface system when the surface is dynamically coupled to the bulk fluid. Inertia is taken into account, thus allowing for nonquasi-static velocity profiles in the massless surface film itself.