The long-term stabilization of foams by proteins for food applications is related to the ability of proteins to form dense and mechanically strong adsorption layers that cover the bubbles in the foams. The hydrophobins represent a class of proteins that form adsorption layers of extraordinary high shear elasticity and mechanical strength, much higher than that of the common milk and egg proteins. Our investigation of pure and mixed (with added beta-casein) hydrophobin layers revealed that their rheological behavior obeys a compound rheological model, which represents a combination of the Maxwell and Herschel-Bulkley laws. It is remarkable that the combined law is obeyed not only in the simplest regime of constant shear rate (angle ramp), but also in the regime of oscillatory shear strain. The surface shear elasticity and viscosity, E(sh) and eta(sh), are determined as functions of the shear rate by processing the data for the storage and loss moduli, G' and G''. At greater strain amplitudes, the spectrum of the stress contains not only the first Fourier mode, but also the third one. The method is extended to this non-linear regime, where the rheological parameters are determined by theoretical fit of the experimental Lissajous plot. The addition of beta-casein to the hydrophobin leads to softer adsorption layers, as indicated by their lower shear elasticity and viscosity. The developed approach to the rheological characterization of interfacial layers allows optimization and control of the performance of mixed protein adsorption layers with applications in food foams.

The surface shear rheology of hydrophobin HFBII adsorption layers is studied in angle-ramp/relaxation regime by means of a rotational rheometer. The behavior of the system is investigated at different shear rates and concentrations of added β-casein. In angle-ramp regime, the experimental data comply with the Maxwell model of viscoelastic behavior. From the fits of the rheological curves with this model, the surface shear elasticity and viscosity, E(sh) and η(sh), are determined at various fixed shear rates. The dependence of η(sh) on the rate of strain obeys the Herschel-Bulkley law. The data indicate an increasing fluidization (softening) of the layers with the rise of the shear rate. The addition of β-casein leads to more rigid adsorption layers, which exhibit a tendency of faster fluidization at increasing shear rates. In relaxation regime, the system obeys a modified Andrade's (cubic root) law, with two characteristic relaxation times. The fact that the data comply with the Maxwell model in angle-ramp regime, but follow the modified Andrade's low in relaxation regime, can be explained by the different processes occurring in the viscoelastic protein adsorption layer in these two regimes: breakage and restoration of intermolecular bonds at angle-ramp vs solidification of the layer at relaxation.

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Colloidosomes provide a possibility to encapsulate oily substances in water in the form of core-in-shell structures. In this study, we produced microcapsules with shell from colloidal particles, where the interparticle openings are blocked by mixed layers from polymer and surfactant that prevent the leakage of cargo molecules. In other words, the particles and polymer play the role of bricks and mortar. For this goal, we used hydrophilic silica particles, which were partially hydrophobized by the adsorption of potassium oleate to enable them to stabilize Pickering emulsions. Various polymers were tested to select the most appropriate one. The procedure of encapsulation is simple and includes single homogenization by ultrasound. The produced capsules are pH responsive. They are stable in aqueous phase of pH in the range 3 -6, but at pH > 6 they are destabilized and their cargo is released. With the optimized formulation of silica particles, polymer, oleate and NaCl, we were able to encapsulate various oils and fragrances, such as tetradecane, limonene, benzyl salicylate and citronellol. All of them have a limited and not too high solubility in water. In contrast, no stable microcapsules were obtained with oils that either have zero water solubility (mineral and silicone oil) or higher water solubility (phenoxyethanol and benzyl alcohol). By analysis of results from additional interfacial-tension and thin-film experiments, we concluded that a key factor for obtaining stable capsules is the irreversible adsorption of the polymer at the oil/water interface. The hydrophobization of the particles by surfactant adsorption (instead of silanization) plays an important role for the pH responsiveness of the produced capsules. The obtained information about the role of various factors for the stabilization of microcapsules, which are based on the brick-and-mortar concept, can be further used to achieve better stability; selection of polymers that are appropriate for different classes of oils, as well as for the production of smaller capsules stabilized by nanoparticles. (P.A. Kralchevsky). Introduction.The development of micro-and nanocapsules with controlled composition and properties has been a subject of intensive research in the last decade. The stimuli responsive release of cargo molecules from the carrier gains a remarkable attention for in vivo and in vitro delivery of contrast agents, genes, and pharmaceuticals [1]. The colloidal capsules find another broad field of applications in house-hold and personal-care detergency, cosmetics and food industry, e.g. for the encapsulation of fragrances, flavors, colorants and preservatives [2,3].By their chemical nature, the colloidal carriers are classified as inorganic, organic and hybrid, e.g. mineralized protein capsules [1,4]. Different classes of colloidal carriers can be distinguished in relation to their structure and morphology: micelles; dendrimers; liposomes; niosomes; polymersomes; cubosomes and hexosomes; colloidosomes, and emulsion-based micro-and nanocapsules [1,5...

This is a review article on the rheological properties of mixed solutions of sulfonated methyl esters (SME) and cocamidopropyl betaine (CAPB), which are related to the synergistic growth of giant micelles. Effects of additives, such as fatty alcohols, cocamide monoethanolamine (CMEA) and salt, which are expected to boost the growth of wormlike micelles, are studied. We report and systematize the most significant observed effects with an emphasis on the interpretation at molecular level and understanding the rheological behavior of these systems. The experiments show that the mixing of SME and CAPB produces a significant rise of viscosity, which is greater than in the mixed solutions of sodium dodecyl sulfate and CAPB. The addition of fatty alcohols, CMEA and cationic polymer, leads to broadening of the synergistic peak in viscosity without any pronounced effect on its height. The addition of NaCl leads to a typical salt curve with high maximum, but in the presence of dodecanol this maximum is much lower. At lower salt concentrations, the fatty alcohol acts as a thickener, whereas at higher salt concentrations -as a thinning agent. Depending on the shape of the frequency dependences of the measured storage and loss moduli, G' and G", the investigated micellar solutions behave as systems of standard or nonstandard rheological behavior. The systems with standard behavior obey the Maxwell viscoelastic model (at least) up to the crossover point (G' = G") and can be analyzed in terms of the Cates reptationreaction model. The systems with nonstandard rheological behavior obey the Maxwell model only in a restricted domain below the crossover frequency; they can be analyzed in the framework of an augmented version of the Maxwell model. The methodology for data analysis and interpretation could be applied to any other viscoelastic micellar system.