Krastanka G. Marinova

Surface Rheology of Saponin Adsorption Layers

Extracts of the Quillaja saponaria tree contain natural surfactant molecules called saponins that very efficiently stabilize foams and emulsions. Therefore, such extracts are widely used in several technologies. In addition, saponins have demonstrated nontrivial bioactivity and are currently used as essential ingredients in vaccines, food supplements, and other health products. Previous preliminary studies showed that saponins have some peculiar surface properties, such as a very high surface modulus, that may have an important impact on the mechanisms of foam and emulsion stabilization. Here we present a detailed characterization of the main surface properties of highly purified aqueous extracts of Quillaja saponins. Surface tension isotherms showed that the purified Quillaja saponins behave as nonionic surfactants with a relatively high cmc (0.025 wt %). The saponin adsorption isotherm is described well by the Volmer equation, with an area per molecule of close to 1 nm(2). By comparing this area to the molecular dimensions, we deduce that the hydrophobic triterpenoid rings of the saponin molecules lie parallel to the air-water interface, with the hydrophilic glucoside tails protruding into the aqueous phase. Upon small deformation, the saponin adsorption layers exhibit a very high surface dilatational elasticity (280 ± 30 mN/m), a much lower shear elasticity (26 ± 15 mN/m), and a negligible true dilatational surface viscosity. The measured dilatational elasticity is in very good agreement with the theoretical predictions of the Volmer adsorption model (260 mN/m). The measured characteristic adsorption time of the saponin molecules is 4 to 5 orders of magnitude longer than that predicted theoretically for diffusion-controlled adsorption, which means that the saponin adsorption is barrier-controlled around and above the cmc. The perturbed saponin layers relax toward equilibrium in a complex manner, with several relaxation times, the longest of them being around 3 min. Molecular interpretations of the observed trends are proposed when possible. Surprisingly, in the course of our study we found experimentally that the drop shape analysis method (DSA method) shows a systematically lower surface elasticity, in comparison with the other two methods used: Langmuir trough and capillary pressure tensiometry with spherical drops. The possible reasons for the observed discrepancy are discussed, and the final conclusion is that the DSA method has specific problems and may give incorrect results when applied to study the dynamic properties of systems with high surface elasticity, such as adsorption layers of saponins, lipids, fatty acids, solid particles, and some proteins. The last conclusion is particularly important because the DSA method recently became the preferred method for the characterization of fluid interfaces because of its convenience.

Interfacial layers from the protein HFBII hydrophobin: Dynamic surface tension, dilatational elasticity and relaxation times

The pendant-drop method (with drop-shape analysis) and Langmuir trough are applied to investigate the characteristic relaxation times and elasticity of interfacial layers from the protein HFBII hydrophobin. Such layers undergo a transition from fluid to elastic solid films. The transition is detected as an increase in the error of the fit of the pendant-drop profile by means of the Laplace equation of capillarity. The relaxation of surface tension after interfacial expansion follows an exponential-decay law, which indicates adsorption kinetics under barrier control. The experimental data for the relaxation time suggest that the adsorption rate is determined by the balance of two opposing factors: (i) the barrier to detachment of protein molecules from bulk aggregates and (ii) the attraction of the detached molecules by the adsorption layer due to the hydrophobic surface force. The hydrophobic attraction can explain why a greater surface coverage leads to a faster adsorption. The relaxation of surface tension after interfacial compression follows a different, square-root law. Such behavior can be attributed to surface diffusion of adsorbed protein molecules that are condensing at the periphery of interfacial protein aggregates. The surface dilatational elasticity, E, is determined in experiments on quick expansion or compression of the interfacial protein layers. At lower surface pressures (<11 mN/m) the experiments on expansion, compression and oscillations give close values of E that are increasing with the rise of surface pressure. At higher surface pressures, E exhibits the opposite tendency and the data are scattered. The latter behavior can be explained with a two-dimensional condensation of adsorbed protein molecules at the higher surface pressures. The results could be important for the understanding and control of dynamic processes in foams and emulsions stabilized by hydrophobins, as well as for the modification of solid surfaces by adsorption of such proteins.

Instrument and methods for surface dilatational rheology measurements

We describe an instrument combining the advantages of two methods, axisymmetric drop shape analysis for well-deformed drops and capillary pressure tensiometry for spherical drops, both used for measuring the interfacial tension and interfacial rheological parameters. The rheological parameters are the complex interfacial elasticity, and the surface elasticity and viscosity of Kelvin-Voigt and Maxwell rheological models. The instrument is applicable for investigation of the effect of different types of surfactants (nonionic, ionic, proteins, and polymers) on the interfacial rheological properties both of air/water and oil/water interfaces, and of interfaces between liquids with equal mass densities. A piezodriven system and a specially designed interface unit, implemented in the instrument, ensure precise control for standard periodic waveforms of surface deformation (sine, square, triangle, and sawtooth) at a fixed frequency, or produce surface deformation at constant rate. The interface unit ensures accurate synchronization between the pressure measurement and the surface control, which is used for real-time data processing and feedback control of drop area in some of the applications.

The role of additives for the behaviour of thin emulsion films stabilized by proteins

Abstract Experimental results obtained with thin aqueous films of emulsion type stabilized by bovine serum albumin (BSA) and β-casein are presented. The film behaviour is time dependent. The contact angle increases with ageing and exhibits pronounced hysteresis. With BSA one observes slow reversible aggregation on the surface (but not in the bulk) and the protein lumps are gradually squashed by the capillary pressure as the film thins. The findings can be explained by slow surface denaturation, accompanied by developing attraction and partial entanglement of the BSA molecules. These processes are promoted by oleic acid dissolved in the oil phase. Electrostatic interactions were found to be important: without salt the films remain thick, whereas in the presence of 0.15 M NaCl one obtains Newton black films whose contact angle depends upon the molecular charge. A marked difference in the surface mobility is observed with foam and emulsion films stabilized by BSA. Lenses, containing protein aggregates and liquid, when surrounded by an area which has reached the black film stage, remain entrapped in foam films but are slowly squeezed out in emulsion films. Hydrophobization of the protein molecules may be responsible for this behaviour. With β-casein, ageing effects in films are observed only at the isoelectric point. This protein strongly aggregates in the bulk, but the lumps are readily flattened on the film interfaces. Addition of Ca 2+ ions leads to a decrease in film thickness, depending on the concentration.

Surface dilatational rheology measurements for oil/water systems with viscous oils.

This work presents an application of the capillary pressure tensiometry (CPT) for accurate measurements of the surface dilatational elastic and loss moduli of the interface between water and transparent oil phases with viscosities up to 10,000mPas. Surface rheological studies involving viscous oils are not possible with other available methods due to the considerable bulk viscous forces. Theoretical estimations show that successful measurements with such systems are possible by using a suitable frequency range of the oscillating spherical drop method by CPT. Measurements with oils having viscosities between 5 and 10,000mPas at a frequency smaller than 1Hz were performed using the oil as outer phase and the aqueous surfactant solution as inner (drop) phase. As predicted by the theory the measured surface elastic modulus did not depend on the viscosity (within experimental accuracy). Three different approaches to account for the contribution of the bulk shear viscosity to the measured pressure signal were analyzed and applied. The results showed that if exact numerical corrections are used the calculated loss modulus also did not depend on the viscosities of the bulk phases. The two other methods used lead to errors, sometimes significant.

Effect of the surfactant concentration on the kinetic stability of thin foam and emulsion films

The thinning and the lifetime of foam and emulsion films formed in a model experimental cell have been investigated. The foam films were stabilised by either sodium dodecyl sulfate or sodium dodecyl polyoxyethylene-2 sulfate. The emulsion films contained either Tween 20 or Span 20. The time of hydrodynamic drainage of the films increased linearly as the logarithm of the surfactant concentration. This linear dependence was valid whatever the type of film or surfactant and not only below the critical micelle concentration (c.m.c.) but also much above this concentration threshold. The experimental results are relevant to the hydrodynamic basis of foam and emulsion stabilisation. They are compared with the earlier hydrodynamic theories of film drainage. A reasonable, but not excellent, agreement between the experimental data and the theory could be achieved in the region below the c.m.c. of the surfactant. The data about the complex system above the c.m.c. still remain unexplained by an adequate theory. The investigation provides some guidelines for choosing the optimal type and concentration of surfactant in colloid systems of practical importance.

Encapsulation of oils and fragrances by core-in-shell structures from silica particles, polymers and surfactants: The brick-and-mortar concept

Abstract 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.