Krastanka G. Marinova

A new approach for determination the refractive index of a transparent thin film on top of an arbitrary substrate from reflectivity data taken at different layer thickness is proposed. It is shown that the layer refractive index can be found solely from minimum and maximum reflectivity values, without requiring prior knowledge of the substrate’s properties. The substrate can be composed of multiple plane-parallel homogeneous layers with complex refractive indices or may exhibit an arbitrary depth-dependent refractive index profile. These results can also be applied to spectroscopic data but are limited to substrates that are homogeneous and exhibit low refractive index dispersion within the wavelength range used. The proposed theoretical approach is demonstrated by applying it to real experimental reflectivity data from interference fringes images and spectroscopic measurements taken onto a simple substrate and simulated data for a multilayer system.

A systematic study on the mechanisms of cleansing artificial skin by solutions of widely used in personal care surfactants disodium laureth sulfosuccinate (DSLSS), sodium laureth sulfate (SLES), sodium dodecyl sulfate (SDS), dodecyl trimethyl ammonium bromide (DTAB), and coco glucoside (CG), is presented. The systematic characterization of soil removal from artificial skin revealed two primary cleansing mechanisms: emulsification and roll-up. Emulsification occurs in systems with very low interfacial tension, such as sebum in SLES solutions, while dimethicone soil was only removed by roll-up. The roll-up effectiveness depends on the surfactant’s interfacial activity and its adsorption on the soiled surface. Thus, the strong adsorption of DTAB on the skin leads to dimethicone roll-up at a relatively high interfacial tension of 11 mN/m. The anionic and nonionic surfactants adsorbed less at the artificial skin surface, and the oil/water interfacial tension value lowering below 5 mN/m is necessary for the roll-up to occur. Nonionic CG removed dimethicone at a lower concentration than ionic surfactants. Combining CG with ionic surfactants improved cleaning at lower total concentrations. Surfactant mixtures are used to formulate simple cleansing formulations, whose performance is also investigated by the developed in vitro approach. The results obtained allow for a good rating of the formulations, which correlates well with the performance of the surfactant mixtures and their interfacial activity.

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 nm². 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.