Saponin Adsorption at the Air-Water Interface-Neutron Reflectivity and Surface Tension Study.

Saponins are a large group of glycosides present in many plant species. They exhibit high surface activity, which arises from a hydrophobic scaffold of triterpenoid or steroid groups and attached hydrophilic saccharide chains. The diversity of molecular structures, present in various plants, gives rise to a rich variety of physicochemical properties and biological activity and results in a wide range of applications in foods, cosmetics, medicine, and several other industrial sectors. Saponin surface activity is a key property in such applications and here the adsorption of three triterpenoid saponins, escin, tea saponins, and Quillaja saponin, is studied at the air-water interface by neutron reflectivity and surface tension. All these saponins form adsorption layers with very high surface visco-elasticity. The structure of the adsorbed layers has been determined from the neutron reflectivity data and is related to the molecular structure of the saponins. The results indicate that the structure of the saturated adsorption layers is governed by densely packed hydrophilic saccharide groups. The tight molecular packing and the strong hydrogen bonds between the neighboring saccharide groups are the main reasons for the unusual rheological properties of the saponin adsorption layers.

Micellar solubilization of poorly water-soluble drugs: effect of surfactant and solubilizate molecular structure.

OBJECTIVE: This study aims to clarify the role of surfactant and drug molecular structures on drug solubility in micellar surfactant solutions. SIGNIFICANCE: (1) Rationale for surfactant selection is provided; (2) the large data set can be used for validation of the drug solubility parameters used in oral absorption models. METHODS: Equilibrium solubility of two hydrophobic drugs and one model hydrophobic steroid in micellar solutions of 19 surfactants was measured by HPLC. The drug solubilization locus in the micelles was assessed by UV spectrometry. RESULTS: Danazol is solubilized much more efficiently than fenofibrate by ionic surfactants due to ion-dipole interactions between the charged surfactant head groups and the polar steroid backbone. Drug solubilization increases linearly with the increase of hydrophobic chain length for all studied surfactant types. Addition of 1-3 ethylene oxide (EO) units in the head group of dodecyl sulfate surfactants reduces significantly the solubilization of both studied drugs and decreases linearly the solubilization locus polarity of fenofibrate. The locus of fenofibrate solubilization is in the hydrophobic core of nonionic surfactant micelles and in the palisade layer of ionic surfactant micelles. CONCLUSIONS: Highest drug solubility can be obtained by using surfactants molecules with long chain length coupled with hydrophilic head group that provides additional drug-surfactant interactions (i.e. ion-dipole) in the micelles.

Temperature response of sucrose palmitate solutions: Role of ratio between monoesters and diesters.

HYPOTHESIS: Aqueous solutions of long-chain water-soluble sucrose ester surfactants exhibit non-trivial response to temperature variations, revealing a peak in viscosity around 40-50 °C. While previous investigations have explored the structures within sucrose stearate systems at various constant temperatures, a comprehensive understanding of the entire temperature dependence and the underlying molecular factors, contributing to this phenomenon is currently missing. EXPERIMENTS: Temperature dependent properties and supramolecular structures formed in aqueous solutions of commercial sucrose palmitate were examined using SAXS/WAXS, DSC, optical microscopy, rheological measurements, NMR, and cryo-TEM. FINDINGS: The underlying mechanism governing this unusual behavior is revealed and is shown to relate to the mono- to di-esters ratio in the solutions. Solutions primarily containing sucrose monoesters (monoesters molecules ≳ 98% of all surfactant molecules) exhibit behavior typical of nonionic surfactants, with minimal changes with temperature. In contrast, the coexistence of mono- and di-esters results in the formation of discrete monodisperse diester particles and a network of partially fused diester particles at low temperature. As the temperature approaches the diesters' melting point, wormlike mixed micelles form, causing a viscosity peak. The height of this peak increases significantly with the diester concentration. Further temperature increase leads to fluidization of surfactant tails and formation of branched micelles, while excess diester molecules phase separate into distinct droplets.

Efficient control of the rheological and surface properties of surfactant solutions containing C8-C18 fatty acids as cosurfactants.

Systematic experimental study is performed about the effects of chain length (varied between C8 and C18) and concentration of fatty acids (FAc), used as cosurfactants to the mixture of the anionic surfactant SLES and the zwitterionic surfactant CAPB. The following properties are studied: bulk viscosity of the concentrated solutions (10 wt % surfactants), dynamic and equilibrium surface tensions, surface modulus, and foam rheological properties for the diluted foaming solutions (0.5 wt % surfactants). The obtained results show that C8-C10 FAc induce formation of wormlike micelles in the concentrated surfactant solutions, which leads to transformation of these solutions into viscoelastic fluids with very high apparent viscosity. The same FAc shorten the characteristic adsorption time of the diluted solutions by more than 10 times. In contrast, C14-C18 FAc have small effect on the viscosity of the concentrated solutions but increase the surface modulus above 350 mN/m, which leads to higher friction inside sheared foams and to much smaller bubbles in the formed foams. The intermediate chain C12 FAc combines some of the properties seen with C10 FAc and other properties seen with C14 FAc. These results clearly demonstrate how appropriate cosurfactants can be used for efficient control of the rheological properties of concentrated surfactant solutions and of some important foam attributes, such as bubble size and foam rheology.

Foaming and foam stability for mixed polymer-surfactant solutions: effects of surfactant type and polymer charge.

Solutions of surfactant-polymer mixtures often exhibit different foaming properties, compared to the solutions of the individual components, due to the strong tendency for formation of polymer-surfactant complexes in the bulk and on the surface of the mixed solutions. A generally shared view in the literature is that electrostatic interactions govern the formation of these complexes, for example between anionic surfactants and cationic polymers. In this study we combine foam tests with model experiments to evaluate and explain the effect of several polymer-surfactant mixtures on the foaminess and foam stability of the respective solutions. Anionic, cationic, and nonionic surfactants (SDS, C(12)TAB, and C(12)EO(23)) were studied to clarify the role of surfactant charge. Highly hydrophilic cationic and nonionic polymers (polyvinylamine and polyvinylformamide, respectivey) were chosen to eliminate the (more trivial) effect of direct hydrophobic interactions between the surfactant tails and the hydrophobic regions on the polymer chains. Our experiments showed clearly that the presence of opposite charges is not a necessary condition for boosting the foaminess and foam stability in the surfactant-polymer mixtures studied. Clear foam boosting (synergistic) effects were observed in the mixtures of cationic surfactant and cationic polymer, cationic surfactant and nonionic polymer, and anionic surfactant and nonionic polymer. The mixtures of anionic surfactant and cationic polymer showed improved foam stability, however, the foaminess was strongly reduced, as compared to the surfactant solutions without polymer. No significant synergistic or antagonistic effects were observed for the mixture of nonionic surfactant (with low critical micelle concentration) and nonionic polymer. The results from the model experiments allowed us to explain the observed trends by the different adsorption dynamics and complex formation pattern in the systems studied.

Effect of cationic polymers on foam rheological properties.

We study the effect of two cationic polymers, with trade names Jaguar C13s and Merquat 100, on the rheological properties of foams stabilized with a mixture of anionic and zwitterionic surfactants (sodium lauryloxyethylene sulfate and cocoamidopropyl betaine). A series of five cosurfactants are used to compare the effect of these polymers on foaming systems with high and low surface dilatational moduli. The experiments revealed that the addition of Jaguar to the foaming solutions leads to (1) a significant increase of the foam yield stress for all systems studied, (2) the presence of consecutive maximum and minimum in the stress vs shear rate rheological curve for foams stabilized by cosurfactants with a high surface modulus (these systems cannot be described by the Herschel-Bulkley model anymore), and (3) the presence of significant foam-wall yield stress for all foaming solutions. These effects are explained with the formation of polymer bridges between the neighboring bubbles in slowly sheared foams (for inside foam friction) and between the bubbles and the confining solid wall (for foam-wall friction). Upon addition of 150 mM NaCl, the effect of Jaguar disappears. The addition of Merquat does not noticeably affect any of the foam rheological properties studied. Optical observations of foam films, formed from all these systems, show a very good correlation between the polymer bridging of the foam film surfaces and the strong polymer effect on the foam rheological properties. The obtained results demonstrate that the bubble-bubble attraction can be used for efficient control of the foam yield stress and foam-wall yield stress, without significantly affecting the viscous friction in sheared foams.

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.

Foamability of aqueous solutions: Role of surfactant type and concentration.

In this paper we study the main surface characteristics which control the foamability of solutions of various surfactants. Systematic series of experiments with anionic, cationic and nonionic surfactants with different head groups and chain lengths are performed in a wide concentration range, from 0.001 mM to 100 mM. The electrolyte (NaCl) concentration is also varied from 0 up to 100 mM. For all surfactants studied, three regions in the dependence of the foamability, VA, on the logarithm of surfactant concentration, lgCS, are observed. In Region 1, VA is very low and depends weakly on CS. In Region 2, VA increases steeply with CS. In Region 3, VA reaches a plateau. To analyse these results, the dynamic and equilibrium surface tensions of the foamed solutions are measured. A key new element in our interpretation of the foaming data is that we use the surface tension measurements to determine the dependence of the main surface properties (surfactant adsorption, surface coverage and surface elasticity) on the surface age of the bubbles. In this way we interpret the results from the foaming tests by considering the properties of the dynamic adsorption layers, formed during foaming. The performed analysis reveals a large qualitative difference between the nonionic and ionic surfactants with respect to their foaming profiles. The data for the nonionic and ionic surfactants merge around two master curves when plotted as a function of the surface coverage, the surface mobility factor, or the Gibbs elasticity of the dynamic adsorption layers. This difference between the ionic and nonionic surfactants is explained with the important contribution of the electrostatic repulsion between the foam film surfaces for the ionic surfactants which stabilizes the dynamic foam films even at moderate surface coverage and at relatively high ionic strength (up to 100 mM). In contrast, the films formed from solutions of nonionic surfactants are stabilized via steric repulsion which becomes sufficiently high to prevent bubble coalescence only at rather high surface coverage (> 90%) which corresponds to related high Gibbs elasticity (> 150 mN/m) and low surface mobility of the dynamic adsorption layers. Mechanistic explanations of all observed trends are provided and some important similarities and differences with the process of emulsification are outlined.

Breakup of bubbles and drops in steadily sheared foams and concentrated emulsions.

This experimental study is focused on the process of bubble breakup in steadily sheared foams, at constant shear rate or constant shear stress. Two different types of surfactants were used and glycerol was added to the aqueous phase, to check how the bubble breakup depends on the surface modulus and on bulk viscosity of the foaming solutions. The experiments show that bubble breakup in foams occurs above a well defined critical dimensionless stress, tau[over]CR identical with(tauCRR/sigma) approximately 0.40, which is independent of surfactant used, solution viscosity, and bubble volume fraction (varied between 92 and 98%). Here tauCR is the dimensional shear stress, above which a bubble with radius R and surface tension sigma would break in sheared foam. The value of the critical stress experimentally found by us tau[over]CR approximately 0.40, is about two orders of magnitude lower than the critical stress for breakup of single bubbles in sheared Newtonian liquids, tau[over]CR approximately 25. This large difference in the critical stress is explained by the strong interaction between neighboring bubbles in densely populated foams, which facilitates bubble subdivision into smaller bubbles. A strong effect of bubble polydispersity on the kinetics of bubble breakup (at similar mean bubble size) was observed and explained. Experiments were also performed with hexadecane-in-water emulsions of drop volume fraction 83%

Theoretical model of viscous friction inside steadily sheared foams and concentrated emulsions.

In a recent Letter [N. D. Denkov, Phys. Rev. Lett. 100, 138301 (2008)] we calculated theoretically the macroscopic viscous stress of steadily sheared foam or emulsion from the energy dissipated inside the transient planar films, formed between neighboring bubbles or drops in the shear flow. The model predicts that the viscous stress in these systems should be proportional to Ca 1/2, where Ca is a capillary number and n=1/2 is the power-law index. In the current paper we explain our model in detail and develop it further in several aspects: First, we extend the model to account for the effects of viscous friction in the curved meniscus regions, surrounding the planar films, on the dynamics of film formation and on the total viscous stress. Second, we consider the effects of surface forces (electrostatic, van der Waals, etc.) acting between the surfaces of the neighboring bubbles or drops and show that these forces could be important in emulsions, due to the relatively small thickness of emulsion films (often comparable to the range of action of surface forces). In contrast, the surface forces are usually negligible in steadily sheared foams, because the dynamic foam films are thicker than the extent of surface forces, except for foams containing micrometer-sized bubbles and/or at very low shear rates. Third, additional consideration is made for bubbles or drops exhibiting high surface viscosity, for which we demonstrate an additional contribution to the macroscopic viscous stress, created by the surface dissipation of energy. The new upgraded model predicts that the energy dissipation at the bubble or drop surface leads to power-law index n<1/2 , whereas the contribution of the surface forces leads to n>1/2 , which explains the rich variety of foam or emulsion behaviors observed upon steady shear. Various comparisons are made between model predictions and experimental results for both foams and emulsions, and very good agreement is found.

Role of Pickering stabilization and bulk gelation for the preparation and properties of solid silica foams.

Foaming of particulate suspensions, followed by foam drying, is developed as an efficient method for production of highly porous materials with various applications. A key factor for success is the appropriate choice of surfactants which both modify the particle surface and stabilize the foam. Here we compare the efficiency of this method for silica suspensions containing two surfactants which lead to very different types of foam stabilization. Cationic TTAB leads to particle-stabilized foams (Pickering stabilization) whereas zwitterionic CAPB - to surfactant-stabilized foams. Thus we determined the general (common) features shared between the various surfactant systems: (1) The foaminess is controlled exclusively by the suspension viscosity under shearing conditions which mimic precisely the foaming process; (2) The foam stability to drainage and coarsening is controlled exclusively by the suspension yield stress; (3) The surfactant adsorption on the particle surface should occur in the time scale of seconds to minutes, thus ensuring appropriate rheological properties of the foaming suspension. Similar kinetic effects could be of high interest to other colloid systems and processes, e.g. for kinetic control of the internal structure and properties of aerogels produced from sheared suspensions, and for control of the transient rheological properties and non-Newtonian flow of particulate gels.

Factors controlling the formation and stability of foams used as precursors of porous materials.

The remarkable stability of particle-stabilized foams and the opportunity to use them for production of novel porous materials have been attracting the researchers' attention in the recent years. The major aim of the current study is to clarify the factors, controlling the foamability and stability of foams, formed from concentrated silica suspensions in the presence of the amphoteric surfactant CAPB. The experiments showed that: (1) two regions can be defined with respect to suspension foaminess: Region 1 - good foaming and Region 2 - strongly suppressed foaming. The foam volume decreased linearly with the increase of suspension viscosity, so that Region 2 appears as a result of the excessively high suspension viscosity. (2) Based on foam stability four sub-regions were observed in Region 1: region 1S - stable foams, which can be dried to form stable porous materials; 1UD - foams which are unstable with respect to water drainage and collapse upon drying; 1UC - foams which are stable to drainage, but are unstable to drying, due to crack formation; 1UF - unstable foams which completely fall apart upon drying. (3) Foams in Regions 1S and 1UC had yield stress above 10 Pa which prevented liquid drainage, while foams from Region 1UD drained because of their lower yield stress. (4) The particles in the foams assembled in a 3D network in the Plateau channels and the nodes, while surfactant stabilized the foam films between the bubbles. These results define the conditions, appropriate for formation of stable, highly porous silica materials with low mass density, which can be further modified (sintered, impregnated, hydrophobized, etc.) to serve as catalyst supports, porous filters, insulating materials, etc.

Jamming in sheared foams and emulsions, explained by critical instability of the films between neighboring bubbles and drops.

Foam and emulsion jamming at low shear rates is explained by considering the thinning dynamics of the transient films, formed between neighboring bubbles and drops. After thinning gradually to a critical thickness, these films undergo an instability transition, which leads to the formation of very thin "black films" providing strong adhesion between the dispersed particles. Analysis shows that such film thickness instability occurs only if the contact time between particles is sufficiently long-an explicit expression for the respective critical shear rate is derived and compared to experimental data.

Comparison of solid particles, globular proteins and surfactants as emulsifiers.

The aim of this paper is to present a short overview of the main mechanisms operative in the formation and stabilization of emulsions by solid particles and, on this basis, to make comparisons between solid particles, surfactants and globular proteins as emulsifiers. When available, simple quantitative relations are presented, with the respective numerical estimates and discussion of the applicability of these relations to particle-stabilized systems. Non-obvious similarities between the different types of emulsifiers are outlined in several cases in which the description of the system can be performed at a phenomenological level. Examples are presented for the process of emulsification, where we show that several simple theoretical expressions, derived originally in the studies of surfactants and protein emulsifiers, can be successfully applied to particle-stabilized emulsions. In contrast, for the phenomena in which the detailed mechanisms of particle adsorption and film stabilization are important, the differences between the various emulsifiers prevail, thus making it impossible to use the same theoretical description. The most important specific characteristics of the solid particles which strongly affect their behavior are the high barrier to particle adsorption, high desorption energy and strong capillary forces between particles trapped in liquid films, which all originate in the relatively large particle size (as compared to the size of surfactant and protein molecules). The capillary mechanism of stabilization of liquid films by solid particles is reviewed in some detail, to emphasize its specific features and to demonstrate the applicability of several simple expressions for approximate estimates. Interestingly, we found that the hypothesis for some exceptionally high coalescence stability of the particle-stabilized emulsions is not supported by the experimental data available in literature. On the other hand, the particles are able to completely arrest the process of Ostwald ripening in foams and emulsions, and this effect can be easily explained with the high desorption energy of the particles and the resulting capillary effects.

Surfactant mixtures for control of bubble surface mobility in foam studies.

A new class of surfactant mixtures is described, which is particularly suitable for studies related to foam dynamics, such as studies of foam rheology, liquid drainage from foams and foam films, and bubble coarsening and rearrangement. These mixtures contain an anionic surfactant, a zwitterionic surfactant, and fatty acids (e.g., myristic or lauric) of low concentration. Solutions of these surfactant mixtures exhibit Newtonian behavior, and their viscosity could be varied by using glycerol. Most importantly, the dynamic surface properties of these solutions, such as their surface dilatational modulus, strongly depend on the presence and on the chain-length of fatty acid(s). Illustrative results are shown to demonstrate the dependence of solution properties on the composition of the surfactant mixture, and the resulting effects on foam rheological properties, foam film drainage, and bubble Ostwald ripening. The observed high surface modulus in the presence of fatty acids is explained with the formation of a surface condensed phase of fatty acid molecules in the surfactant adsorption layer.

Viscous friction in foams and concentrated emulsions under steady shear.

We present a model for the viscous friction in foams and concentrated emulsions, subject to steady shear flow. First, we calculate the energy dissipated due to viscous friction inside the films between two neighboring bubbles or drops, which slide along each other in the flow. Next, from this energy we calculate the macroscopic viscous stress of the sheared foam or emulsion. The model predictions agree well with experimental results obtained with foams and emulsions.

Latex-particle-stabilized emulsions of anti-Bancroft type.

Here, we investigate water-in-oil (W/O) emulsions that are stabilized by polystyrene latex particles with sulfate surface groups. The particles, which play the role of emulsifier, are initially contained in the disperse (water) phase. The existence of such emulsions formally contradicts the empirical Bancroft rule. Theoretical considerations predict that the drop diameter has to be inversely proportional to the particle concentration, but should be independent of the volume fraction of water. In addition, there should be a second emulsification regime, in which the drop diameter is determined by the input mechanical energy during the homogenization. The existence of these two regimes has been experimentally confirmed, and the obtained data agree well with the theoretical model. Stable W/O emulsions have been produced with hexadecane and tetradecane, while, in the case of more viscous and polar oils (soybean and silicone oil), the particles enter into the oily phase, and Pickering emulsions cannot be obtained. The formation of stable emulsions demands the presence of a relatively high concentration of electrolyte that lowers the electrostatic barrier to particle adsorption at the oil-water interface. Because the attachment of particles at the drop surfaces represents a kind of coagulation, it turns out that the Schulze-Hardy rule for the critical concentration of coagulation is applicable also to emulsification, which has been confirmed with suspensions containing Na(+), Mg(2+), and Al(3+) counterions. The increase of the particle and electrolyte concentrations and the decrease of the volume fraction of water are other factors that facilitate emulsification in the investigated system. To quantify the combined action of these factors, an experimental stability-instability diagram has been obtained.