Mixing Natural and Synthetic Surfactants: Co-Adsorption of Triterpenoid Saponins and Sodium Dodecyl Sulfate at the Air-Water Interface.

Saponins are highly surface active glycosides, derived from a wide range of plant species. Their ability to produce stable foams and emulsions has stimulated their applications in beverages, foods, and cosmetics. To explore a wider range of potential applications, their surface mixing properties with conventional surfactants have been investigated. The competitive adsorption of the triterpenoid saponin escin with an anionic surfactant sodium dodecyl sulfate, SDS, at the air-water interface has been studied by neutron reflectivity, NR, and surface tension. The NR measurements, at concentrations above the mixed critical micelle concentration, demonstrate the impact of the relative surface activities of the two components. The surface mixing is highly nonideal and can be described quantitatively by the pseudophase approximation with the inclusion of the quadratic and cubic terms in the excess free energy of mixing. Hence, the surface mixing is highly asymmetrical and reflects both the electrostatic and steric contributions to the intermolecular interactions. The relative importance of the steric contribution is reinforced by the observation that the micelle mixing is even more nonideal than the surface mixing. The mixing properties result in the surface adsorption being largely dominated by the SDS over the composition and concentration range explored. The results and their interpretation provide an important insight into the wider potential for mixing saponins with more conventional surfactants.

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.

Nature of the Intermicellar Interactions in Ethoxylated Polysorbate Surfactants with High Degrees of Ethoxylation.

Ethoxylated polysorbate Tween nonionic surfactants are extensively used as foam and emulsion stabilizers and in aqueous solution form globular micelles. The ethoxylated polysorbate surfactants with higher degrees of ethoxylation than the Tween surfactants exhibit some interesting self-assembly properties. Small-angle neutron scattering, SANS, measurements have revealed intermicellar interactions which are more pronounced than the hard-sphere excluded volume interactions normally associated with nonionic surfactant micelles. The interactions are interpreted as arising from the partial charge on the ether oxygen of the ethylene oxide groups. This gives rise to an effective net negative charge on the micelles, which has been determined from the SANS data and zeta potential measurements. For degrees of ethoxylation of ⩽20, the effect is relatively small. The interaction increases with increasing ethoxylation such that for a degree of ethoxylation of 50 the interaction is comparable to that of ionic surfactant micelles. Unlike the intermicellar interaction in ionic surfactant micellar solutions, which results from the charge on the micelle arising from the partial binding of counterions, the interaction between ethoxthylated polysorbate surfactant micelles is unaffected by the addition of electrolyte.

Tuning Polyelectrolyte-Surfactant Interactions: Modification of Poly(ethylenimine) with Propylene Oxide and Blocks of Ethylene Oxide.

Significantly enhanced adsorption at the air-water interface arises in polyelectrolyte/ionic surfactant mixtures, such as poly(ethylenimine)/sodium dodecyl sulfate (PEI/SDS), down to relatively low surfactant concentrations due to a strong surface interaction between the polyelectrolyte and surfactant. In the region of charge neutralization this can result in precipitation or coacervation and give rise to undesirable properties in many applications. Ethoxylation of the PEI can avoid precipitation, but can also considerably weaken the interaction. Localization of the ethoxylation can overcome these shortcomings. Further manipulation of the polyelectrolyte-surfactant interaction can be achieved by selective ethoxylation and propoxylation of the PEI amine groups. Neutron reflectivity and surface tension data are presented here which show how the polyelectrolyte-surfactant interaction can be manipulated by tuning the PEI structure. Using deuterium labeled surfactant and polymer the neutron reflectivity measurements provide details of the surface composition and structure of the adsorbed layer. The general pattern of behavior is that at low surfactant concentrations there is enhanced surfactant adsorption due to the strong surface interaction; whereas around the region of the SDS critical micellar concentration, cmc, the surface is partially depleted of surfactant in favor bulk aggregate structures. The results presented here show how these characteristic features of the adsorption are affected by the degree of ethoxylation and propoxylation. Increasing the degree of propoxylation enhances the surfactant adsorption, whereas varying the degree of ethoxylation has a less pronounced effect. In the region of surfactant surface depletion increasing both the degree of ethoxylation and propoxylation result in an increased surface depletion.

Membrane thickness and the mechanism of action of the short peptaibol trichogin GA IV.

Trichogin GA IV (GAIV) is an antimicrobial peptide of the peptaibol family, like the extensively studied alamethicin (Alm). GAIV acts by perturbing membrane permeability. Previous data have shown that pore formation is related to GAIV aggregation and insertion in the hydrophobic core of the membrane. This behavior is similar to that of Alm and in agreement with a barrel-stave mechanism, in which transmembrane oriented peptides aggregate to form a channel. However, while the 19-amino acid long Alm has a length comparable to the membrane thickness, GAIV comprises only 10 amino acids, and its helix is about half the normal bilayer thickness. Here, we report the results of neutron reflectivity measurements, showing that GAIV inserts in the hydrophobic region of the membrane, causing a significant thinning of the bilayer. Molecular dynamics simulations of GAIV/membrane systems were also performed. For these studies we developed a novel approach for constructing the initial configuration, by embedding the short peptide in the hydrophobic core of the bilayer. These calculations indicated that in the transmembrane orientation GAIV interacts strongly with the polar phospholipid headgroups, drawing them towards its N- and C-termini, inducing membrane thinning and becoming able to span the bilayer. Finally, vesicle leakage experiments demonstrated that GAIV activity is significantly higher with thinner membranes, becoming similar to that of Alm when the bilayer thickness is comparable to its size. Overall, these data indicate that a barrel-stave mechanism of pore formation might be possible for GAIV and for similarly short peptaibols despite their relatively small size.

Manipulating the hydrophilic / hydrophobic balance in novel cationic surfactants by ethoxylation: The impact on adsorption and self-assembly.

HYPOTHESIS: Cationic surfactants have a wide range of applications, often associated with their affinity for a range of solid surfaces and their anti-microbial properties. Manipulating their adsorption and self-assembly properties is key to most applications, and this is commonly achieved through surfactant mixtures or manipulating their headgroup or alkyl chain structure. Achieving this through adjustments to their headgroup structure is less common in cationic surfactants than in anionic surfactants. Ethoxylation provides the ability to adjust the hydrophilic / hydrophobic balance, as extensively demonstrated in a range of anionic surfactants. EXPERIMENTS: This same approach has been applied here to a range of ethoxylated cationic surfactants in the form of the quaternary ammonium salts, and their tertiary nonionic equivalents before quaternisation. Their adsorption and self-assembly properties are investigated using predominantly the neutron scattering techniques of neutron reflectivity, NR, and small angle neutron scattering, SANS. FINDINGS: The trends in the adsorption at the air-water interface and the self-assembly in aqueous solution demonstrate how the hydrophilic / hydrophobic balance can be adjusted by varying the degree of ethoxylation and the alkyl chain length, and illustrate the degree of interdependence of the different structural changes. The variation in the adsorption and the micelle structure shows how the surfactant conformation / packing changes as the degree of ethoxylation and alkyl chain length increases and how the introduction of charge induces further changes.

Solution pH and oligoamine molecular weight dependence of the transition from monolayer to multilayer adsorption at the air-water interface from sodium dodecyl sulfate/oligoamine mixtures.

Neutron reflectivity and surface tension have been used to investigate the solution pH and oligoamine molecular weight dependence of the adsorption of sodium dodecyl sulfate (SDS)/oligoamine mixtures at the air-water interface. For diethylenetriamine, triamine, or triethylenetetramine, tetramine mixed with SDS, there is monolayer adsorption at pH 7 and 10, and multilayer adsorption at pH 3. For the slightly higher molecular weight tetraethylenepentamine, pentamine, and pentaethylenehexamine, hexamine, the adsorption is in the form of a monolayer at pH 3 and multilayers at pH 7 and 10. Hence, there is a pH driven transition from monolayer to multilayer adsorption, which shifts from low pH to higher pH as the oligoamine molecular weight increases from tetramine to pentamine. This results from the relative balance between the electrostatic attraction between the SDS and amine nitrogen group which decreases as the charge density decreases with increasing pH, the ion-dipole interaction between the amine nitrogen and SDS sulfate group which is dominant at higher pH, and the hydrophobic interalkyl chain interaction between bound SDS molecules which changes with oligoamine molecular weight.

The adsorption and self-assembly of surfactant mixtures: How the detailed evaluation of adsorption properties provides access to the bulk behaviour.

The nature of surfactant mixing at interfaces and in bulk solution is key to understanding and optimising the diverse industrial, technological, biological and domestic applications of surfactants. The use of neutron reflectivity, NR, and small angle neutron scattering, SANS, in combination with isotopic substitution, has transformed the ability to quantify and understand the nature of surfactant mixing at the air-water interface and in self-assembled aggregates or micelles in solution. The accuracy and scope of the compositional data from NR, the application of recent developments in the pseudo phase approximation, PPA, and the availability of complementary critical micelle concentration, cmc, and micelle composition data, enables a detailed thermodynamical quantification of the mixing properties to be made. The NR data in particular, and the SANS data to a lesser extent, provides constraints on the thermodynamical analysis which reveals important properties and trends about the bulk phase which are not available from the analysis of data such as the variation in the cmc alone. The importance and impact of this approach is illustrated with an overview of a range of mixed surfactant examples from the recent literature, and which encompass mixtures with different degrees of departure from ideality.

Promoting the adsorption of saponins at the hydrophilic solid-aqueous solution interface by the coadsorption with cationic surfactants.

HYPOTHESIS: Saponins are highly surface active glycosides, and are extensively used to stabilise emulsions and foams in beverages, foods, and cosmetics. Derived from a variety of plant species these naturally occurring biosurfactants have wider potential for inclusion in many low carbon and or sustainably sourced products. Although their adsorption at the air-solution and liquid-liquid interfaces has been extensively studied, the nature of their adsorption at solid surfaces is much less clear. The aim of this study was to establish the criteria for and nature of the adsorption of saponins at both hydrophilic and hydrophobic solid surfaces. EXPERIMENTS: Adsorption at the hydrophilic and hydrophobic solid surfaces was investigated using neutron reflectivity. Measurements were made for the saponins escin, quillaja and glycyrrhizic acid. At the hydrophilic surface measurements were also made for escin / cetyltrimethyl ammonium bromide, C16TAB, mixtures; using deuterium labelling to determine the surface structure and composition. FINDINGS: At a range of solution concentrations, from below to well in excess of the critical micelle concentration, cmc, there was no saponin adsorption evident at either the hydrophilic or hydrophobic surface. This implies an inherent incompatibility between the surface OH- groups at the hydrophilic surface and the saponin sugar groups, and a reluctance for the hydrophobic triterpenoid group of the saponin to interact with the octadecyltrichlorosilane, OTS, hydrophobic solid surface. Above a critical composition or concentration escin / C16TAB mixtures adsorb at the hydrophilic solid surface; with a surface composition which is dominated by the escin, and a structure which reflects the disparity in the molecular arrangement of the two surfactant components. The results provide an important insight into how cooperative adsorption can be utilised to promote adsorption of saponins at the solid- solution interface.

Adsorption of the linear poly(ethyleneimine) precursor poly(2-ethyl-2-oxazoline) and sodium dodecyl sulfate mixtures at the air-water interface: the impact of modification of the poly(ethyleneimine) functionality.

The adsorption of the polymer-surfactant mixture of poly(2-ethyl-2-oxazoline)-sodium dodecyl sulfate at the air-water interface has been studied by neutron reflectivity and surface tension. The observed patterns of adsorption more closely resemble those encountered in weakly interacting polymer-surfactant mixtures, rather than the pronounced enhancements in adsorption observed in strongly interacting polymer-surfactant mixtures, such as in the related poly(ethyleneimine)-sodium dodecyl sulfate mixtures. The adsorption was found to be strongly dependent on solution pH, polymer molecular weight, and polymer concentration. At the lower and higher molecular weights studied, there was little enhancement in the sodium dodecyl sulfate adsorption at low sodium dodecyl sulfate concentrations, whereas at the intermediate polymer molecular weights, some enhancement in the adsorption was observed. For the higher-molecular-weight polymers and at increasingly higher polymer concentrations, a significant reduction of the surfactant at the interface compared to pure sodium dodecyl sulfate occurred for sodium dodecyl sulfate concentrations between the critical aggregation concentration and the critical micellar concentration. The results illustrate the important role of modifying the functionality of poly(ethyleneimine) on surface adsorption.

Kinetics of surfactant desorption at an air-solution interface.

The kinetics of re-equilibration of the anionic surfactant sodium dodecylbenzene sulfonate at the air-solution interface have been studied using neutron reflectivity. The experimental arrangement incorporates a novel flow cell in which the subphase can be exchanged (diluted) using a laminar flow while the surface region remains unaltered. The rate of the re-equilibration is relatively slow and occurs over many tens of minutes, which is comparable with the dilution time scale of approximately 10-30 min. A detailed mathematical model, in which the rate of the desorption is determined by transport through a near-surface diffusion layer into a diluted bulk solution below, is developed and provides a good description of the time-dependent adsorption data. A key parameter of the model is the ratio of the depth of the diffusion layer, H(c), to the depth of the fluid, H(f), and we find that this is related to the reduced Péclet number, Pe*, for the system, via H(c)/H(f) = C/Pe*(1/2). Although from a highly idealized experimental arrangement, the results provide an important insight into the "rinse mechanism", which is applicable to a wide variety of domestic and industrial circumstances.

Self-assembly of mixed anionic and nonionic surfactants in aqueous solution.

We present the phase diagram and the microstructure of the binary surfactant mixture of AOT and C(12)E(4) in D(2)O as characterized by surface tension and small angle neutron scattering. The micellar region is considerably extended in composition and concentration compared to that observed for the pure surfactant systems, and two types of aggregates are formed. Spherical micelles are present for AOT-rich composition, whereas cylindrical micelles with a mean length between 80 and 300 Å are present in the nonionic-rich region. The size of the micelles depends on both concentration and molar ratio of the surfactant mixtures. At higher concentration, a swollen lamellar phase is formed, where electrostatic repulsions dominate over the Helfrich interaction in the mixed bilayers. At intermediate concentrations, a mixed micellar/lamellar phase exists.

Neutron reflectometry of quaternary gemini surfactants as a function of alkyl chain length: anomalies arising from ion association and premicellar aggregation.

We have measured the structure and properties of a series of dicationic quaternary ammonium compounds α,ω-bis(N-alkyl dimethyl ammonium)hexane halides (Cn-C6-Cn) for values of the alkyl chain length n of 8, 9, 10, 11, 12, and 16, and a series of α,ω-bis(N-alkyl dimethyl ammonium)diethylether halides (Cn-C2OC2-Cn) for values of n of 8, 12, and 16, as well as C8-C12-C8 and C12-C10-C12 at the air/water interface. Although the critical micelle concentration (CMC) in the two series decreases in the normal way, that is, logarithmically, with increasing chain length, the limiting surface tension at the CMC and the limiting area per molecule both increase with chain length, in the opposite direction from comparable single chain surfactants. The structures of the surface layers, which were determined by neutron reflectometry, indicate that the anomalous behavior of the surface tension and area are probably caused by poor packing of the gemini side chains between adjacent molecules. Comparison of the directly determined surface coverage using neutron reflectometry and the apparent coverage determined by application of the Gibbs equation to surface tension data gives an experimental measurement of the prefactor in the Gibbs equation, which should be 3 for these geminis. It was found to vary from about 3 for the two C16 geminis down to about 1.5 for the two C8 geminis. We have devised a simple quantitative model that explains this variation and earlier observations that the Gibbs prefactor for C12-Cn-C12 (n varying from 3 to 12) is around 2. The model is consistent with the conductivity, NMR, and fluorescence measurements of other authors. This model shows that both dimerization and ion association are required to explain the surface tension behavior of cationic gemini bromide surfactants and that, in many cases, the prefactor itself varies with concentration.

Adsorption of polyelectrolyte/surfactant mixtures at the air-water interface: modified poly(ethyleneimine) and sodium dodecyl sulfate.

The adsorption of surfactant/polyelectrolyte mixtures of sodium dodecyl sulfate (SDS) and different modified poly(ethyleneimine) (PEI) polyelectrolytes at the air-water interface has been studied using neutron reflectivity and surface tension. Modification of the PEI by the addition of short ethylene oxide (EO) or propylene oxide (PO) groups is shown to have an impact upon the surface adsorption behavior. This is due to a modification of the polymer/surfactant interaction, an increase in the intrinsic surface activity of the modified polyelectrolyte, and changes in the relative importance of surface and solution complex formation. For the polyelectrolyte PEI, there is a marked change in the surface adsorption behavior between the addition of a single EO group and that of the (EO)3 group. The addition of a single EO or PO group to the PEI results in an SDS concentration and solution pH adsorption dependence that is broadly similar in behavior to that of the unmodified PEI/SDS mixture. That is, there is strong surface complexation and adsorption down to low SDS concentrations, and there is evidence of a strong interaction at high pH in addition to the strong electrostatic attraction at low pH. The addition of a larger ethylene oxide group, triethylene oxide (EO)3, results in a surface adsorption behavior that more closely resembles that of a neutral polymer/ionic surfactant mixture, similar to that observed for PEI with a larger ethylene oxide group, notably PEI-(EO)7. In that case, the adsorption of the polymer/surfactant complex is much less pronounced. The adsorption arises predominantly from competition between the polymer and surfactant and indicates a decrease in the polymer/surfactant interaction with increasing pH. That is, increasing the size of the ethylene oxide group induces a transition from a strong surface polymer/surfactant interaction to a weak polymer/surfactant interaction.

The adsorption and self-assembly of mixtures of alkylbenzene sulfonate isomers and the role of divalent electrolyte.

In this paper, the role of the different structural isomers of the anionic surfactant sodium para-dodecyl benzene sulfonate, LAS, on surface adsorption and solution self-assembly has been studied. Using a combination of neutron reflectivity, NR, and small angle neutron scattering, SANS, the effect of mixing an isomer with a short symmetric hydrocarbon chain with one which has an asymmetric hydrocarbon chain on both the equilibrium surface adsorption behavior and the solution microstructure of the mixtures, both in the presence and absence of a divalent cation (Ca(2+)), has been investigated. In the absence of electrolyte, the LAS isomer mixtures form small charged globular micelles throughout the composition range studied. The micelle aggregation number increases with the increase in the asymmetric isomer content, reflecting an increase in the packing efficiency within the micelle. The addition of calcium ions promotes the formation of planar aggregates, as multilamellar vesicles, but only when the symmetric LAS isomer is the major component of the mixture. At a surfactant concentration just above the critical micelle concentration, CMC, and in the absence of electrolyte, the variation in the surface composition is close to the solution composition. Regular solution theory, RST, calculations show that this variation is also close to what is expected for ideal mixing. The addition of Ca(2+) ions induces a different surface behavior, resulting in the formation of multilayer structures at the interface throughout the entire composition range.

Adsorption and self-assembly properties of the plant based biosurfactant, Glycyrrhizic acid.

There is an increased interest in the use of natural surfactant as replacements for synthetic surfactants due to their biosustainable and biocompatible properties. A category of natural surfactants which are attracting much current interest is the triterpenoid saponins; surface active components found extensively in a wide range of plant species. A wide range of different saponin structures exist, depending upon the plant species they are extracted from; but regardless of the variation in structural details they are all highly surface active glycosides. Greater exploitation and application requires a characterisation and understanding of their basic adsorption and self-assembly properties. HYPOTHESIS: Glycyrrhizic acid, extracted from Licorice root, is a monodesmosidic triterpenoid saponin. It is widely used in cosmetic and pharmaceutical applications due to its anti-inflammatory properties, and is an ingredient in foods as a sweetener additive. It has an additional attraction due to its gel forming properties at relatively low concentrations. Although it has attracted much recent attention, many of its basic surface active characteristics, adsorption and self-assembly, remain relatively unexplored. How the structure of the Glycyrrhizic acid saponin affects its surface active properties and the impact of gelation on these properties are important considerations, and to investigate these are the focus of the study. EXPERIMENTS: In this paper the adsorption properties at the air-water interface and the self-assembly in solution have been investigated using by neutron reflectivity and small angle neutron scattering; in non-gelling and gelling conditions. FINDINGS: The adsorption isotherm is determined in water and in the presence of gelling additives, and compared with the adsorption behaviour of other saponins. Gelation has minimal impact on the adsorption; apart from producing a rougher surface with a surface texture on a macroscopic length scale. Globular micelles are formed in aqueous solution with modest anisotropy, and are compared with the structure of other saponin micelles. The addition of gelling agents results in only minimal micelle growth, and the solutions remain isotropic under applied shear flow.

Adsorption of nonionic and mixed nonionic/cationic surfactants onto hydrophilic and hydrophobic cellulose thin films.

The adsorption of the nonionic surfactant hexaethylene monododecyl ether, C(12)E(6), and the mixed nonionic/cationic surfactants C(12)E(6) and hexadecyl trimethyl ammonium bromide, C(16)TAB, onto the hydrophilic and hydrophobic surfaces of thin cellulose films, formed by Langmuir-Blodgett, L-B, deposition, have been studied by neutron reflectivity. For the surfactant mixtures, considerable nonideal mixing is observed at both hydrophobic and hydrophilic surfaces. The results demonstrate that the C(12)E(6), C(12)E(6)/C(16)TAB mixture and solvent have a greater penetration into the cellulose film upon adsorption, compared to that observed in previous studies of C(16)TAB adsorbed onto cellulose, due to the presence of the nonionic surfactant. From the range of measurements made, it is concluded that both the presence of the nonionic surfactant and the nature of the cellulose films are both contributing factors to this increased penetration and swelling of the cellulose film.

Surface and solution properties of anionic/nonionic surfactant mixtures of alkylbenzene sulfonate and triethyleneglycol decyl ether.

The surface adsorption behavior and the solution microstructure of mixtures of the C(6) isomer of anionic surfactant sodium para-dodecyl benzene sulfonate, ABS, with nonionic surfactant monodecyl triethyleneglycol ether, C(10)E(3,) have been investigated using a combination of neutron reflectivity, NR, and small-angle neutron scattering, SANS. In solution, the mixing of C(10)E(3) and ABS results in the formation of small globular micelles over most of the composition range (100:0 to 20:80 ABS/C(10)E(3)). Planar aggregates (lamellar or unilamellar vesicles, ULV) are observed for solution compositions rich in the nonionic surfactant (>80 mol % nonionic). Prior to the transition to planar aggregates, the micelle aggregation number increases with increasing nonionic composition. The lamellar-phase region is preceded by a narrow range of composition over which mixtures of micelles and small unilamellar vesicles coexist. The variation in surface absorption behavior with solution composition shows a strong surface partitioning of the more surface-active component, C(10)E(3). This pronounced departure from ideal mixing is not readily explained by existing surfactant mixing theories. In the presence of Ca(2+) ions, a more complex evolution of solution phase behavior with solution composition is observed. The lamellar-phase region occurs over a broader range of solution compositions at the expense of the small-vesicle phase. The phase boundaries are shifted to lower nonionic compositions, and the extent to which the solution-phase diagrams are modified increases with increasing calcium ion concentration. The SANS data for the large planar aggregates are consistent with large polydisperse flexible unilamellar vesicles. In the presence of Ca(2+) ions, the surface adsorption patterns become more consistent with ideal mixing in the nonionic-rich region of the surface-phase diagram. However, in the ABS-rich regions the surface behavior is more complex because of the spontaneous formation of more complex surface microstructures (bilayers to multilayers). Both in water and in the presence of Ca(2+) ions the variations in the surface adsorption behavior and in the solution mesophase structure do not appear to be closely correlated.

Mixing behavior of the biosurfactant, rhamnolipid, with a conventional anionic surfactant, sodium dodecyl benzene sulfonate.

The use of small angle neutron scattering, SANS, neutron reflectivity, NR, and surface tension to study the mixing properties of the biosurfactant rhamnolipid with a conventional anionic surfactant, sodium dodecyl 6-benzene sulfonate, LAS, is reported. The monorhamnose rhamnolipid, R1, mixes close to ideally with LAS at the air-water interface, whereas for mixtures of LAS with the dirhamnose rhamnolipid, R2, the LAS strongly partitions to the air-water interface relative to R2, probably because of the steric hindrance of the larger R2 headgroup. These trends in the binary mixtures are also reflected in the ternary R1/R2/LAS mixtures. However, for these ternary mixtures, there is also a pronounced synergy in the total adsorption, which reaches a maximum for a LAS/rhamnolipid mole ratio of about 0.6 and a R1/R2 mol ratio of about 0.5, an effect which is not observed in the binary mixtures. In solution, the R1/LAS mixtures form relatively small globular micelles, L(1), at low surfactant concentrations (<20 mM), more planar structures (lamellar, L(α), unilamellar/multilamellar vesicles, ulv/mlv) are formed at higher surfactant concentrations for R1 and LAS rich compositions, and a large mixed phase (L(α)/L(1) and L(1)/L(α)) region forms at intermediate surfactant compositions. In contrast, for the R2/LAS mixtures, the higher preferred curvature of R2 dominates the phase behavior. The predominant microstructure is in the form of small globular micelles, except for solution compositions rich in LAS (>80 mol % LAS) where more planar structures are formed. For the ternary mixtures, there is an evolution in the resulting phase behavior from one dominated by L(1) (R2 rich) to one dominated by planar structures, L(α), (R1, LAS rich), and which strongly depends upon the LAS/rhamnolipid and R1/R2 mole ratio.

Solution self-assembly and adsorption at the air-water interface of the monorhamnose and dirhamnose rhamnolipids and their mixtures.

The self-assembly in solution and adsorption at the air-water interface, measured by small-angle neutron scattering, SANS, and neutron reflectivity, NR, of the monorhamnose and dirhamnose rhamnolipids (R1, R2) and their mixtures, are discussed. The production of the deuterium-labeled rhamnolipids (required for the NR studies) from a Pseudomonas aeruginosa culture and their separation into the pure R1 and R2 components is described. At the air-water interface, R1 and R2 exhibit Langmuir-like adsorption isotherms, with saturated area/molecule values of about 60 and 75 Å(2), respectively. In R1/R2 mixtures, there is a strong partitioning of R1 to the surface and R2 competes less favorably because of the steric or packing constraints of the larger R2 dirhamnose headgroup. In dilute solution (<20 mM), R1 and R2 form small globular micelles, L(1), with aggregation numbers of about 50 and 30, respectively. At higher solution concentrations, R1 has a predominantly planar structure, L(α) (unilamellar, ULV, or bilamellar, BLV, vesicles) whereas R2 remains globular, with an aggregation number that increases with increasing surfactant concentration. For R1/R2 mixtures, solutions rich in R2 are predominantly micellar whereas solutions rich in R1 have a more planar structure. At an intermediate composition (60 to 80 mol % R1), there are mixed L(α)/L(1) and L(1)/L(α) regions. However, the higher preferred curvature associated with R2 tends to dominate the mixed R1/R2 microstructure and its associated phase behavior.