Surfactant tail-group

It should be noted that high concentrations of ionic species can alter the phase stability of microemulsions based upon ionic surfactant systems. Nonionic surfactant systems are much less susceptible to this effect. The curvature of the interfacial film of the microemulsion droplet is determined by a balance between the electrostatic interactions of the head groups and repulsive interactions of the surfactant tail group. Addition of ionic solutes can upset this delicate balance and induce phase separation. By changing the structure of the surfactant or through the addition of cosurfactants one can restore this balance and thus allow the dissolution of high concentrations of ionic species. 

Figure 2. Schematic illustration of three-dimensional network formed by binding of affinity surfactant to multi-binding site biomolecule and subsequent hydrophobic aggregation of surfactant tail groups.

As an example of the modification of the oil phase, one can consider an emulsion of mineral oil (8 = 14.4) in water. A typical surfactant tail group [e.g., lauryl, CH3(CH2)n—] has a partial solubihty parameter of 16.7. In order to improve the match between surfactant tail and oil phase, one might add a more polar solute such as cetyl alcohol [CH2(CH2)ieOH, 8 20], thereby increasing the polarity of the oil phase. Alternatively, one can decrease the cohesion between the aqueous phase and the surfaetant head group by the addition of a less polar solute such as propylene glycol (8 = 30.7). 

Surfactants employed for w/o-ME formation, listed in Table 1, are more lipophilic than those employed in aqueous systems, e.g., for micelles or oil-in-water emulsions, having a hydrophilic-lipophilic balance (HLB) value of around 8-11 [4-40]. The most commonly employed surfactant for w/o-ME formation is Aerosol-OT, or AOT [sodium bis(2-ethylhexyl) sulfosuccinate], containing an anionic sulfonate headgroup and two hydrocarbon tails. Common cationic surfactants, such as cetyl trimethyl ammonium bromide (CTAB) and trioctylmethyl ammonium bromide (TOMAC), have also fulfilled this purpose however, cosurfactants (e.g., fatty alcohols, such as 1-butanol or 1-octanol) must be added for a monophasic w/o-ME (Winsor IV) system to occur. Nonionic and mixed ionic-nonionic surfactant systems have received a great deal of attention recently because they are more biocompatible and they promote less inactivation of biomolecules compared to ionic surfactants. Surfactants with two or more hydrophobic tail groups of different lengths frequently form w/o-MEs more readily than one-tailed surfactants without the requirement of cosurfactant, perhaps because of their wedge-shaped molecular structure [17,41]. 

Exploiting the properties of aqueous surfactant solutions in which the surfactants aggregate to form micelles consisting of apolar cores comprised of the hydrophobic tail groups stabilized by coronae formed by the hydrophilic surfactant heads (Fendler and Fendler, 1975 Bunton, 1991). The apolar core plays the role of the organic solvent, whereas the palisade layer can provide a medium of intermediate polarity. 

In MEKC, the supporting electrolyte medium contains a surfactant at a concentration above its critical micelle concentration (CMC). The surfactant self-aggregates in the aqueous medium and forms micelles whose hydrophilic head groups and hydrophobic tail groups form a nonpolar core into which the solutes can partition. The micelles are anionic on their surface, and they migrate in the opposite direction to the electroosmotic flow under the applied current. The differential partitioning of neutral molecules between the buffered aqueous mobile phase and the micellar pseudostationary phase is the sole basis for separation as the buffer and micelles form a two-phase system, and the analyte partitions between them (Smyth and McClean 1998). 

Chaiyasit, W., Silvestre, M.P.C., McClements, D.J., Decker, E.A. (2000). Ability of surfactant hydrophobic tail group size to alter lipid oxidation in oil-in-water emulsions. Journal of Agricultural and Food Chemistry, 48, 3077-3080. 

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