Mixed Anionic-Nonionic Micelles

Mixed Anionic-Nonionic Micelles An investigation of the solubilization of Yellow OB by mixed micelles of anionics and a POE nonionic, Q 2 5(002114)9-OH, indicated that increased solubilization of the dye occurs when there is interaction between the POE chain and the benzenesulfonate groups, 

1973a). The degree of interaction of the aromatic nucleus with the POE chain decreased with separation of the ring from the sulfonate groups, giving the following order of interaction  

Only the first compound increased the extent of solubilization of Yellow OB by the nonionic. The addition of C10H21SO3 Na1 to the nonionic decreased its solubilization of Yellow OB. 

rather than the phenyl or sulfonate groups alone (Tokiwa, 

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Small micelles in dilute solution close to the CMC are generally beheved to be spherical. Under other conditions, micellar materials can assume stmctures such as oblate and prolate spheroids, vesicles (double layers), rods, and lamellae (36,37). AH of these stmctures have been demonstrated under certain conditions, and a single surfactant can assume a number of stmctures, depending on surfactant, salt concentration, and temperature. In mixed surfactant solutions, micelles of each species may coexist, but usually mixed micelles are formed. Anionic-nonionic mixtures are of technical importance and their properties have been studied (38,39). 

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]. 

The critical micellar concentrations of anionic/nonionic surfactant mixtures examined are low in a saline medium, so that, at the concentrations injected in practice, the chromatographic effects resulting from the respective adsorption of monomers are masked. Such surfactants propagate simultaneously in the medium in the form of mixed micelles. 

If the mixed micelle model already presented is used to predict the ionic surfactant monomer concentration, and a simple concentration—based solubility product is assumed to hold between the unbound counterion and monomer, the salinity tolerance of an anionic/nonionic surfactant mixture can be accurately predicted (91). supporting this view of the mechanism of tolerance enhancement by nonionic surfactant. 

Marszall (1988) studied the effect of electrolytes on the cloud point of mixed ionic-nonionic surfactant solutions such as SDS and Triton X-100. It was found that the cloud point of the mixed micellar solutions is drastically lowered by a variety of electrolytes at considerably lower concentrations than those affecting the cloud point of nonionic surfactants used alone. The results indicate that the factors affecting the cloud point phenomena of mixed surfactants at very low concentrations of ionic surfactants and electrolytes are primarily electrostatic in nature. The change in the original charge distribution of mixed micelles at a Lxed SDS-Triton X-100 ratio (one molecule per micelle), as indicated by the cloud point measurements as a function of electrolyte concentration, depends mostly on the valency number of the cations (counterions) and to some extent on the kind of the anion (co-ion) and is independent of the type of monovalent cation. 

A recent study on electrokinetic removal of ethyl benzene from contaminated clay showed a promising use of anionic-nonionic mixed surfactants. Surfactant addition resulted in 1.6-2.4-fold more removal than afforded by EK alone, and a mixed surfactant system, including 0.5% SDS and 2.0% PANNOX 110 (nonyl phenol polyethylene glycol ether) permitted optimal ethyl benzene removal (98%). This indicated that, in the presence of mixed surfactant micelles, the zeta potential of the soil particles significantly increased compared with that seen when anionic surfactant micelles were formed, and electrolytic mobility was thus enhanced (Yuan and Weng, 2004). The use of anionic-nonionic mixed surfactants in EK will also improve the desorption and migration of PAHs. 

Dubin et al. studied the formation of polyelectrolyte-micelle complexes between poly(dimethyldiallylammonium chloride) and anionic/nonionic mixed micelles by static and dynamic light scattering [21-23]. Dynamic light scattering yields the hydrodynamic radius of the particles investigated (very useful information), especially in combination with SLS, allowing an assessment of the particle architecture. 

Research on the micelle structure and interactions of fluorinated surfactants is ongoing with the main focus on mixed-surfactant systems. Mixtures of fluorinated and nonfluorinated surfactants may consist of anionic, nonionic, or cationic components. Most of the systems investigated so far have contained a fluorinated anionic surfactant and an anionic hydrocarbon surfactant. Anionic fluorinated surfactant mixtures with nonionic or cationic hydrocarbon-type surfactants have been investigated as well. The nonionic fluorinated hydrocarbon surfactant mixtures and cationic fluorinated hydrocarbon surfactant mixtures have been the subject of only a few studies. 

The values of rate constants for oxidation of rosaniline hydrochloride in mixed micellar solutions (CTABr + Tween-20, CTABr + Tween-80) are less than those in pure CTABr solution but are higher than those in pure nonionic surfactant solutions, whereas the values of rate constants in mixed micellar solutions (SDS + Triton X-100, SDS + Triton X-102) are less than those in pure anionic as well as in nonionic surfactants. The effects of mixed micelles of cationic-cationic, cationic-nonionic, and anionic-nonionic surfactants on the rate of alkaline hydrolysis of A-phenylbenzohydroxamic acid have been studied at 55°C where the addition of cationic surfactant to nonionic surfactant accelerates the rate of hydrolysis, and the kinetic data have been analyzed by the Monger s enzyme-kinetic-type model. ... 

The target HLB can be obtained by using a mixture of anionic surfactant (HLB = 9.4) and nonionic surfactant HLB = 16.7) in the right proportions (1 3.75 based on the formula in Table 3). Such mixing of anionic and nonionic surfactants is expected to lower the individual CMC s and thus an increase of the soil solubilization capacity. The surfactants in the product should be in spherical micelle phase to give a transparent/translucent appearance and small viscosity (Table 6). 

Zhang et al. [135] have studied the physicochemical behavior of mixtures of -dodecyl-/l-D-maltoside with anionic, cationic and nonionic surfactants in aqueous solutions. To acquire information on the property of mixed micelles, the characteristic change of pyrene with changes in polarity was monitored. The polarity parameter at low concentrations was found to be 0.5-0.6. 

Mixed Micelles Showing Negative Deviation -from Ideality. In an aqueous solution containing a mixture o-f Cll an ionic sur-factant and a nonionic sur-factant, or C21 an anionic sur-factant and a cationic sur-factant, or C33 a zwitterionic sur-factant and an anionic sur-factant, the CMC o-f the mixed sur-factant system exhibits a CMC which is substantially less than that predicted by Equation 1 (9.12.18-37). This means that the mixed micelle -formation is enhanced and that the mixing process in the micelle shows negative deviation -from ideality. This is demonstrated -for a cationic/nonionic system in Figure 1. 

Below the CMC, the surfactant mixing in monolayers composed of similarly structured surfactants approximately obeys ideal solution theory. This means that the total surfactant concentration required to attain a specified surface tension for a mixture is intermediate between those concentrations for the pure surfactants involved. For mixtures of ionic/nonionic or anionic/cationic surfactants, below the CMC, the surfactant mixing in the monolayer exhibits negative deviation from ideality (i.e., the surfactant concentration required to attain a specified surface tension is less than that predicted from ideal solution theory). The same guidelines already discussed to select surfactant mixtures which have low monomer concentrations when micelles are present would also apply to the selection of surfactants which would reduce surface tension below the CMC. 

The variation of the mixture critical micelle concentration (CMCf ) with temperature and with overall surfactant composition has been studied using ultrafiltration for two binary mixed nonionic/anionic systems. 

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