Cationic surfactants micellar solutions

Since N will be larger than S+, all anionic surfactants are negatively charged. Similarly, cationic micelles will be positively charged. For instance, the cationic surfactant cetyltrimethyl ammonium bromide (CTAB), we have following equilibrium in micellar solutions ... 

Literature on reactions involving micellar counterions is particularly rich and for good reasons. The local concentration of counterions in the micellar Stern region is extremely high compared to typical aqueous solutions. As a result, bimolecular reactions involving bases such as hydroxide and acetate or oxidants such as perchlorate can be accelerated significantly by using these as a counterion for cationic surfactants. Discussion here will be restricted to a selected number of relatively recent examples of particular interest. This should not, however, distract from the merit of many of the other publications in this field. 

It is noteworthy that the indenyl complex RuCl(ri -C9H7)(PPh3)2l4 provides an efficient catalyst precursor for the anti-Markovnikov hydration of terminal alkynes in aqueous media, especially in micellar solutions with either anionic (sodium dode-cylsulfate (SDS)) or cationic (hexadecyltrimethylammonium bromide (CTAB)) surfactants [38]. This system can be applied to the hydration of propargylic alcohols to selectively produce P-hydroxyaldehydes, whereas RuCl(Cp)(PMe3)2 gives a,P-unsat-urated aldehydes (the Meyer Schuster rearrangement products)(Scheme 10.8) [39]. 

The effect of various surfactants, the cationics-eetyl trimethyl ammonium bromide (CTAB), and cetyl pyridinium chloride (CPC), the anionic-sodium lauryl sulfate (SLS), and the nonionic-polysorbate 80 (Tween 80), on the solubility and ionization constants of some sparingly soluble weak acids of pharmaceutical interest was studied (Gerakis et al., 1993). Benzoic acid (and its 3-methyl-, 3-nitro-, and 4-tert-butyl-derivatives), acetylsalicylic acid, naproxen, and iopanoic acid were chosen as model drugs. The cationics, CTAB and CPC, were found to considerably increase th< ionization constant of the weak acidS Ka ranged from-0.21 to-3.57), while the anionic, SLS, showed a negligible effect and the nonionic, Tween 80, generally decreased the ionization constants Solubility of the acids increased in aqueous micellar and in acidiLed micellar solutions. 

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. 

Clearly, the infrared spectra of the sodium and potassium decanoate micellar solutions are considerably different, as are their pressure dependencies. Since the only difference between these two micellar systems is the size, and thus the charge density of the counterions, the different infrared spectra must be taken as evidence that in the alkali decanoate micelles the sodium or potassium counter cations interact differently with the carboxylate groups of the surfactant molecules. 

It seems likely that the cationic CPC micelles, which have a large positive charge at or near the micellar surface, interact attractively with the n-molecular orbital system of benzene, and that this interaction contributes to the fact that the solubilization constant for benzene in CPC is approximately twice as large as that in SDS micelles. A preferential interaction between cationic surfactants and aromatic solutes has been reported by several groups of investigators (25-27), and recent work in our laboratory shows that 1-hexadecyltrimethylammonium bromide micelles also solubilize benzene more effectively than do the anionic alkylsulfate surfactant micelles (28). Thus, the tendency of benzene molecules to solubilize near the surface of the cationic micelles, at low XB values, may lead to a partial saturation of surface "sites" by benzene, diminishing the ability of additional benzene molecules to bind near the surface. Such an effect could be responsible for the initial increase in activity coefficient that occurs, particularly in the CPC solutions, as Xg increases. 

The functionalization of the reverse micelles will create a novel application in bioseparation processes in the analytical and medical sciences. It is therefore important to reveal the recognition mechanism of proteins at the liquid-liquid interface in reversed micellar solutions. DNA is also successfully extracted in a few hours by reversed micelles formed by cationic surfactants in isooctane. The driving force of the DNA transfer is the electrostatic interaction between the cationic surfactants and the negatively charged DNA. Another important factor is the hydrophobicity of the cationic surfactants. Doublechain type cationic surfactants are found to be one of the best surfactants ensuring the efficient extraction of DNA. These results have shown that reverse micellar solutions will become a useful tool not only for protein separation, but also for DNA separation. 

H -tetramethylbenzidine in anionic-cationic mixed micelles has been studied in detail by ESR . The photochemistry of the semi-oxidised forms of eosin Y and rose bengal have been investigated in colloidal solutions. Relevant to the fluorescence of proteins is a study of fluorescence quenching of indolic compounds by amino-acids in SOS, CTAB, and CTAC micelles O Rate constants for proton transfer of several hydroxyaromatic compounds have been measured in a variety of surfactant solutions. Photoprotolytic dissociation does not require exit of the reactant molecules from the micelles. Micellar solutions can be used to improve the fluorescence determination of 2-naphthol by inhibiting proton transfer or proton inducing reactions z2. jpe decay of the radical pair composed of diphenylphosphonyl and 2,4,6-trimethyl benzoyl radicals in SDS is affected by magnetic... 

In accordance with the observation that the anti-microbial effect of gases like nitrogen dioxide, carbon dioxide or xenon can be related to the effects of general anaesthetics, it seems natural to relate the well-knovm anti-microbial effect of cationic surfactants to local anaesthetic agents. The first type of perturbants shifts the actual transition in the direction La - whereas the second t)rpe of agent is expected to shift the transition in the opposite direction. It should be mentioned that quaternary ammonium surfactants such as cetyltrimethyl ammonium bromide in micellar solution in water were found to transform the cubic phase into the La phase [34]. 

Micelles and cyclodextrins are the most common reagents used for this technique. Micellar electrokinetic capillary chromatography (MECC or MEKC) is generally used for the separation of small molecules [6], Sodium dodecyl sulfate at concentrations from 20 to 150 mM in conjunction with 20 mM borate buffer (pH 9.3) or phosphate buffer (pH 7.0) represent the most common operating conditions. The mechanism of separation is related to reversed-phase liquid chromatography, at least for neutral solutes. Organic solvents such as 5-20% methanol or acetonitrile are useful to modify selectivity when there is too much retention in the system. Alternative surfactants such as bile salts (sodium cholate), cationic surfactants (cetyltrimethy-lammonium bromide), nonionic surfactants (poly-oxyethylene-23-lauryl ether), and alkyl glucosides can be used as well. 

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