Organic solvents, nonionic surfactant micelles

Structure of Nonionic Surfactant Micelles in Organic Solvents A SAXS Study... 

Certain comb-type silicone surfactants have been shown to stabilize emulsions in the presence of salts, alcohol and organic solvents that normally cause failure of emulsions stabilized using conventional hydrocarbon surfactants and a study by Wang et al. [66,67] investigated the cause of this stability. Interaction forces due to silicone surfactants at an interface were measured using AFM. Steric repulsion provided by the SPE molecules persisted up to an 80% or higher ethanol level, much higher than for conventional hydrocarbon surfactants. Nonionic hydrocarbon surfactants lose their surface activity and ability to form micelles in... 

Common surfactants that have been used in MEKC, are listed in Table 3.1 with the respective critical micelle concentrations the most popular are SDS, bile salts, and hydrophobic chain quaternary ammonium salts. Selectivity can also be modulated by the addition to the aqueous buffer of organic solvents (methanol, isopropanol, acetonitrile, tetrahydrofuran, up to a concentration of 50%). These agents will reduce the hydrophobic interactions between analytes and micelles in a way similar to reversed-phase chromatography. Organic modifiers also reduce the cohesion of the hydrophobic core of the micelles, increasing the mass transfer kinetics and, consequently, efficiency. Nonionic... 

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. 

The impact of different surfactants (SDS, DOSS, CTAB and hexadimethrine bromide, bile salts °), nonionic and mixed micelles, and additives (neutral and anionic CDs," " tetraalkylammonium salts, organic solvents in EKC separations has been demonstrated with phenol test mixtures. In addition, phenols have been chosen to introduce the applicability of more exotic EKC secondary phases such as SDS modified by bovine serum albumin, water-soluble calixarene, " starburstdendrimers, " " cationic replaceable polymeric phases, ionenes, amphiphilic block copolymers,polyelectrolye complexes,and liposome-coated capillaries. The separation of phenols of environmental interest as well as the sources and transformations of chlorophenols in the natural environment have been revised. Examples of the investigation of phenols by EKC methodologies in aquatic systems, soil," " and gas phase are compiled in Table 31.3. Figure 31.3 illustrates the electromigration separation of phenols by both CZE and EKC modes. 

It is well known that a small amount of water induces micellization of the poly(oxyethylene)-type nonionic surfactants in nonpolar organic solvents. Even when surfactant aggregation does not occur, or the aggregation number is very small in a particular solvent in the absence of other materials, the addition of an insoluble solvent like water, may give rise to aggregation with consequent solubilization of the additives [83]. Addition of water is expected to decrease the spontaneous curvature as a result of increase in the headgroup repulsion. Besides, the added water solubilized in the interior of the micelle core in the nonpolar medium... 

Anionic surfactants are the most commonly used type in the emulsion polymerization. These include sulfates (sodium lauryl sulfate), sulfonates (sodium dodecylbenzene sulfonate), fatty acid soaps (sodium or potassium stearate, laurate, palmitate), and the Aerosol series (sodium dialkyl sulphosuccinates) such as Aerosol OT (AOT, sodium bis(2-ethylhexyl) sulfosuccinate) and Aerosol MA (AMA, sodium dihexyl sulphosuccinates). The sulfates and sulfonates are useful for polymerization in acidic medium where fatty acid soaps are unstable or where the final product must be stable toward either acid or heavy-metal ions. The AOT is usually dissolved in organic solvents to form the thermodynamically stable reverse micelles. [22] Nonionic surfactants usually include the Brij type, Span-Tween 80 (a commercial mixture of sorbitol monooleate and polysorbate 80), TritonX-100[polyoxyethylene(9)4-(l,l,3,3-tetramethylbutyl)-phenyl... 

The catalytic behavior and the stability of enzymes in reverse micelles are highly dependent on the composition and the structure of the micioanulsion. The activity of entrapped enzymes strongly depends on the water content, the nature of the organic solvent, as well as the nature and the concentration of surfactant. Various surfactants, including the anionic AOT, the cationic CTAB, nonionics such as Triton, Brij, ethoxylated fatty alcohols, and zwitterionic phospholipids (phosphatidylcholine), were used for the preparation of reverse miceUar systems-containing enzymes (Table 13.1). Most inveshgated systans used AOT as the surfactant because its phase behavior is well understood. The activity of some enzymes has been reported to depend on the surfactant concentration and in some cases it was attributed to the interaction of the enzymes with the miceUar membrane [8,26,27]. Recent developments in this area inclnde the use of modified surfactants or their mixtures with other additives and cosurfactants such as alcohols and sugars or the use of aprotic solvents for the reduction of the ionic interactions between the enzyme molecules and the micellar interface in order to improve the enzyme catalytic behavior and operational stabihty [8,17,28-34]. 

Microemulsions are thermodynamically stable systems. Oil-in-water (0/W) microemulsions are mixtures of monomer(s), water, surfactant, and, in some cases, cosurfactant. The cosurfactant is a surface-active compound that, in combination with the surfactant, reduces the interfacial tension between the monomer and the aqueous phase to very low values, ensuring the thermodynamic stability of the microemulsion. Alcohols are often used as cosurfactants. The low interfacial tension results in a frequent fluctuation in size and shape of the microemulsion droplets. In water-in-oil (W/0) microemulsions, a mixture of water-soluble monomers and water are dispersed in an organic solvent with the help of a surfactant. The use of a cosurfactant is not needed often because the monomers are surface active. The amount of surfactant required in microemulsion polymerization (>10wt%) is substantially higher than that used in emulsion polymerization. The droplet (swollen micelle) size of the both 0/W and W/0 microemulsions is in the range of 5-20 nm in diameter. Since these small droplets only weakly scatter light, the microemulsions are transparent. Bicontinuous microemulsions are sometimes formed using blends of nonionic surfactants [100]. Microemulsion polymerization has been reviewed [101]. 

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