Hydrophobizing microemulsions

Nagy,A., Kennedy,J.R.,Wang, R,Wesdemiotis, C., Hanton, S.D. (2006) Extent of coverage of surfaces treated with hydrophobizing microemulsions a mass spectrometry and contact angle study. App/. Surf. Sci.,252,3751-3759. 

It is of particular interest to be able to correlate solubility and partitioning with the molecular stmcture of the surfactant and solute. Likes dissolve like is a well-wom plirase that appears applicable, as we see in microemulsion fonnation where reverse micelles solubilize water and nonnal micelles solubilize hydrocarbons. Surfactant interactions, geometrical factors and solute loading produce limitations, however. There appear to be no universal models for solubilization that are readily available and that rest on molecular stmcture. Correlations of homologous solutes in various micellar solutions have been reviewed by Nagarajan [52]. Some examples of solubilization, such as for polycyclic aromatics in dodecyl sulphonate micelles, are driven by hydrophobic... 

A (macro)emulsion is formed when two immiscible Hquids, usually water and a hydrophobic organic solvent, an oil, are mechanically agitated (5) so that one Hquid forms droplets in the other one. A microemulsion, on the other hand, forms spontaneously because of the self-association of added amphiphilic molecules. During the emulsification agitation both Hquids form droplets, and with no stabilization, two emulsion layers are formed, one with oil droplets in water (o /w) and one of water in oil (w/o). However, if not stabilized the droplets separate into two phases when the agitation ceases. If an emulsifier (a stabilizing compound) is added to the two immiscible Hquids, one of them becomes continuous and the other one remains in droplet form. 

Solubilization of a graft copolymer comprising a hydrophobic poly(dodecyl-methacrylate) backbone and hydrophilic poly(ethylene glycol) monomethyl ether side chains in water/AOT/cyclohexane w/o microemulsions was rationalized in terms of the backbone dissolved in the continuous apolar phase and the side chains entrapped within the aqueous micellar cores [189],... 

Since some structural and dynamic features of w/o microemulsions are similar to those of cellular membranes, such as dominance of interfacial effects and coexistence of spatially separated hydrophilic and hydrophobic nanoscopic domains, the formation of nanoparticles of some inorganic salts in microemulsions could be a very simple and realistic way to model or to mimic some aspects of biomineralization processes [216,217]. 

Hilder, E.F. et al.. Separation of hydrophobic polymer additives by microemulsion electrokinetic chromatography, J. Chromatogr A, 922, 293, 2001. 

The rates of multiphase reactions are often controlled by mass tran.sfer across the interface. An enlargement of the interfacial surface area can then speed up reactions and also affect selectivity. Formation of micelles (these are aggregates of surfactants, typically 400-800 nm in size, which can solubilize large quantities of hydrophobic substance) can lead to an enormous increase of the interfacial area, even at low concentrations. A qualitatively similar effect can be reached if microemulsions or hydrotropes are created. Microemulsions are colloidal dispersions that consist of monodisperse droplets of water-in-oil or oil-in-water, which are thermodynamically stable. Typically, droplets are 10 to 100 pm in diameter. Hydrotropes are substances like toluene/xylene/cumene sulphonic acids or their Na/K salts, glycol.s, urea, etc. These. substances are highly soluble in water and enormously increase the solubility of sparingly. soluble solutes. 

Ishihama, Y., Oda, Y., Uchikawa, K., Asakawa, N. Evaluation of solute hydrophobicity by microemulsion electrokinetic chromatography. Anal. Chem. 1995, 67, 1588-1595. 

Hydrophobic solubilizates such as styrene (S) decrease the saponification rate of the EUP. Accordingly, the EUP-molecules in micelles containing S are more resistant against hydrolytic degradation than molecularly dissolved EUP-mole-cules. Obviously, the access of the base to the hydrophobic interior of these micelles and microemulsion droplets is more difficult. 

Studies of chemical reactivity in self-assembling colloids were initially based on reactions in aqueous micelles, but recently reactivity has been examined in other colloidal systems such as microemulsions and synthetic vesicles (Mackay, 1981 Fendler, 1982 O Connor et al., 1982, 1984 Cuccovia et al. 1982b). Some hydrophobic trialkylammonium salts, which are phase-... 

The fractional ionization, a, of ionic micelles is increased by hydrophobic non-ionic solutes which decrease the charge density at the micellar surface and the binding of counterions (Larsen and Tepley, 1974 Zana, 1980 Bunton and de Buzzaccarini, 1982). Consistently, microemulsion droplets are less effective at binding counterions than otherwise similar micelles. 

R. Abu-Reziq, J. Blum and D. Avnir, Three-Phase Microemulsion/ Sol-Gel System for Aqueous Catalysis with Hydrophobic Chemicals, Chem. Eur. J., 2004, 10, 958. 

In a reverse microemulsion, the hydrolysis and polymerization of the silicate precursor occur in the water droplet, therefore, to dope dyes in the silica nanoparticles they must be water soluble. However, a number of organic dye molecules are hydrophobic, requiring modifications prior to doping. Several methods are available to link a hydrophobic dye molecule to a water soluble group. A simple and effective example is to link a hydrophilic dextran to the dye molecules [8]. This modification can greatly enhance the water solubility of hydrophobic dye molecules, but will increase the cost of resultant DDSNs. 

Usually, activities of enzymes (hydrogenases included) are investigated in solutions with water as the solvent. However, enhancement of enzyme activity is sometimes described for non-aqueous or water-limiting surroundings, particular for hydrophobic (or oily) substrates. Ternary phase systems such as water-in-oil microemulsions are useful tools for investigations in this field. Microemulsions are prepared by dispersion of small amounts of water and surfactant in organic solvents. In these systems, small droplets of water (l-50nm in diameter) are surrounded by a monolayer of surfactant molecules (Fig. 9.15). The water pool inside the so-called reverse micelle represents a combination of properties of aqueous and non-aqueous environments. Enzymes entrapped inside reverse micelles depend in their catalytic activity on the size of the micelle, i.e. the water content of the system (at constant surfactant concentrations). 

The rate of metal complex formation is often modified (usually enhanced) by the presence of a charged interface in the aqueous phase. This may be provided by ionic micelles, e. g., SDS, microemulsions or polyelectrolytes. jjjg reactions of Ni + and Co with hydrophobic ligands pan, pap and pad 14-16 are popular ones for examining effects, since they are well characterized in the bulk water. The simple model (4.126)... 

On the other hand, with microemulsions based on an anionic surfactant and a long chain alcohol, was fairly low for certain concentrations, indicating that distinct water droplets in a hydrophobic medium may form. The system investigated by Lindman et al (29-34) was based on octanoic acid - decanol -octane-water. This means that the anionic "surfactant" used contains only seven carbon atoms in the alkyl chain which is fairly short. With longer chain surfactants, one would expect well defined "water cores" provided the alcohol is also long-chain. Such well defined "water cores" have also been confirmed by Lindman et a (34) for the Aerosol OT - hydrocarbon system. 

Thus, in summary, self diffusion measurements by Lindman et a (29-34) have clearly indicated that the structure of microemulsions depends to a large extent on the chain length of the oosurfactant (alcohol), the surfactant and the type of system. With short chain alcohols (hydrophilic domains and the structure is best described by a bicontinuous solution with easily deformable and flexible interfaces. This picture is consistent with the percolative behaviour observed when the conductivity is measured as a function of water volume fraction (see above). With long chain alcohols (> Cg) on the other hand, well defined "cores" may be distinguished with a more pronounced separation into hydrophobic and hydrophilic regions. 

It is important to consider the different stages when producing microemulsions from macroemulsions. It was mentioned earlier that surfactant molecules orient with the hydrophobic group inside the oil phase, while the polar group orients toward the water phase. The orientation of surfactants at the interfaces cannot be measured by any direct method, although much useful information can be obtained from mono-layer studies of the air-water or oil-water interfaces. 

Y Ishihama, Y Oda, N Asakawa. A hydrophobicity scale based on the migration index from microemulsion electrokinetic chromatography of anionic solutes. Anal. Chem. 68 1028-1032 (1996). 

To obtain a true k in MEEKC, it is important to trace the migration of the pseudostationary phase accurately. Sudan III, timepidium bromide, and quine, which have generally been used as tracers for micelles in MEKC, could not be employed as tracers for microemulsions consisting of sodium dodecylsulfate salt (SDS) or cetyltrimethylammonium bromide (CTAB), n-butanol and heptane (12). An iteration method based on a linear relationship between log k and the carbon number for alkylbenzenes (13) seems to provide a reasonable value of the migration time of the microemulsions. Dodecylbenzene shows a migration time larger than the value calculated by the iteration method and those of other hydrophobic compounds, such as phenanthrene, fluoranthrene, and Sudan III (Table 1). Methanol and ethanol were used as tracers for the aqueous phase. 

The plots of log k vs. log P w and the plots of log k (v) vs. log k (z) were studied for seven cephalosporins. A linear relationship was obtained in micellar solution and in microemulsion solution (Tables 3 and 4). The results obtained indicate that the capacity factor determined by EKC could be used both as parameter to characterize the partition behavior of drugs in ME and MC and as hydrophobic parameter instead of log Pow. k appears to be an evident parameter, and it shows a better diversification than P w. In the 1-octanol/water system, we did not found high values of the partition coefficients. In contrast, the ME systems used provide a better characterization of the drugs according to their hydrophilic/lipophilic properties. 

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