Limiting microemulsions

In three-phase systems the top phase, T, is an oleic phase, the middle phase, Af, is a microemulsion, and the bottom phase, B, is an aqueous phase. Microemulsions that occur ia equiUbrium with oae or two other phases are sometimes called "limiting microemulsions," because they occur at the limits of the siagle-phase regioa. 

Limiting drawability ratio, 7 735 Limiting equivalence ratio, 13 855, 856 Limiting microemulsions, 16 423 Limiting oxygen concentration (LOC), 21 840... 

Other solubilization and partitioning phenomena are important, both within the context of microemulsions and in the absence of added immiscible solvent. In regular micellar solutions, micelles promote the solubility of many compounds otherwise insoluble in water. The amount of chemical component solubilized in a micellar solution will, typically, be much smaller than can be accommodated in microemulsion fonnation, such as when only a few molecules per micelle are solubilized. Such limited solubilization is nevertheless quite useful. The incoriDoration of minor quantities of pyrene and related optical probes into micelles are a key to the use of fluorescence depolarization in quantifying micellar aggregation numbers and micellar microviscosities [48]. Micellar solubilization makes it possible to measure acid-base or electrochemical properties of compounds otherwise insoluble in aqueous solution. Micellar solubilization facilitates micellar catalysis (see section C2.3.10) and emulsion polymerization (see section C2.3.12). On the other hand, there are untoward effects of micellar solubilization in practical applications of surfactants. Wlren one has a multiphase... 

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... 

The application of microemulsions in foods is limited by the types of surfactants used to facilitate microemulsion formation. Many surfactants are not permitted in foods or only at low levels. The solubilization of long-chain triglycerides (LCTs) such as edible oils is more difficult to achieve than the solubilization of short- or medium-chain triglycerides, a reason why few publications on microemulsions are available, especially because food-grade additives are not allowed to contain short-chain alcohols (C3-C5). 

High pressure homogenization may also be used to form microemulsions but the process of emulsification is generally inefficient (due to the dissipation of heat) and extremely limited as the water-oil-surfactant mixture may be highly viscous prior to microemulsion formation. ... 

The majority of RDC studies have concentrated on the measurement of solute transfer resistances, in particular, focusing on their relevance as model systems for drug transfer across skin [14,39-41]. In these studies, isopropyl myristate is commonly used as a solvent, since it is considered to serve as a model compound for skin lipids. However, it has since been reported that the true interfacial kinetics cannot be resolved with the RDC due to the severe mass transport limitations inherent in the technique [15]. The RDC has also been used to study more complicated interfacial processes such as kinetics in a microemulsion system [42], where one of the compartments contains an emulsion. 

The draft-tube airlift bioreactor was studied using water-in-kerosene microemulsions [263], The effect of draft tube area vs. the top-section area on various parameters was studied. The effect of gas flow rates on recirculation and gas carry over due to incomplete gas disengagement were studied [264], Additionally, the effect of riser to downcomer volume was also studied. The effect of W/O ratio and viscosity was tested on gas hold-up and mass transfer coefficient [265], One limitation of these studies was the use of plain water as the aqueous phase in the cold model. The absence of biocatalyst or any fermentation broth from the experiments makes these results of little value. The effect of the parameters studied will greatly depend on the change in viscosity, hold-up, phase distribution caused due to the presence of biocatalyst, such as IGTS8, due to production of biosurfactants, etc., by the biocatalyst. Thus, further work including biocatalyst is necessary to truly assess the utility of the draft-tube airlift bioreactor for biodesulfurization. 

A number of matrices have also been used for the preparation of semiconductor nanoparticles, whereby the particulate material is grown within and subsequently fills the cavities of the host material. These includes zeolites,361 glasses,362 and molecular sieves,363-365 and can be viewed as nanochambers which limit the size to which crystallites can grow. Other synthetic methods include micelles/microemulsions,366-369 sol-gels,370,371 polymers,372-377 and layered solids.378... 

Because the presence of an electrolyte increases the dimensions of micelles and microemulsion droplets [115], it may be expected that in presence of ions the size of microgels is also increased. This expectation could be confirmed external electrolyte increases Mw (Fig. 21) as well as dz and [r ] (Fig. 22) up to the limit of the emulsion stability. Therefore, the addition of an external electrolyte to the reaction mixture for the ECP of EUP and comonomers is a means to vary the molar mass, the diameter and the intrinsic viscosity of microgels from EUP and comonomers deliberately. 

Large amounts of water and oil can be admixed in microemulsions which find wide application in household and pharmaceutical products and have potential for enhanced oil recovery (Mackay, 1981 Bellocq et al., 1984). Microemulsions have been reported to form in the absence of surfactant over a very limited range of concentration, but there is a question as to the nature of these dispersions (Barden and Holt, 1979). 

The reverse microemulsion method can be used to manipulate the size of silica nanoparticles [25]. It was found that the concentration of alkoxide (TEOS) slightly affects the size of silica nanoparticles. The majority of excess TEOS remained unhydrolyzed, and did not participate in the polycondensation. The amount of basic catalyst, ammonia, is an important factor for controlling the size of nanoparticles. When the concentration of ammonium hydroxide increased from 0.5 (wt%) to 2.0%, the size of silica nanoparticles decreased from 82 to 50 nm. Most importantly, in a reverse microemulsion, the formation of silica nanoparticles is limited by the size of micelles. The sizes of micelles are related to the water to surfactant molar ratio. Therefore, this ratio plays an important role for manipulation of the size of nanoparticles. In a Triton X-100/n-hexanol/cyclohexane/water microemulsion, the sizes of obtained silica nanoparticles increased from 69 to 178 nm, as the water to Triton X-100 molar ratio decreased from 15 to 5. The cosurfactant, n-hexanol, slightly influences the curvature of the radius of the water droplets in the micelles, and the molar ratio of the cosurfactant to surfactant faintly affects the size of nanoparticles as well. 

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 procedure chosen for the preparation of lipid complexes of AmB was nanoprecipitation. This procedure has been developed in our laboratory for a number of years and can be applied to the formulation of a number of different colloidal systems liposomes, microemulsions, polymeric nanoparticles (nanospheres and nanocapsules), complexes, and pure drug particles (14-16). Briefly, the substances of interest are dissolved in a solvent A and this solution is poured into a nonsolvent B of the substance that is miscible with the solvent A. As the solvent diffuses, the dissolved material is stranded as small particles, typically 100 to 400 nm in diameter. The solvent is usually an alcohol, acetone, or tetrahydrofuran and the nonsolvent A is usually water or aqueous buffer, with or without a hydrophilic surfactant to improve colloid stability after formation. Solvent A can be removed by evaporation under vacuum, which can also be used to concentrate the suspension. The concentration of the substance of interest in the organic solvent and the proportions of the two solvents are the main parameters influencing the final size of the particles. For liposomes, this method is similar to the ethanol injection technique proposed by Batzii and Korn in 1973 (17), which is however limited to 40 mM of lipids in ethanol and 10% of ethanol in final aqueous suspension. 

Demarconnay et al. used a method derived from that of the so-called water-in-oil microemulsion method to prepare well dispersed Ag/C catalysts [116]. The onset of the oxygen reduction wave is only shifted by 50 mV towards lower potentials on an Ag/C catalyst compared with that obtained on a Pt/C catalyst and the limiting current... 

---