Microemulsions application

Another area of microemulsion application is in the synthesis of certain polymers. The process is called emulsion polymerization, a misnomer since micelles rather than emulsion drops are the site of the polymerization reaction. Because of the commercial importance of polymers, this process has been extensively researched and is quite well understood. We only consider some highlights of the process. 

For the study of colloidal interactions, SANS gives higher signal to noise ratio and can be used to lower Q than SAXS. It has been widely used for the characterization of synthetic microemulsions. Application to food systems has been more limited, but one example is described below. A study of voids in food solids is noted. 

In this prospect of microemulsion applications we have chosen some crucial areas where microemulsions are in use. 

In snmmary, a general overview of microemulsion applications has been iUnstrated in petrolenm-processing technologies, where dynamic mass transfer phenomena across interfaces and enhanced solubility levels are requirements that are perfectly fulfilled by the physicochemical nature of these self-assembled systems. This is further corroborated by the possibility of microemulsions recycling. 

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... 

Shah D O (ed) 1985 Macro- and Microemulsions—Theory and Applications (Washington, DC American Chemical Society)... 

Dunn A S 1989 Polymerization in micelles and microemulsions Comprehensive Polymer Science—the Synthesis, Characterization, Reactions and Applications of Polymers vo 4, ed G C Eastmond, A Ledwith, S Russo and P Sigwalt (New York Pergamon) pp 219-24... 

D. O. Shah, Macro and Microemulsions Theory and Applications, American Chemical Society, Washington, D.C., 1985. 

C. Solans and H. Kunieda, eds.. Industrial Applications of Microemulsions, Marcel Dekker, New York, 1996. 

Industrial Applications of Microemulsions, edited by Conxita Solans and Hironobu Kunieda... 

Emulsifiers are used in many technical applications. Emulsions of the oil-in-water and the water-in-oil type are produced on a large scale in the cosmetic industry. Other fields of employment are polymerization of monomers in emulsions and emulsification of oily and aqueous solutions in lubricants and cutting oils. In enhanced oil recovery dispersing of crude oil to emulsions or even microemulsions is the decisive step. 

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). 

Different methods are used in microemulsion formation a low-energy emulsification method by dilution of an oil surfactant mixture with water and dilution of a water-surfactant mixture with oil and mixing all the components together in the final composition. These methods involve the spontaneous formation of microemulsions and the order of ingredient addition may determine the formation of the microemulsion. Such applications have been performed with lutein and lutein esters. ... 

Tenjarla, S., Microemulsions an overview and pharmaceutical applications, Crit. Rev. Then Drug, 16, 461, 1999. 

Garti, N., Aserin, A., and Fanun, M., Non-ionic sucrose esters microemulsions for food applications. Part 1. Water solubilization. Colloid Surface A, 164, 27, 2000. 

Garti, N., Microemulsions as microreactors for food applications, Curr. Opin. Colloid Int., 8, 197, 2003. 

Huie, C. W. Recent applications of microemulsion electrokinetic chromatography. Electrophoresis 2006, 27, 60-75. 

Applied Surface Thermodynamics, edited by A. 14/. Neumann and Jan K. Spelt Surfactants in Solution, edited by Arun K. Chattopadhyay and K. L. Mittal Detergents in the Environment, edited by Milan Johann Schwuger Industrial Applications of Microemulsions, edited by Conxita Solans and Hironobu Kunieda... 

Lagues et al. [17] found that the percolation theory for hard spheres could be used to describe dramatic increases in electrical conductivity in reverse microemulsions as the volume fraction of water was increased. They also showed how certain scaling theoretical tools were applicable to the analysis of such percolation phenomena. Cazabat et al. [18] also examined percolation in reverse microemulsions with increasing disperse phase volume fraction. They reasoned the percolation came about as a result of formation of clusters of reverse microemulsion droplets. They envisioned increased transport as arising from a transformation of linear droplet clusters to tubular microstructures, to form wormlike reverse microemulsion tubules. 

The ITIES with an adsorbed monolayer of surfactant has been studied as a model system of the interface between microphases in a bicontinuous microemulsion [39]. This latter system has important applications in electrochemical synthesis and catalysis [88-92]. Quantitative measurements of the kinetics of electrochemical processes in microemulsions are difficult to perform directly, due to uncertainties in the area over which the organic and aqueous reactants contact. The SECM feedback mode allowed the rate of catalytic reduction of tra 5-l,2-dibromocyclohexane in benzonitrile by the Co(I) form of vitamin B12, generated electrochemically in an aqueous phase to be measured as a function of interfacial potential drop and adsorbed surfactants [39]. It was found that the reaction at the ITIES could not be interpreted as a simple second-order process. In the absence of surfactant at the ITIES the overall rate of the interfacial reaction was virtually independent of the potential drop across the interface and a similar rate constant was obtained when a cationic surfactant (didodecyldimethylammonium bromide) was adsorbed at the ITIES. In contrast a threefold decrease in the rate constant was observed when an anionic surfactant (dihexadecyl phosphate) was used. 

Depicted in Fig. 2, microemulsion-based liquid liquid extraction (LLE) of biomolecules consists of the contacting of a biomolecule-containing aqueous solution with a surfactant-containing lipophilic phase. Upon contact, some of the water and biomolecules will transfer to the organic phase, depending on the phase equilibrium position, resulting in a biphasic Winsor II system (w/o-ME phase in equilibrium with an excess aqueous phase). Besides serving as a means to solubilize biomolecules in w/o-MEs, LLE has been frequently used to isolate and separate amino acids, peptides and proteins [4, and references therein]. In addition, LLE has recently been employed to isolate vitamins, antibiotics, and nucleotides [6,19,40,77-79]. Industrially relevant applications of LLE are listed in Table 2 [14,15,20,80-90]. 

The homocoupling of aryl halide to diaryl compounds, known as Ull-mann coupling, is a synthetically useful reaction and has wide applications in material research. Such couplings have been studied in aqueous conditions. In 1970, arylsulfinic acids were coupled with Pd(II) in aqueous solvents to biaryls (Eq. 6.25).53 However, the reaction required the use of a stoichiometric amount of palladium. In the presence of hydrogen gas, aryl halides homocoupled to give biaryl compounds in moderate yields (30-50%) in an aqueous/organic microemulsion (Eq. 6.26).54... 

In 1959, J. H. Schulman introduced the term microemulsion for transparent-solutions of a model four-component system [126]. Basically, microemulsions consist of water, an oily component, surfactant, and co-surfactant. A three phase diagram illustrating the area of existence of microemulsions is presented in Fig. 6 [24]. The phase equilibria, structures, applications, and chemical reactions of microemulsion have been reviewed by Sjoblom et al. [127]. In contrast to macroemulsions, microemulsions are optically transparent, isotropic, and thermodynamically stable [128, 129]. Microemulsions have been subject of various... 

J Sjoblom, R Lindberg, SE Friberg. Microemulsions-phase equilibria characterization, structures, applications and chemical reactions, Adv Colloid Interf Sci 65 125-287, 1996. 

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