Microemulsions cosurfactant

In that case the self diffusion coefficient - concentration curve shows a behaviour distinctly different from the cosurfactant microemulsions. has a quite low value throughout the extension of the isotropic solution phase up to the highest water content. This implies that a model with closed droplets surrounded by surfactant emions in a hydrocarbon medium gives an adequate description of these solutions, found to be significantly higher them D, the conclusion that a non-negligible eimount of water must exist between the emulsion droplets. 

Thevenin, M. A., Grossiord, J. L., and Poelman, M. C. (1996), Sucrose esters cosurfactant microemulsion systems for transdermal delivery—assessment of bicontinuous structures,/. I. Pharm., 137(2), 177-186. 

Microemulsions are thermodynamically stable, isotropically clear dispersions composed of a polar solvent, oil, a surfactant, and a cosurfactant. Microemulsions have much potential for drug delivery as very hydro-phobic molecules can be solubilized and formulated for oral administration. All of the commercial products are actually non-aqueous microemulsions, also known as microemulsion preconcentrates or SEDDS, as the polar solvent is not water. Upon contact with aqueous media such as gastrointestinal fluids, a SEDDS formulation spontaneously forms a fine dispersion or aqueous microemulsion. 

Gu6ring, P. and Lindman, B. (1985) Droplet and bicontinuous structures in cosurfactant microemulsions from multi-component self-diffusion measurements. Langmuir, 1,464-A68. 

MiCToemulsions are stable, transparent solutions of water, oil, and surfactant, either with or without a cosurfactant. Microemulsions have been described as consisting of spherical droplets of a disperse phase separated from a continuous phase by a film of surfactant [1-4] and they are highly dynamic structures. The components organize themselves in time and space by means of different interactions or colhsions, giving rise to coalescence and redispersion processes. Numerous studies have been carried out with the aim of determining the structure, dimensions, and internal dynamics of these systems. Among these studies we can... 

L.M.M. Nazario, J.P.S.G. Crespo, J.F. Holzwarth, and T.A. Hatton, Dynamics of AOT and AOT/nonionic cosurfactant microemulsions. An iodine-laser temperature jump study, 2000, Langmuir 16, 5892-5899. 

The previous stability discussion does not apply to microemulsions because they are thermodynamically stable isotropic solutions. Microemulsions differ from macroemulsions in that their oil-surfactant components can exist as cylindrical or bicontinuous strucmres in addition to spheroids (9). The stability and structure of nonionic microemulsions is governed by temperature. As the temperature is increased to the phase inversion temperature (PIT), the structure converts to bicontinuous and then it inverts as the PIT is exceeded. Similar effects can be accomplished for ionic microemulsions by adding electrolyte and certain cosurfactants. Microemulsions may also lose stability when diluted. 

Decyl glucoside cosurfactant, liq. soaps Hostapon SCI 78 C Rewopol SB FA 30 cosurfactant, microemulsions Labrafil M 1944 CS Labrafll M 2125 CS Lauraglycol 90 Lauroglycol FCC Plurol Isostearique Polyglyceryl-6 isostearate... 

Since the work of Stofifer and Bone in 1980, most work was done in four or five component (including cosurfactant) microemulsion. However, the presence of a fourth component, such as alcohol cosuifactant, substantially limits the utility of microemulsion, mainly for two reasons. First, the cosurfactant complicates the... 

A beautiful and elegant example of the intricacies of surface science is the formation of transparent, thermodynamically stable microemulsions. Discovered about 50 years ago by Winsor [76] and characterized by Schulman [77, 78], microemulsions display a variety of useful and interesting properties that have generated much interest in the past decade. Early formulations, still under study today, involve the use of a long-chain alcohol as a cosurfactant to stabilize oil droplets 10-50 nm in diameter. Although transparent to the naked eye, microemulsions are readily characterized by a variety of scattering, microscopic, and spectroscopic techniques, described below. 

Cationic surfactants may be used [94] and the effect of salinity and valence of electrolyte on charged systems has been investigated [95-98]. The phospholipid lecithin can also produce microemulsions when combined with an alcohol cosolvent [99]. Microemulsions formed with a double-tailed surfactant such as Aerosol OT (AOT) do not require a cosurfactant for stability (see, for instance. Refs. 100, 101). Morphological hysteresis has been observed in the inversion process and the formation of stable mixtures of microemulsion indicated [102]. 

The locations of the tietriangle and biaodal curves ia the phase diagram depead oa the molecular stmctures of the amphiphile and oil, on the concentration of cosurfactant and/or electrolyte if either of these components is added, and on the temperature (and, especially for compressible oils such as propane or carbon dioxide, on the pressure (29,30)). Unfortunately for the laboratory worker, only by measuriag (or correcdy estimatiag) the compositions of T, Af, and B can one be certain whether a certain pair of Hquid layers are a microemulsion and conjugate aqueous phase, a microemulsion and oleic phase, or simply a pair of aqueous and oleic phases. 

However, in the case of mini- and microemulsions, processing methods reduce the size of the monomer droplets close to the size of the micelle, leading to significant particle nucleation in the monomer droplets (17). Intense agitation, cosurfactant, and dilution are used to reduce monomer droplet size. Additives like cetyl alcohol are used to retard the diffusion of monomer from the droplets to the micelles, in order to further promote monomer droplet nucleation (18). The benefits of miniemulsions include faster reaction rates (19), improved shear stabiHty, and the control of particle size distributions to produce high soHds latices (20). 

A microemulsion (p.E) is a thermodynamically stable, transparent (in the visible) droplet type dispersion of water (W) and oil (O a saturated or unsaturated hydrocarbon) stabilized by a surfactant (S) and a cosurfactant (CoS a short amphiphile compound such as an alcohol or an amine) [67]. Sometimes the oil is a water-insoluble organic compound which is also a reactant and the water may contain mineral acids or salts. Because of the small dispersion size, a large amount of surfactant is required to stabilize microemulsions. The droplets are very small (about 100-1000 A [68]), about 100 times smaller than those of a typical emulsion. The existence of giant microemulsions (dispersion size about 6000 A) has been demonstrated [58]. 

The diastereoselection of the Diels Alder reaction of methyl acrylate with cyclopentadiene was investigated [74] in microemulsions prepared with isooctane oil, CTAB as surfactant and 1-butanol as cosurfactant, and the results were compared with those found in pure solvents and water (Table 6.12). In emulsions rich in 1-butanol and formamide (entries 1 and 4) the reaction was slow (72 h) and the diastereoselectivity was practically the same as that... 

MEEKC is a CE mode similar to MEKC, based on the partitioning of compounds between an aqueous and a microemulsion phase. The buffer solution consists of an aqueous solution containing nanometer-sized oil droplets as a pseudo-stationary phase. The most widely used microemulsion is made up of heptane as a water-immiscible solvent, SDS as a surfactant and 1-butanol as a cosurfactant. Surfactants and cosurfactants act as stabilizers at the surface of the droplet. 

Electrochemical redox studies of electroactive species solubilized in the water core of reverse microemulsions of water, toluene, cosurfactant, and AOT [28,29] have illustrated a percolation phenomenon in faradaic electron transfer. This phenomenon was observed when the cosurfactant used was acrylamide or other primary amide [28,30]. The oxidation or reduction chemistry appeared to switch on when cosurfactant chemical potential was raised above a certain threshold value. This switching phenomenon was later confirmed to coincide with percolation in electrical conductivity [31], as suggested by earlier work from the group of Francoise Candau [32]. The explanations for this amide-cosurfactant-induced percolation center around increases in interfacial flexibility [32] and increased disorder in surfactant chain packing [33]. These increases in flexibility and disorder appear to lead to increased interdroplet attraction, coalescence, and cluster formation. 

Another example of chemical-potential-driven percolation is in the recent report on the use of simple poly(oxyethylene)alkyl ethers, C, ), as cosurfactants in reverse water, alkane, and AOT microemulsions [27]. While studying temperature-driven percolation, Nazario et al. also examined the effects of added C, ) as cosurfactants, and found that these cosurfactants decreased the temperature threshold for percolation. Based on these collective observations one can conclude that linear alcohols as cosurfactants tend to stiffen the surfactant interface, and that amides and poly(oxyethylene) alkyl ethers as cosurfactants tend to make this interface more flexible and enhance clustering, leading to more facile percolation. 

As described in the introduction, certain cosurfactants appear able to drive percolation transitions. Variations in the cosurfactant chemical potential, RT n (where is cosurfactant concentration or activity), holding other compositional features constant, provide the driving force for these percolation transitions. A water, toluene, and AOT microemulsion system using acrylamide as cosurfactant exhibited percolation type behavior for a variety of redox electron-transfer processes. The corresponding low-frequency electrical conductivity data for such a system is illustrated in Fig. 8, where the water, toluene, and AOT mole ratio (11.2 19.2 1.00) is held approximately constant, and the acrylamide concentration, is varied from 0 to 6% (w/w). At about = 1.2%, the arrow labeled in Fig. 8 indicates the onset of percolation in electrical conductivity. 

FIG. 8 Low-frequency conductivity (a) of water, toluene, and AOT reverse microemulsions at 25°C as a function of acrylamide (cosurfactant) concentration, (wt%). The Op and arrow at f = 1.2% shows the approximate onset of percolation in low-frequency conductivity. 

FIG. 9 Measured self-diffusion coefficients at 25°C for toluene (A), water ( ), acrylamide ( , and AOT ( ) in water, toluene, and AOT reverse microemulsions as a function of cosurfactant (acrylamide) concentration, f (wt%). The breakpoint at about 1.2% acrylamide approximately denotes, the onset of percolation in electrical conductivity. 

These microdroplets can act as a reaction medium, as do micelles or vesicles. They affect indicator equilibria and can change overall rates of chemical reactions, and the cosurfactant may react nucleophilically with substrate in a microemulsion droplet. Mixtures of surfactants and cosurfactants, e.g. medium chain length alcohols or amines, are similar to o/w microemulsions in that they have ionic head groups and cosurfactant at their surface in contact with water. They are probably best described as swollen micelles, but it is convenient to consider their effects upon reaction rates as being similar to those of microemulsions (Athanassakis et al., 1982). 

A microemulsion droplet is a multicomponent system containing oil, surfactant, cosurfactant, and probably water therefore there may be considerable variation in size and shape depending upon the overall composition. The packing constraints which dictate size and shape of normal micelles (Section 1) should be relaxed in microemulsions because of the presence of cosurfactant and oil. However, it is possible to draw analogies between the behavior of micelles and microemulsion droplets, at least in the more aqueous media. 

Microemulsions can be generated using n-alkylamines as cosurfactant. These amines react with a substrate, e.g. 2,4-dinitrochlorobenzene, bound to the droplet, and the rate data can be analysed satisfactorily in terms of the concentration of amine in the droplet (Bunton and de Buzzaccarini, 1981b). 

An additional point is that relatively high concentrations of surfactant, oil and cosurfactant are often used in microemulsions. Thus the volume of the microemulsion pseudophase is large and droplet-bound reactants are therefore diluted. Generally speaking, rate enhancements increase in the sequence microemulsions < micelles < vesicles simply because of a decrease in the volume of the micellar or droplet pseudophase. 

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. 

Before describing how microemulsion nature and structure are determined by the structure and chain length of surfactant and cosurfactant, it is necessary first to briefly review the theories of microemulsion formation and stability. These theories will highlight the important factors required for microemulsion formation. This constitutes the first part of this review. The second part describes the factors that determine whether a w/o or o/w microemulsion is formed. This is then... 

Solubilisation can best be illustrated by considering the phase diagrams of non-ionic surfactants containing poly(oxyethylene oxide) head groups. Such surfactants do not generally need a cosurfactant for microemulsion formation. At low temperatures, the ethoxylated surfactant is soluble in water... 

This transition may j-.e. reducing the specific surface energy, f. The reduction of f to sufficiently small values was accounted for by Ruckenstein (15) in terms of the so called dilution effect". Accumulation of surfactant and cosurfactant at the interface not only causes significant reduction in the interfacial tension, but also results in reduction of the chemical potential of surfactant and cosurfactant in bulk solution. The latter reduction may exceed the positive free energy caused by the total interfacial tension and hence the overall Ag of the system may become negative. Further analysis by Ruckenstein and Krishnan (16) have showed that micelle formation encountered with water soluble surfactants reduces the dilution effect as a result of the association of the the surfactants molecules. However, if a cosurfactant is added, it can reduce the interfacial tension by further adsorption and introduces a dilution effect. The treatment of Ruckenstein and Krishnan (16) also highlighted the role of interfacial tension in the formation of microemulsions. When the contribution of surfactant and cosurfactant adsorption is taken into account, the entropy of the drops becomes negligible and the interfacial tension does not need to attain ultralow values before stable microemulsions form. 

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