Water solubilization in reverse micelles

FACTORS AFFECTING WATER SOLUBILIZATION IN REVERSE MICELLES... 

In Section 3.3 we have briefly indicated that there are various factors that can affect water solubilization in reverse micelles. The importance of the oil-water interface in the context of water solubilization cannot just be overemphasized, and the entity that first comes to the forefront is the surfactant film that separates the two immiscible phases. At the very beginning, therefore, some basic and relevant points on the surfactant film are described below in brief [113, 114, 124, 125, 3]. The interfacial surfactant film can be described as a two-dimensional system in which one can consider a pressure term n [113] this term, characteristic of the film, defines the difference in the oil/water interfacial tension before and after addition of the surfactant to form an interfacial film ... 

Figure 10.19. Solid surface drying by water solubilization in reversed micelles (a) wet metal surface (b) drying surfactant micelles begin to absorb water (c) dry surface and solubilized waters.

The aqueous cores of reverse micelles are of particular interest because of their analogy with the water pockets in bioaggregates and the active sites of enzymes. Moreover, enzymes solubilized in reverse micelles can exhibit an enhanced catalytic efficiency. Figure B4.3.1 shows a reverse micelle of bis(2-ethylhexyl)sulfosuccinate (AOT) in heptane with three naphthalenic fluorescent probes whose excited-state pK values are much lower than the ground-state pK (see Table 4.4) 2-naphthol (NOH), sodium 2-naphthol sulfonate (NSOH), potassium 2-naphthol-6,8-disulfonate (NSOH). The spectra and the rate constants for deprotonation and back-recombination (determined by time-resolved experiments) provide information on the location of the probes and the corresponding ability of their microenvironment to accept a proton , (i) NDSOH is located around the center of the water pool, and at water contents w = [H20]/[A0T] >... 

Martinek, K., Levashov, A. V, Pantin, V. I., and Berezin, I. V. (1978). Model of biological membranes or surface-layer (active center) of protein globules (enzymes) - reactivity of water solubilized by reversed micelles of aerosol OT in octane during neutral hydrolysis of picrylchloride. Doklady Akademii Nauk SSSR, 238, 626-9. 

FIG. 3 a-Chymotrypsin solubility (protein concentration) in reverse micelles of 0.1 M AOT in octane, as a dependence on the degree of surfactant hydration (water-to-AOT molar ratio), for protein molecules with chemically modified surface groups. ( ) Acetyl-a -ch5miotrypsin (O) succinyl-a-chymotrypsin (—) maximal concentration of nonmodified native a -ch5miotrypsin solubilized in reverse micelles. 

Horse liver alcohol dehydrogenase (HLADH) is an enzyme known to stereo-selectively oxidize and reduce a wide range of alcohol and ketone substrates. In a study that appeared in 1987, HLADH was solubilized in reverse micelles formed with AOT/cyclohexane and the oxidation of ethanol and reduction of cyclohexanone in a coupled substrate/coenzyme recycling system was investigated [147]. Activity and stability studies showed that the enzyme remains active and stable for at least 2 weeks while the charged coenzyme is retained within the dispersed water droplets. 

The conformation of bovine myelin basic protein (MBP) in AOT/isooctane/water reversed micellar systems was studied by Waks et al. 67). This MBP is an extrinsic water soluble protein which attains an extended conformation in aqueous solution 68 but is more density packed at the membrane surface. The solubilization of MBP in the AOT reversed micelles depends on the water/AOT-ratio w0 68). The maximum of solubilization was observed at a w0-value as low as 5.56. The same value was obtained for another major protein component of myelin, the Folch-Pi proteolipid 69). According to fluorescence emission spectra of MBP, accessibility of the single tryptophane residue seems to be decreased in AOT reversed micelles. From CD-spectra one can conclude that there is a higher conformational rigidity in reversed micelles and a more ordered aqueous environment. 

Obviously, water, aqueous solutions of salts, and mixtures of highly hydrophilic solvents have also been found to be solubilized in the micellar core [13,44]. The maximum amount of such solubilizates that can be dissolved in reversed micelles varies widely, strongly depending on the nature of the surfactant and the apolar solvent, on the concentrations of surfactant and of additives, and on temperature [24,45-47]. 

Electrolytes are obviously solubilized only in the aqueous micellar core. Adding electrolytes in water-containing AOT-reversed micelles has an effect that is opposite to that observed for direct micelles, i.e., a decrease in the micellar radius and in the intermicellar attractive interactions is observed. This has been attributed to the stabilization of AOT ions at the water/surfactant interface [128]. 

By IR spectroscopy it was emphasized that the solubilization of amino acids or ohgopeptides in water-containing lecithin-reversed micelles involves structural changes in the aqueous micellar core [159]. 

At the present time, "interest in reversed micelles is intense for several reasons. The rates of several types of reactions in apolar solvents are strongly enhanced by certain amphiphiles, and this "micellar catalysis" has been regarded as a model for enzyme activity (. Aside from such "biomimetic" features, rate enhancement by these surfactants may be important for applications in synthetic chemistry. Lastly, the aqueous "pools" solubilized within reversed micelles may be spectrally probed to provide structural information on the otherwise elusive state of water in small clusters. 

Although anation and aquation rates of vitamin B12 are not affected appreciably by aqueous micelles, the solubilized water in reversed micelles, in contrast, influences the rate and equilibrium constants for the formation and decomposition of glycine, imidazole, and sodium azide adducts of vitamin Bl2 (Fendler et al., 1974). A vitamin B12 molecule is conceivably shielded from the apolar solvent (benzene) by some 300 surfactant molecules. 

The behavior of metal ions in reversed micelles may be more interesting, since the reversed micelle provides less solvated metal ions in its core (Sunamoto and Hamada, 1978). Through kinetic studies on the hydrolysis of the p-nitrophenyl ester of norleucine in reversed micelles of Aerosol OT and CC14 which solubilize aqueous cupric nitrate, Sunamoto et al. (1978) observed the formation of naked copper(II) ion this easily formed a complex with the substrate ester (formation constant kc = 108—109). The complexed substrate was rapidly hydrolyzed by free water molecules acting as effective nucleophiles. 

It appears from a survey of the literature that the essential properties of micelles in nonpolar solvents are understood, namely their stability and variations of size, the dissociation behavior, and their solubilizing capacities. Reverse micelles can dissolve relatively large amounts of water (1-10% w/v depending on emulsion formula) as well as polar solutes and, of course, water-soluble compounds. Consequently, they can be used as media for a number of reactions, including enzyme-catalyzed reactions. Very few attempts to investigate such reverse micelles at subzero temperatures are known, in spite of the fact that hydrocarbon solutions present very low freezing points. 

The amount of water solubilized in a reverse micelle solution is commonly referred to as W, the molar ratio of water to surfactant, and this is also a good qualitative indicator of micelle size. This is an extremely important parameter since it will determine the number of surfactant molecules per micelle and is the main factor affecting micelle size. For an (AOT)/iso-octane/H20 system, the maximum Wq is around 60 [16], and above this value the transparent reverse micelle solution becomes a turbid emulsion, and phase separation may occur. The effect of salt type and concentration on water solubilization is important. Cations with a smaller hydration size, but the same ionic charge, result in less solubilization than cations with a large hydration size [17,18]. Micelle size depends on the salt type and concentration, solvent, surfactant type and concentration, and also temperature. 

Surfactants having an appropriate hydrophobic/hydrophilic balance (sodium bis(-2-ethylhexyl)sufosuccinate, or AOT, for example) undergo concentration-dependent self association in apolar solvents to form reversed or inverted micelles (Fig. 33) [256-262]. Reversed micelles are capable of solubilizing a large number of water molecules (AOT reversed micelles in hexane are able to take up 60 water molecules per surfactant molecule, for example). Reversed-micelle-entrapped water pools are unique they differ significantly from bulk water. At relatively small water-to-surfactant ratios (w = 8-10, where w = [H20]/[Surfactant]), all of the water molecules are strongly bound to the surfactant headgroups. Substrate solubilization in the restricted water pools of reversed micelles results in altered dissociation constants [256, 257, 263-265], reactivities [256, 258, 266], and reaction products [267]. 

A solute (additive) can be located in reverse micelles in different solubilization sites in the water core, in the interfacial region or in the bulk solvent. Solubilization into the water cores increases the inner volume at constant interfacial area, resulting in radial growth. If the micelle is too small to receive a solute molecule without deformation, e.g., at low water content, a segregation occurs between small free molecules and the large objects which are covered with surfactant (Chatenay et al., 1987 Encinas and Lissi, 1986 Pileni et al., 1985). 

Much interest has been focused on solubilizing various amounts of water in reverse micelles. The micellar solutions can solubilize considerable amounts of water this is bound to the polar groups of the surfactant molecules by ion-dipole or dipole-dipole attraction. The properties of water solubilized by RMs are different from those of bulk water and are sensitive to the water pool parameter, Wo = [H20]/[Surfactant]. Assuming the water molecules in the oil droplets are spherical, the radius of the sphere is expressed as (Luisi et al., 1988) ... 

Solubilization of water. Detergency is defined as the ability of surfactant molecules to solubilize water molecules or polar substances in soft-core and hardcore RMs. Thus, micellization and solubilization are competitive processes. Any solubilized probe molecule causes a decrease in the CMC. Solubilization describes the dissolution of a solid, liquid or gas by an interaction with surfactant molecules. Addition of water has a dramatic effect on surfactant aggregation in hydrocarbons because hydrogen bonding has an appreciable stabilizing effect on reverse micelles. Solubilization for reverse micelles is phenomenologically similar to the adsorption processes (Eicke and Christen, 1978 Kitahara, 1980 Kitahara et al., 1976 Singleterry, 1955). 

The water in the RMs is considered to be a composite of two different types the "bound water" region, and the remaining "free water" region. On the basis of the IR data up to a Wo = 4, the water solvates the AOT ion-pair, further increasing in the water concentration up to a Wo = 10, probably giving rise to a hydration shell around the new-separated ions of AOT. Further increasing water concentration gives rise to the so called "free water". It has been shown by various physico-chemical techniques that the water of the reverse micelle behaves differently from normal water, especially at low concentrations (Wo < 10). Solubilization of water by such micelles promotes dissociation of ion pairs in the micelle to form micellar free ions. 

Effective pH values in soft-core RMs. Characterization of the acidity in the aqueous soft-core is important as ionizable compounds are solubilized in the water pool. The micellar core has a very high degree of organization of water. The water pool within reverse micelles is a different solvent than bulk water. The most interesting range of water content corresponds to rather small water pools (water-to-surfactant ratio of 3 to 10) in which peculiar properties of water cause the largest changes in behavior as compared to their behavior in bulk water. A water to surfactant ratio of 1 1 represents a very small, almost undetectable, quantity of... 

It is tempting to use the classical concept of pH and pKa, but several difficulties arise when applying these concepts to confined water in reverse micelles. Since the water in reverse micelles is a new solvent, the conventional determination of pH of the water pool is difficult. The micellar solubilization of oil-insoluble dyes is a well known phenomenon (Arkin and Singleterry, 1948 Fendler, 1984 Klevens, 1950 Rodgers, 1981 Ross, 1951). 

The difference is ascribed to the smaller micelle cavity of succinimides relative to sulfonates. Mixed micelles of naphthalene-sulfonate-succinimide show weaker solubilization capacity than that of individual additives. The solubilization of water in a micellar system is closely related to the micelle core (Fontana, 1968). Addition of water to this non-polar solution, as engine lubricating oil is, produces a new set of phenomena. For small amounts of water, the micellar aggregates show swelling by uptake of water. The highly bounded water in reversed micelles makes surfactants less effective. 

Zhou N, Li Q, Wu J et al (2001) Spectroscopic characterization of solubilized water in reversed micelles and microemulsions sodium bis(2-ethylhexyl) sulfosuccinate and sodium bis(2-ethylhexyl) phosphate in n-heptane. Langmuir 17(15) 4505-4509... 

The phase boundary lines for supercritical ethane at 250 and 350 bar are shown in Figure 2. The surfactant was found to be only slightly soluble in ethane below 200 bar at 37 C, so that the ternary phase behavior was studied at higher pressures where the AOT/ethane binary system is a single phase. As pressure is increased, more water is solubilized in the micelle core and larger micelles can exist in the supercritical fluid continuous phase. The maximum amount of water solubilized in the supercritical ethane-reverse micelle phase is relatively low, reaching a W value of 4 at 350 bar. 

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