Water micelle surfaces

In otlier words, tire micelle surface is not densely packed witli headgroups, but also comprises intennediate and end of chain segments of tire tailgroups. Such segments reasonably interact witli water, consistent witli dynamical measurements. Given tliat tire lifetime of individual surfactants in micelles is of tire order of microseconds and tliat of micelles is of tire order of milliseconds, it is clear tliat tire dynamical equilibria associated witli micellar stmctures is one tliat brings most segments of surfactant into contact witli water. The core of nonnal micelles probably remains fairly dry , however. 

At the end of the 1960s, Subba Rao et al. examined the influence of the interface on the CMC values [56]. They found a decrease in the CMC at the oil-water interface compared with the air-water interface. The CMC decreased by about 10% in the presence of heptane and by about 30-40% in the presence of benzene. The solubilization of the hydrocarbon in the micelle interior results in an increase in the micelle size and a slight change in the curvature of the micelle surface. The electrical potential and hence the electrical work of... 

But this static picture is clearly inadequate, because solutes and surfactant monomers move rapidly from water to micelles, and the surfactant head groups will oscillate about some mean position at the micelle surface (Aniansson, 1978). Non-ionic substrates are not localized within the micelle or its Stern layer and there is no reason to believe that they are distributed uniformly within the Stern layer. 

Firstly, the (negative) values of the NOE for residues of the unstructured N-terminus that do not interact with the DPC micelle surface are larger. This result is most probably due to increased saturation transfer from the water and results from increased exchange of amide protons at the used pH of 6.0 compared to that used in the absence of DPC (pH 3.1). Secondly, the values for residues from the C-terminal pentapeptide are negative in the case of NPY free in solution whereas they are positive in the micelle-bound form. This clearly indicates that the C-terminal pentapeptide is significantly rigidified upon binding to the micelle. The result is supported by the structure calculation that displays rather low RMSD values for that part... 

A pseudophase ion exchange model has been applied to reactions in micellar systems with varying success (1-7). According to this model, the distribution of nucleophile is considered to depend on the ion-exchange equilibrium between the nucleophile and the surfactant counterion at the micelle surface. This leads to a dependence on the ion-exchange constant (K g) as well as on the degree of dissociation (a) of the surfactant counterion. The ion exchange (IE) model has recently been extended to oil in water microemulsions (8). 

The rough water-hydrocarbon surface of the core introduced in Figure 8.3c suggests that the core of the micelle should really be considered as two distinct regions an inner core that is essentially water-free and a hydrated shell between the inner core and the polar heads. This partly aqueous shell is sometimes called the palisade layer. The extent to which the hydrocarbon chains protrude into the water is problematic, but we can get an idea of the volume of the palisade layer as follows. 

Dynamics of water at surface of complex systems Study of aqueous micelles and proteins... 

Micelles are colloidal dispersions that form spontaneously, under certain concentrations, from amphiphilic or surface-active agents (surfactants), molecules of which consist of two distinct regions with opposite afL nities toward a given solvent such as water (Torchilin, 2007). Micelles form when the concentration of these amphiphiles is above the critical micelle concentration (CMC). They consist of an inner core of assembled hydrophobic segments and an outer hydrophilic shell serving as a stabilizing interface between the hydrophobic core and the external aqueous environment. Micelles solubilize molecules of poorly soluble nonpolar pharmaceuticals within the micelle core, while polar molecules could be adsorbed on the micelle surface, and substances with intermediate polarity distributed along surfactant molecules in intermediate positions. 

FIGURE 28.1 Chemical modification of the protein with a water-insoluble reagent in the reverse micelles of Aerosol OT in octane. The protein molecule is entrapped in the reverse micelle surrounded by a cover of hydrated surfactant molecules. The water-insoluble reagent is located in the bulk organic phase and can be incorporated into the micelle surface layer coming into contact with the reactive group in the protein. After completion of the reaction the reverse micelle system is disintegrated and the protein is precipitated by cold acetone. 

The inhomogeneous structure of a micelle (or inverse micelle) can influence the course of a photoinduced electron transfer. Such a micelle is biphasic, containing a hydrocarbon-like core and a water-like surface. If the photoinduced electron transfer produces a product which has lower solubility in the aqueous phase (a situation which might obtain if a cationic acceptor is reduced to a neutral product), this product will be directed by solubility considerations to move toward the hydrophobic center of the micelle, i.e., remote from the site of the forward electron transfer. This spatial separation, shown conceptually in Scheme 4, in turn will retard the rate of the back reaction compared with that of the forward reaction. 

Solubilization is the formation of a thermodynamically stable, isotropic solution of a substance (the solubilizate), normally insoluble or slightly soluble in water, by the addition of a surfactant (the solublizer). The micelles of the surfactant cause solubilization of the substrate, producing an isotropic solution of the chemical. The solubilizate can be incorporated in the surfactant micelle in different ways, depending on the nature of the substrate and the surfactant micelles. For hydrophobic substrates, the molecules become incorporated in the hydrocarbon core of the micelle. With more polar substrates, the molecules may become incorporated in the hydrophilic PEO chains of the micelle or they may be simply adsorbed at the micelle surface. 

The ability of micellar solutions and mlcroemulslons to dissolve and compartmentalize both polar and non-polar reactants has a significant effect on chemical reactivity. An Idealized representation of a typical micelle catalyzed reaction is depicted In Figure 2. Here the non-polar reactant is solubilized within the micelle while the ionic reactant is at the surface. The polar head groups of the surfactants generate a charge at the micelle surface which serves to attract an oppositely charged water soluble reactant increasing the concentration of that reactant near the micelle. The result Is an enhanced reaction rate. 

Fig. 4.19 is a cross-section the actual micelle structure is three-dimensional. The assembled structure is completely nonregular rapid exchange between micelle molecules and monomeric soluble molecules occurs. Therefore, a micelle can be regarded as a disordered dynamic supramolecular assembly. In a micellar structure, the hydrophilic part of the component molecule is located on the outer surface of the micelle, in contact with the aqueous phase, which minimizes the unfavorable contact of the hydrophobic part with water. Micelles can trap organic materials hke oils in the inner hydrophobic core, so micelle formation is used in many cleaning agents. 

Inside the column, solutes are affected by the presence of micelles in the mobile phase and by the nature of the alkyl-bonded stationary phase, which is coated with monomers of surfactant (Fig. 1). As a consequence, at least two partition equilibria can affect the retention behavior. In the mobile phase, solutes can remain in the bulk water, be associated to the free surfactant monomers or micelle surface, be inserted into the micelle palisade layer, or penetrate into the micelle core. The surface of the surfactant-modified stationary phase is micelle-like and can give rise to similar interactions with the solutes, which are mainly hydrophobic in nature. With ionic surfactants, the charged heads of the surfactant in micelles and monomers adsorbed on the stationary phase are in contact with the polar solution, producing additional electrostatic interactions with charged solutes. Finally, the association of solutes with the nonmodified bonded stationary phase and free silanol groups still exists. 

Methanol, which has the shortest carbon chain, is more polar and soluble than other alcohols. SDS monomers are more easily solvated in an aqueous-methanol medium. This inhibits them from interacting and forming micelles. A similar behavior is expected for acetonitrile. Ethanol and propanol, which are also miscible with water, remain outside the micelles, dissolved in the bulk liquid, but interact with the micelle surface. Repulsion among the... 

---