Micelles, solubilization

Micelles are mainly important because they solubilize immiscible solvents in their cores. Nonnal micelles solubilize relatively large quantities of oil or hydrocarbon and reverse micelles solubilize large quantities of water. This is because the headgroups are water loving and the tailgroups are oil loving. These simple solubilization trends produce microemulsions (see section C2.3.11). 

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... 

Figure 27.1 A soap micelle solubilizing a grease particle in water. An electrostatic potential map of a fatty acid carboxylate shows how the negative charge is located in the head group.

At infinite dilution, 1-pentanol monomers distribute between AOT-reversed micelles and the continuous organic phase, whereas at finite alcohol concentration, given the ability of alcohol to self-assemble in the apolar organic solvent, a coexistence between reversed micelles (solubilizing 1-pentanol) and alcoholic aggregates (incorporating AOT molecules) is realized [25],... 

FIG. 6 Representation of spherical water-containing reversed micelles solubilizing a polar molecule (p) in the micellar core (A) or an amphiphilic molecule (a) in the palisade layer (B). 

GE Amidon, WI Higuchi, NSF Ho. Theoretical and experimental studies of transport of micelle-solubilized solutes. J Pharm Sci 71 77-84 (1982). 

P Singh, S Desai, D Flanagan, A Simonelli, W Higuchi. Mechanistic study of the influence of micelle solubilization and hydrodynamic factors on the dissolution rate of solid drugs. J Pharm Sci 57 959, 1968. 

A method used to describe the enhanced dissolution rate following micelle-facilitated dissolution is to compare the dissolution of the drug in the surfactant solution to that of the dissolution rate in water this is often termed the reaction factor method. The reaction factor, ( vM, which is the total flux of the micelle-solubilized solute plus the free solute divided by the flux of the free solute, is given by... 

K. L. Mittel, Micellization, Solubilization, and Microemulsions, Plenum Press, New York, 1977. 

Haapakka and Kankare have studied this phenomenon and used it to determine various analytes that are active at the electrode surface [44-46], Some metal ions have been shown to catalyze ECL at oxide-covered aluminum electrodes during the reduction of hydrogen peroxide in particular. These include mercu-ry(I), mercury(II), copper(II), silver , and thallium , the latter determined to a detection limit of <10 10 M. The emission is enhanced by organic compounds that are themselves fluorescent or that form fluorescent chelates with the aluminum ion. Both salicylic acid and micelle solubilized polyaromatic hydrocarbons have been determined in this way to a limit of detection in the order of 10 8M. 

Martinek K, Yatsimirskii AK, Levashov AV, Berezin IV. In Mittal KL, editor. Micellization, solubilization and microemulsions, vol. 2. New York Plenum 1977. pp. 489-508. 

Romsted LS (1977) A general kinetic theory of rate enhancements for reactions between organic substrates and hydrophUic ions in micellar systems. In Mittal KL (ed) Micellization, Solubilization, Microemulsions. Plenum Press, New York... 

ForCaCO, particles in W/O microemulsions of hexaethylene glycol dodecyl ether, however, the values of Nm/Np lie between 0.044 and 0.28, indicating that the particles form by the destruction of micelle-solubilizing aqueous Ca(OH)2 rather than by the intermicellar exchange process (5). In the case of the formation of CaCO-) particles in the Ca salt of Aerosol OT-cyclohexane system, as seen in Table 7.2.2, the particles... 

FIG. 8.4 Determination of the microenvironment of a molecule (a) a portion of the ultraviolet spectrum of benzene in (1) heptane, (2) water, and (3) 0.4 M sodium dodecyl sulfate and (b) ratio of the intensity of the solvent-induced peak to that of the major peak for benzene versus the index of solvent polarity. The relative dielectric constant is also shown versus the index of polarity. (Redrawn, with permission, from P. Mukerjee, J. R. Cardinal, and N. R. Desai, In Micellization, Solubilization and Microemulsions, Vols. 1 and 2 (K. L. Mittal, Ed.), Plenum, New York, 1976.)... 

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. 

Aliphatic hydrocarbon solutes are primarily solubilized within the hydrocarbon core region of the surfactant micelles. Solubilization isotherms (activity coefLcient versus mole fraction, X) for these hydrophobic solutes exhibit curves that decrease from relatively large values at inLnite dilution to lower values as X increases toward unity (Figure 12.6). The aromatic hydrocarbons are intermediate in behavior between highly polar solutes, which are anchored in the micelle surface region, and aliphatic hydrocarbons, which preferentially solubilize in the hydrocarbon core region (Kondo et al., 1993). 

This result indicates that the solubilization of alkanols in micelles depends only on the hydrophobicity of alkanols and that there is no effect of the molecular shape of alkanols on the solubilization in the micelles. Hence, a Lexible micelle solubilization model for alkanols was proposed (Figure 12.12). 

FIGURE 12.12 A possible model of a exible micelle solubilizing alkanols. (Reprinted from Eda, Y. N. Takisawa, and K. Shirahama. 199 ngmuir 12 325-329. With permission from American Chemical Society.)... 

Two models for micelle structure were identiLed in their studies (Xing and Mattice, 1998). In analogy with the structural models for systems involving low molecular weight surfactants, two kinds of aggregates of spherical shape can be pictured, depending on how the solubilizates are located inside the block copolymer micelles. Solubilization takes places in two steps in the Xing and Mattice s simulations (1998). 

In terms of solubilization ability, Gadelle et al. (1995) showed that there were distinct differences between conventional surfactant micelles and polymeric surfactant micelles. Solubilization in block... 

Figure 6.5 Requirement for the presence of detergent while screening micelle-solubilized membrane proteins. In this series of experiments both the target (KcsA) and the reference (OmpA) were immobilized at a solution equivalent of 150pM. The histogram represents the fractional difference in peak amplitude of a known ligand of KcsA in the presence of KcsA and OmpA. The bar labeled control represents the first application of the ligand. Subsequently three injections of the ligand were performed using buffers that contained no detergent. A further three injections were performed where the buffer used to wash the immobilized samples contained deuterated DPC.

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