Micelles mixing

This localization phenomenon has also been shown to be important in a case of catalysis by premicellar aggregates. In such a case [ ] premicellar aggregates of cetylpyridinium chloride (CPC) were shown to enhance tire rate of tire Fe(III) catalysed oxidation of sulphanilic acid by potassium periodate in tire presence of 1,10-phenantliroline as activator. This chemistry provides a lowering of tire detection limit for Fe(III) by seven orders of magnitude. It must also be appreciated, however, tliat such premicellar aggregates of CPC actually constitute mixed micelles of CPC and 1,10-phenantliroline tliat are smaller tlian conventional CPC micelles. 

Inspired by the many hydrolytically-active metallo enzymes encountered in nature, extensive studies have been performed on so-called metallo micelles. These investigations usually focus on mixed micelles of a common surfactant together with a special chelating surfactant that exhibits a high affinity for transition-metal ions. These aggregates can have remarkable catalytic effects on the hydrolysis of activated carboxylic acid esters, phosphate esters and amides. In these reactions the exact role of the metal ion is not clear and may vary from one system to another. However, there are strong indications that the major function of the metal ion is the coordination of hydroxide anion in the Stem region of the micelle where it is in the proximity of the micelle-bound substrate. The first report of catalysis of a hydrolysis reaction by me tall omi cell es stems from 1978. In the years that... 

Small micelles in dilute solution close to the CMC are generally beheved to be spherical. Under other conditions, micellar materials can assume stmctures such as oblate and prolate spheroids, vesicles (double layers), rods, and lamellae (36,37). AH of these stmctures have been demonstrated under certain conditions, and a single surfactant can assume a number of stmctures, depending on surfactant, salt concentration, and temperature. In mixed surfactant solutions, micelles of each species may coexist, but usually mixed micelles are formed. Anionic-nonionic mixtures are of technical importance and their properties have been studied (38,39). 

FIGURE 24.4 In the small intestine, fatty acids combine with bile salts in mixed micelles, which deliver fatty acids to epithelial cells that cover the intestinal villi. Triacylglycerols are formed within the epithelial cells. 

Their results in Fig. 2 show that LAS-AOS mixtures which are rich in LAS have smaller CMC values than LAS alone. This indicates that the addition of small amounts of AOS promotes the formation of mixed micelles in the solution. A minimum in the CMC plot is observed for mixtures containing 20 wt%... 

In another study of the physical behavior of soap-LSDA blends, Weil and Linfield [35] showed that the mechanism of action of such mixtures is based on a close association between the two components. In deionized water this association is mixed micellar. Surface tension curves confirm the presence of mixed micelles in deionized water and show a combination of optimum surface active properties, such as low CMC, high surface concentration, and low surface concentration above the CMC. Solubilization of high Krafft point soap by an LSDA and of a difficulty soluble LSDA by soap are related results of this association. Analysis of dispersions of soap-LSDA mixtures in hard water shows that the dispersed particles are mixtures of soap and LSDA in the same proportion as they were originally added. These findings are inconsistent with the view that soap reacts separately with hard water ions and that the resulting lime soap is suspended by surface adsorption of LSDA. The suspended particles are responsible for surface-active properties and detergency and do not permit deposits on washed fabric unlike those found after washing with soap alone. 

The substituents at C-2, C-3 within diene 97 and those at C-1, C-2 within dienophiles 98-100 are electronically and/or sterically equivalent with respect to diene and dienophile reaction centers, respectively, and therefore cycloaddition should not display regiochemical bias in the absence of orientational effects. The Diels-Alder reactions of 97 prepared in situ with 98-100 gave an excess of 101 (Scheme 4.19) [70b], which are the expected regioisomers if the reagents react in their preferred orientations within a mixed micelle with an ammonium head group at the aggregate-water interface and the remainder in the micelle interior. 

FIGURE 3 Effect of the amount of cholesterol on the particle size. Phosphatidylcholine/cholesterol liposomes were prepared by the octyl glucoside dilution technique. The begin concentration of the mixed micelles was 150 mM octyl glucoside and 10 mM phosphatidylcholine in 10 mM tris(hydroxymethyl)aminomethane and 0.9% NaCl, pH 7.4. Dilution was performed with an automatic titration unit at a dilution rate (= dilution factor, relative to the initial volume, per unit of time) of 0.026 sec"l ( a and ) or 0.69 sec l ( and o). Mean diameters after dilution and ) and after filtration ( L and q) are repi sented. (Adapted from Jiskoot et al, 1986a.)... 

A. (1986a). Preparation of liposomes via detergent removal from mixed micelles by dilution. The effect of bilayer composition and process parameters on liposome characteristics, Pharm. Weekbl. 

Van Bloois, L., Dekker, D. D., and Crommelin, D. J. A. (1987). Solubilization of lipophilic drugs by amphiphiles Improvement of the apparent solubility of almitrine bismesylate by liposomes, mixed micelles and O/W emulsions, Acta Pharmaceut. TechnoL,... 

Irrespective of the physical form of the carotenoid in the plant tissue it needs to be dissolved directly into the bulk lipid phase (emulsion) and then into the mixed micelles formed from the emulsion droplets by the action of lipases and bile. Alternatively it can dissolve directly into the mixed micelles. The micelles then diffuse through the unstirred water layer covering the brush border of the enterocytes and dissociate, and the components are then absorbed. Although lipid absorption at this point is essentially complete, bile salts and sterols (cholesterol) may not be fully absorbed and are not wholly recovered more distally, some being lost into the large intestine. It is not known whether carotenoids incorporated into mixed micelles are fully or only partially absorbed. 

In contrast, the carotenes such as p-carotene and lycopene may position themselves parallel to the membrane surfaces to remain in a more lipophilic environment in the inner cores of the bilayer membranes. To move through an aqueous environment, carotenoids can be incorporated into lipid particles such as mixed micelles in the gut lumen or lipoproteins in the blood circulation and they can also form complexes with proteins with unspecific or specific bindings. 

The configuration of the molecule can also be another factor affecting the degree of micellarization of a compound in the lumen. For instance, cis isomers of P-carotene present a greater solubilization in mixed micelles in vitr(f and in the duodenal micellar phase in vivo than all-trans P-carotene. Despite their higher efficiency of micellarization, cis isomers of p-carotene are less absorbed by Caco-2 cells and also in vivo than the all-trans forms. 

Sugawara, T. et al., Lysophosphatidylcholine enhances carotenoid uptake from mixed micelles by Caco-2 human intestinal cells, J. Nutr, 131, 2921, 2001. 

Levin, G. and Mokady, S., Incorporation of all-trans or 9-cis- 3-carotene into mixed micelles in vitro. Lipids, 30, 177, 1995. 

El-Gorab, M. and Underwood, B.A., Solubilization of P-carotene and retinol into aqueous solutions of mixed micelles, Biochim. Biophys. Acta, 306, 58, 1973. 

Wang, F., The sensitive fluorimetric method for the determination of curcumin using the enhancement of mixed micelle, J. Fluoresc., 16, 53, 2006. 

R., Khaledi, M. G. Quantitative structure-activity relationships studies with micellar electrokinetic chromatography. Influence of surfactant type and mixed micelles on estimation of hydrophobicity and bioavailability. J. Chromatogr. A 1996, 727, 323-335. 

Rundlett, K. L. and Armstrong, D. W., Effect of micelles and mixed micelles on efficiency and selectivity of antibiotic-based capillary electrophoretic separations, Anal. Chem., 67, 2088, 1995. 

Clothier, Jr., J. G. and Tomellini, S. A., Chiral separation of veraprimil and related componds using micellar electrokinetic capillary chromatography with mixed micells of bile salt and polyoxyethylene ethers,. Chromatogr. A, 712, 179,1996. 

B (12.10) Under various reaction conditions, the isomer ratio of A was consistently higher than B. Isomer A is the expected regioisomer if the diene and dienophile react in their preferred orientation within a mixed micelle in which the quaternary ammonium groups are at the aggregate-water interface and the rest of the molecule is extended into the micelle interior (Figure 12.2). Isomer B comes about from the misalignment of the diene and dienophile within the mixed micelles. 

The absorption of drugs from the rectal [32] cavity has been studied in some detail. Muranishi et al. [34] have shown that a significant increase in the absorption and lymphatic uptake of soluble and colloidal macromolecules can be achieved by pretreating the rectal mucosal membrane with lipid-nonionic surfactant mixed micelles. They found no evidence of serious damage of the mucosal membrane. Davis [30] suggested that the vaginal cavity could be an effective delivery site for certain pharmaceuticals, such as calcitonin, used for the treatment of postmenopausal osteoporosis. 

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