Micelles solubility

We continue the surfactant mixture (mixed micelles) solubility example introduced in the first part of this chapter. If only 4 experiments are carried out at the factorial points and the model equation contains 3 coefficients plus the constant term, then the design is saturated. The model will fit the data exactly ... 

Another promising application of supercritical microemulsions is in the broad area of polymerization reactions. An example of one such system is in the work by Beckman et al. [41,74]. In this study, acrylamide monomer dissolved in the surfactant interfacial region of a supercritical ethane-propane microemulsion was catalyzed by azobis(isobutylnitrile) (AIBN) dissolved in the reverse micelle core to produce the micelle-soluble polyacrylamide. 

The Krafft phenomenon is best discussed from the interplay between the temperature-dependence of the surfactant unimer solubility and the temperature dependence of the CMC. As we have learnt above, the latter temperature dependence is very weak and we can consider here that the CMC is, to a good approximation, independent of temperature. On the other hand, we expect the dissolution of the surfactant into the constituent solvated ions to increase markedly with temperature as seen for simple salts. If this solubility is below the CMC, no micelles can form and the total solubility is limited by the (low) unimer solubility. If, on the other hand, the unimer solubility reaches the CMC, micelles may form. It is a characteristic feature of micellization, as we will see later, that as the micelle concentration increases there is virtually no change in the free unimer activity (or concentration). This, together with a very high micelle solubility, explains why a quite small increase in unimer solubility (resulting here from a temperature increase) leads to a dramatic increase in the overall surfactant solubility. 

A mixture of octanol, a little hexadecyltrimethylammonium bromide, and 37% aq. HCl heated at reflux overnight 1-chlorooctane. Y 87% (Y 47% in the absence of micelles). Solubility of alcohols in coned, aq. HCl is considerably enhanced in micellar media, thereby effecting an inexpensive conversion to alkyl chlorides in high yield. F.e.s. B. Jursic, Synthesis 1988, 868-71 halogenative cleavage of ethers, inch dichlorides from cyclic ethers, and phenols and alkyl chlorides from phenolethers, s. J. Chem. Res. (S) 1989, 284 5. 

To overcome the use of polar aprotic solvents, enzymes have been incorporated within reverse micelles using the anionic surfactant Aerosol-OT [AOT, bis(2-ethylhexyl)sodium sulfosuccinate]. AOT forms thermodynamic water droplets surrounded by a surfactant monolayer in oil (isooctane). Water entrapped within the reverse micelles resembles the polar pockets in cells(ll). IiKXirporation of enzymes within reverse micelles soluble in non-polar media facilitates productive collisions and reactions between enzymes and non-polar... 

The Kraft point (T ) is the temperature at which the erne of a surfactant equals the solubility. This is an important point in a temperature-solubility phase diagram. Below the surfactant cannot fonn micelles. Above the solubility increases with increasing temperature due to micelle fonnation. has been shown to follow linear empirical relationships for ionic and nonionic surfactants. One found [25] to apply for various ionic surfactants is ... 

The issue of water in reverse micellar cores is important because water swollen reverse micelles (reverse microemulsions) provide means for carrying almost any water-soluble component into a predominantly oil-continuous solution (see discussions of microemulsions and micellar catalysis below). In tire absence of water it appears tliat premicellar aggregates (pairs, trimers etc.) are commonly found in surfactant-in-oil solutions [47]. Critical micelle concentrations do exist (witli some exceptions). 

Other solubilization and partitioning phenomena are important, both within the context of microemulsions and in the absence of added immiscible solvent. In regular micellar solutions, micelles promote the solubility of many compounds otherwise insoluble in water. The amount of chemical component solubilized in a micellar solution will, typically, be much smaller than can be accommodated in microemulsion fonnation, such as when only a few molecules per micelle are solubilized. Such limited solubilization is nevertheless quite useful. The incoriDoration of minor quantities of pyrene and related optical probes into micelles are a key to the use of fluorescence depolarization in quantifying micellar aggregation numbers and micellar microviscosities [48]. Micellar solubilization makes it possible to measure acid-base or electrochemical properties of compounds otherwise insoluble in aqueous solution. Micellar solubilization facilitates micellar catalysis (see section C2.3.10) and emulsion polymerization (see section C2.3.12). On the other hand, there are untoward effects of micellar solubilization in practical applications of surfactants. Wlren one has a multiphase... 

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... 

With the aim of catalysis of the Diels-Alder reaction of 5.1 with 5.2 by metallo micelles, preliminary studies have been performed using the surfactants 5.5a-c and 5.6 (Scheme 5.2). Unfortunately, the limited solubility of these surfactants in the pH region that allows Lewis-acid catalysis of the Diels-... 

Detergents are designed to be effective in hard water meaning water containing calcium salts that form insoluble calcium carboxylates with soaps These precipitates rob the soap of Its cleansing power and form an unpleasant scum The calcium salts of synthetic deter gents such as sodium lauryl sulfate however are soluble and retain their micelle forming ability even m hard water... 

Critical micelle concentration (Section 19 5) Concentration above which substances such as salts of fatty acids aggre gate to form micelles in aqueous solution Crown ether (Section 16 4) A cyclic polyether that via lon-dipole attractive forces forms stable complexes with metal 10ns Such complexes along with their accompany mg anion are soluble in nonpolar solvents C terminus (Section 27 7) The amino acid at the end of a pep tide or protein chain that has its carboxyl group intact—that IS in which the carboxyl group is not part of a peptide bond Cumulated diene (Section 10 5) Diene of the type C=C=C in which a single carbon atom participates in double bonds with two others... 

The elution order for neutral species in MEKC depends on the extent to which they partition into the micelles. Hydrophilic neutrals are insoluble in the micelle s hydrophobic inner environment and elute as a single band as they would in CZE. Neutral solutes that are extremely hydrophobic are completely soluble in the micelle, eluting with the micelles as a single band. Those neutral species that exist in a partition equilibrium between the buffer solution and the micelles elute between the completely hydrophilic and completely hydrophobic neutrals. Those neutral species favoring the buffer solution elute before those favoring the micelles. Micellar electrokinetic chromatography has been used to separate a wide variety of samples, including mixtures of pharmaceutical compounds, vitamins, and explosives. 

The order of elution when using MEKC is vitamin B3 (5.58 min), vitamin Be (6.59 min), vitamin 82 (8.81 min), and vitamin Bi (11.21 min). What conclusions can you make about the solubility of the B vitamins in the sodium dodecylsulfate micelles ... 

Chain-Growth Associative Thickeners. Preparation of hydrophobically modified, water-soluble polymer in aqueous media by a chain-growth mechanism presents a unique challenge in that the hydrophobically modified monomers are surface active and form micelles (50). Although the initiation and propagation occurs primarily in the aqueous phase, when the propagating radical enters the micelle the hydrophobically modified monomers then polymerize in blocks. In addition, the hydrophobically modified monomer possesses a different reactivity ratio (42) than the unmodified monomer, and the composition of the polymer chain therefore varies considerably with conversion (57). The most extensively studied monomer of this class has been acrylamide, but there have been others such as the modification of PVAlc. Pyridine (58) was one of the first chain-growth polymers to be hydrophobically modified. This modification is a post-polymerization alkylation reaction and produces a random distribution of hydrophobic units. 

Sta.g C I Pa.rtlcIeNucIea.tlon, At the start of a typical emulsion polymerization the reaction mass consists of an aqueous phase containing smaU amounts of soluble monomer, smaU spherical micelles, and much larger monomer droplets. The micelles are typicaUy 5—30-nm in diameter and are saturated with monomer emulsified by the surfactant. The monomer droplets are larger, 1,000—10,000-nm in diameter, and are also stabilized by the surfactant. 

Water-soluble initiator is added to the reaction mass, and radicals are generated which enter the micelles. Polymerization starts in the micelle, making it a growing polymer particle. As monomer within the particle converts to polymer, it is replenished by diffusion from the monomer droplets. The concentration of monomer in the particle remains as high as 5—7 molar. The growing polymer particles require more surfactant to remain stable, getting this from the uninitiated micelles. Stage I is complete once the micelles have disappeared, usually at or before 10% monomer conversion. 

Radicals generated from water-soluble initiator might not enter a micelle (14) because of differences in surface-charge density. It is postulated that radical entry is preceded by some polymerization of the monomer in the aqueous phase. The very short oligomer chains are less soluble in the aqueous phase and readily enter the micelles. Other theories exist to explain how water-soluble radicals enter micelles (15). The micelles are presumed to be the principal locus of particle nucleation (16) because of the large surface area of micelles relative to the monomer droplets. 

Bde salts, cholesterol, phosphoHpids, and other minor components are secreted by the Hver. Bile salts serve three significant physiological functions. The hydrophilic carboxylate group, which is attached via an alkyl chain to the hydrophobic steroid skeleton, allows the bile salts to form water-soluble micelles with cholesterol and phosphoHpids in the bile. These micelles assist in the solvation of cholesterol. By solvating cholesterol, bile salts contribute to the homeostatic regulation of the amount of cholesterol in the whole body. Bile salts are also necessary for the intestinal absorption of dietary fats and fat-soluble vitamins (24—26). 

Micellar properties are affected by changes in the environment, eg, temperature, solvents, electrolytes, and solubilized components. These changes include compHcated phase changes, viscosity effects, gel formation, and Hquefication of Hquid crystals. Of the simpler changes, high concentrations of water-soluble alcohols in aqueous solution often dissolve micelles and in nonaqueous solvents addition of water frequendy causes a sharp increase in micellar size. 

Emulsion Polymerization. Emulsion polymerization takes place in a soap micelle where a small amount of monomer dissolves in the micelle. The initiator is water-soluble. Polymerization takes place when the radical enters the monomer-swollen micelle (91,92). Additional monomer is supphed by diffusion through the water phase. Termination takes place in the growing micelle by the usual radical-radical interactions. A theory for tme emulsion polymerization postulates that the rate is proportional to the number of particles [N. N depends on the 0.6 power of the soap concentration [S] and the 0.4 power of initiator concentration [i] the average number of radicals per particle is 0.5 (93). 

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