Micelles micellar behavior

Several models have been developed to interpret micellar behavior (Mukerjee, 1967 Lieberman et al., 1996). Two models, the mass-action and phase-separation models are described here in mor detail. In the mass-action model, micelles are in equilibrium with the unassociated surfactant or monomer. For nonionic surfactants with an aggregation numb itbfe mass-action model predicts thatn molecules of monomeric nonionized surfactaStajeact to form a micelleM ... 

Kitahara, A., Kon-no, K. Micelle formation in nonaqueous media. In Colloidal dispersions and micellar behavior. ACS symposium series No. 9. 225, 1975... 

The reverse micelle phase behavior in supercritical fluids is markedly different than in liquids. By increasing fluid pressure, the maximum amount of solubilized water increases, indicating that these higher molecular weight structures are better solvated by the denser fluid phase. The phase behavior of these systems is in part due to packing constraints of the surfactant molecules and the solubility of large micellar aggregates in the supercritical fluid phase. 

A comparison of all the results reported here reveals that all the models reviewed predict qualitatively similar micellar behavior. Although the magnitudes of quantities such as the cmc or average aggregation number may be quite diflFerent for the different models (e.g., h t-i completely phase separates in Larson s model but forms well-behaved micelles in the simulations of Desplat and Care [31], because of the head-solvent attraction they used), each model predicts similar trends in these properties. This confirms the assumption that the solvophobic effect (i.e., the dislike of the solvophobic tail beads for the solvent) is the major driving force for micellization but also indicates that other forces are present that control specific micellar properties. 

Although most polymers tend to accumulate at the fluid interface, reports involving the transfer of polymeric micelles (micellar shuttle) between two immiscible phases have been pubHshed. Poly(N-isopropylacrylamide) (PNIPAM), a thermally responsive polymer, is insoluble and can undergo a conformation change above its lower critical solution temperature of 32 ° C. The thermo reversible miceUization—demicellization process and micellar shuttle of PNIPAM-PEO diblock copolymer at a water-IL interface were investigated by dissipative particle dynamics (DPD) simulations (Soto-Figueroa et al, 2012). Simulation results confirm that the phase transfer behavior of polymeric micelles is controlled by the temperature effect that changes the diblock copolymer from hydrophilic to hydrophobic (as shown in Fig. 33). 

Kitahara, A. and Kon-No, K., Micelle formation in non-aqueous media, in Colloidal Dispersions and Micellar Behavior, Mittal, K. L. (Ed.), ACS Symposium Series, Vol. 9, American Chemical Society, Washington, DC, 1975, 225-232. 

Kamrath and Franses [85] developed a single-micelle-size mass action model for binary solutions of surfactants with the same hydrophilic group and counterion. The mass action model predicts micellar behavior more accurately than the pseudophase separation model [73] if the number of surfactant monomers in the mixed micelle is less than about 50. 

Surfactants have also been of interest for their ability to support reactions in normally inhospitable environments. Reactions such as hydrolysis, aminolysis, solvolysis, and, in inorganic chemistry, of aquation of complex ions, may be retarded, accelerated, or differently sensitive to catalysts relative to the behavior in ordinary solutions (see Refs. 205 and 206 for reviews). The acid-base chemistry in micellar solutions has been investigated by Drummond and co-workers [207]. A useful model has been the pseudophase model [206-209] in which reactants are either in solution or solubilized in micelles and partition between the two as though two distinct phases were involved. In inverse micelles in nonpolar media, water is concentrated in the micellar core and reactions in the micelle may be greatly accelerated [206, 210]. The confining environment of a solubilized reactant may lead to stereochemical consequences as in photodimerization reactions in micelles [211] or vesicles [212] or in the generation of radical pairs [213]. 

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. 

Differential scanning calorimetry measurements have shown a marked cooling/heat-ing cycle hysteresis and that water entrapped in AOT-reversed micelles is only partially freezable. Moreover, the freezable fraction displays strong supercooling behavior as an effect of the very small size of the aqueous micellar core. The nonfreezable water fraction has been recognized as the water located at the water/surfactant interface engaged in solvation of the surfactant head groups [97,98]. 

Two system-dependent interpretative pictures have been proposed to rationalize this percolative behavior. One attributes percolation to the formation of a bicontinuous structure [270,271], and the other it to the formation of very large, transient aggregates of reversed micelles [249,263,272], In both cases, percolation leads to the formation of a network (static or dynamic) extending over all the system and able to enhance mass, momentum, and charge transport through the system. This network could arise from an increase in the intermicellar interactions or for topological reasons. Then all the variations of external parameters, such as temperature and micellar concentration leading to an extensive intermicellar connectivity, are expected to induce percolation [273]. 

Disperse systems can also be classified on the basis of their aggregation behavior as molecular or micellar (association) systems. Molecular dispersions are composed of single macromolecules distributed uniformly within the medium, e.g., protein and polymer solutions. In micellar systems, the units of the dispersed phase consist of several molecules, which arrange themselves to form aggregates, such as surfactant micelles in aqueous solutions. 

Early studies focused on the behavior of molecular rotors in vesicles [128] and lipid bilayers [18, 26]. Humphrey-Baker et al. [128] found that an indocyanine dye associates with micellar systems in aqueous suspension. The dye migrates into the micelles and shows an increased quantum yield and a bathochromic shift of emission. Although Humphrey-Baker et al. identify modulation of the quantum... 

In the micellar region the trend to decreasing colloid stability is arrested and a partial improvement, in line with the enhanced level of polymer adsorption, is noted until the conditions for gross phase separation are reached. Only the intermediate block copolymer BC 42 shows indications of discontinuities in behavior at the solvent composition for micelle formation. The results presented here do not show the sharp transition from stability to instability found experimentally (4,8,17) by Napper and generally expected on theoretical grounds. However, there are important differences in experimental methodology that must be emphasised. 

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