Micelles orientation

One potential application of the work on oriented nematic phases of rodlike molecules is to solutions containing cylindrical micelles. Orientation could be achieved by a shear field or perhaps by an electric field. Gotz and Heckman (9) confirmed the existence of anisotropic electrical conductivity for a concentrated surfactant solution in a shear field. They used their results to show that the solution contained cylindrical rather than platelike micelles. Of course, the magnitude of the electrical conductivity in an aqueous micellar solution should be quite different from that in the nematic phase of an organic material. So the conditions for and types of electrohydrodynamic instabilities could be different as well. 

A mesomorphic (liquid-crystal) phase of soap micelles, oriented in a hexagonal array of cylinders. Middle soap contains a similar or lower proportion of soap (e.g., 50%) as opposed to water. Middle soap is in contrast to neat soap, which contains more soap than water and is also a mesomorphic phase, but has a lamellar structure rather than a hexagonal array of cylinders. Also termed clotted soap . See Neat Soap. 

Figure 2. Schematic mechanisms of solubilization. Clockwise from 5 o clock ion exchange with the surface solution in interior of micelle oriented adsorption formation of oil-soluble salt...

Winsor [173,174] has postulated a mechanism for this increased solubility of an apolar solubilizate when a polar solubilizate is introduced into the system, based on his theory of intermolecular and intramolecular forces and affinities. He considered a system of water, octanol, undecane-3, sodium sulphate and a saturated aliphatic hydrocarbon fraction. Mixing 5 ml 20% aqueous solution of the surfactant with 5 ml hydrocarbon produced a two-phase system the first composed of the hydrocarbon, the second the aqueous surfactant solution, the micelles of which, according to Winsor, had not solubilized the hydrocarbon to any appreciable extent. Octanol added to such a system penetrated the micelles, orienting with its hydroxyl groups between the sulphate groups of the surfactant... 

The anisotropic micelles forming lyotropic liquid crystals are also oriented by surfaces. Both prolate and oblate micelles orient parallel to flat surfaces [114,115] probably due to hard-core interactions [116]. Prolate micelles can also be azimuthally oriented by grooved surfaces, or homeotropically oriented by two-dimensional topographies [117]. 

For structures with a high curvature (e.g., small micelles) or situations where orientational interactions become important (e.g., the gel phase of a membrane) lattice-based models might be inappropriate. Off-lattice models for amphiphiles, which are quite similar to their counterparts in polymeric systems, have been used to study the self-assembly into micelles [ ], or to explore the phase behaviour of Langmuir monolayers [ ] and bilayers. In those systems, various phases with a nematic ordering of the hydrophobic tails occur. 

Likewise, Grieco, while working with amphiphile-like reactants, observed an enhanced preference for endo-adduct in aqueous solutions, which he attributed to orientational effects within the micelles that were presumed to be present in the reaction mixture ". Although under the conditions used by Grieco, the presence of aggregates cannot be excluded, other studies have clearly demonstrated that micelle formation is not the reason for the improved selectivities . Micellar a peg tes even tend to diminish the preference for endo adduct. ... 

Effects of Surfactants on Solutions. A surfactant changes the properties of a solvent ia which it is dissolved to a much greater extent than is expected from its concentration effects. This marked effect is the result of adsorption at the solution s iaterfaces, orientation of the adsorbed surfactant ions or molecules, micelle formation ia the bulk of the solution, and orientation of the surfactant ions or molecules ia the micelles, which are caused by the amphipathic stmcture of a surfactant molecule. The magnitude of these effects depends to a large extent on the solubiUty balance of the molecule. An efficient surfactant is usually relatively iasoluble as iadividual ions or molecules ia the bulk of a solution, eg, 10 to mol/L. 

Lattice models have the advantage that a number of very clever Monte Carlo moves have been developed for lattice polymers, which do not always carry over to continuum models very easily. For example, Nelson et al. use an algorithm which attempts to move vacancies rather than monomers [120], and thus allows one to simulate the dense cores of micelles very efficiently. This concept cannot be applied to off-lattice models in a straightforward way. On the other hand, a number of problems cannot be treated adequately on a lattice, especially those related to molecular orientations and nematic order. For this reason, chain models in continuous space are attracting growing interest. 

The problem of molecular recognition has attracted biologically oriented chemists since Emil Fischer s lock-and-key theory l0). Within the last two decades, many model compounds have been developed micelle-forming detergents11, modified cyclodextrins 12), many kinds of crown-type compounds13) including podands, coronands, cryptands, and spherands. Very extensive studies using these compounds have, however, not been made from a point of view of whether or not shape similarity affects the discrimination. 

In highly diluted solutions the surfactants are monodispersed and are enriched by hydrophil-hydrophobe-oriented adsorption at the surface. If a certain concentration which is characteristic for each surfactant is exceeded, the surfactant molecules congregate to micelles. The inside of a micelle consists of hydrophobic groups whereas its surface consists of hydrophilic groups. Micelles are dynamic entities that are in equilibrium with their surrounded concentration. If the solution is diluted and remains under the characteristic concentration, micelles dissociate to single molecules. The concentration at which micelle formation starts is called critical micelle concentration (cmc). Its value is characteristic for each surfactant and depends on several parameters [189-191] ... 

Micellar medium has received great attention because it solubilizes, concentrates and orientates the reactants within the micelle core and in this way accelerates the reaction and favors the regio- and stereoselectivity of the process [68], In addition the micellar medium is cheap, can be reused, is more versatile than cyclodextrins and more robust than enzymes. With regard to Diels Alder reactions, we may distinguish between (i) those in which one or both reagents are surfactants which make up the micellar medium, and (ii) those that are carried out in a micellar medium prepared by a suitable surfactant. 

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. 

Parallel studies on the cycloadditions of non-surfactant dienes 106 and 107 and the dienophile 108 (Figure 4.4), analogs of 97,103 and 98-100, respectively, show that the regioisomer adducts were, in this case, obtained in equal amounts, supporting the idea that orientational effects in micelles promote the regioselectivity of a Diels-Alder reaction of a surfactant diene and a surfactant dienophile. 

The main peculiarity of solutions of reversed micelles is their ability to solubilize a wide class of ionic, polar, apolar, and amphiphilic substances. This is because in these systems a multiplicity of domains coexist apolar bulk solvent, the oriented alkyl chains of the surfactant, and the hydrophilic head group region of the reversed micelles. Ionic and polar substances are hosted in the micellar core, apolar substances are solubilized in the bulk apolar solvent, whereas amphiphilic substances are partitioned between the bulk apolar solvent and the domain comprising the alkyl chains and the surfactant polar heads, i.e., the so-called palisade layer [24],... 

In addition, it is of interest to note that investigations of the microscopic processes leading to nucleation, growth, oriented growth by the surfactant monolayer, and growth inhibition of nanoparticles in reversed micelles and of confinement and adsorption effects on such phenomena represent an intriguing and quite unexplored research field [218]. 

In the bilayer or upon interaction with detergent micelles, a structural reorganization of pardaxin aggregates takes place, in which the polar side chains interact with themselves and the hydrophobic residues are externally oriented in the pardaxin aggregate, therefore allowing interactions with the lipid backbone hydrocarbons. 

---