Reverse micelles molecular structure

An enormous literature has been produced in recent decades in the field of molecular aggregation of amphiphilic molecules in liquid systems, emphasizing the extremely wide variety of accessible structures and dynamics. Among these molecular aggregates, in this chapter our attention will be restricted to those formed by some amphiphilic molecules (surfactants) in apolar solvents called reversed micelles [1]. 

Nucleic acids can also be solubilized in reverse micelles, including ribosomes and plasmids, (Imre and Luisi, 1982 Palazzo and Luisi, 1992 Pietrini and Luisi, 2002 2004 Ousfuri et al, 2005), which also gives rise to a series of interesting structural and thermodynamic questions. In particular, high-molecular-weight... 

The lipidic cubic phase has recently been demonstrated as a new system in which to crystallize membrane proteins [143, 144], and several examples [143, 145, 146] have been reported. The molecular mechanism for such crystallization is not yet clear, but the interfacial water and transport are believed to play an important role in nucleation and crystal growth [146, 147], Using a related model system of reverse micelles, drastic differences in water behavior were observed both experimentally [112, 127, 128, 133-135] and theoretically [117, 148, 149]. In contrast to the ultrafast motions of bulk water that occurs in less than several picoseconds, significantly slower water dynamics were observed in hundreds of picoseconds, which indicates a well-ordered water structure in these confinements. 

Surfactants are organic molecules that possess a nonpolar hydrocarbon tail and a polar head. The polar head can be anionic, cationic, or nonionic. Because of the existence of the two moieties in one molecule, surfactants have limited solubility in polar and nonpolar solvents. Their solubility is dependent on the hydrophile-lipophile balance of their molecular structure. At a critical concentration, they form aggregates in either type of solvent. This colloidal aggregation is referred to as micellization, and the concentration at which it occurs is known as the critical micelle concentration. The term micelle was coined by McBain (7) to designate the aggregated solute. In water or other polar solvents, the micellar structure is such that the hydrophobic tails of the surfactant molecules are clustered together and form the interior of a sphere. The surface of the sphere consists of the hydrophilic heads. In nonpolar solvents, the orientation of the molecules is reversed. 

The microemulsion method utilizes a water/oil/surfactant system to construct a micro reactor, in which NCs could be s)mthesized. The microemulsions have a wide range of applications from oil recovery fo fhe s)mfhesis of nanoparticles. Microemulsion is a system of water, oil, and surfactant, and it is an optically isotropic and thermod3mamically stable solution. At molecular scale, the microemulsion is heterogeneous with an internal structure either of nanospherical monosized droplefs (micelles or reverse micelles) or a bicontinuous phase, depending on the given temperature as well as the ratio of its constituents (Eriksson et al., 2004). The small droplets could be utilized as microreactors in order to s)mthesize the fine NCs in a controllable way. 

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. 

In this chapter, the recent progress in the understanding of the nature and dynamics of excess (solvated) electrons in molecular fluids composed of polar molecules with no electron affinity (EA), such as liquid water (hydrated electron, and aliphatic alcohols, is examined. Our group has recently reviewed the literature on solvated electron in liquefied ammonia and saturated hydrocarbons and we refer the reader to these publications for an introduction to the excess electron states in such liquids. We narrowed this review to bulk neat liquids and (to a much lesser degree) large water anion clusters in the gas phase that serve as useful reference systems for solvated electrons in the bulk. The excess electrons trapped by supramolecular structures (including single macrocycle molecules ), such as clusters of polar molecules and water pools of reverse micelles in nonpolar liquids and complexes of the electrons with cations in concentrated salt solutions, are examined elsewhere. 

Phospholipids are the major lipid building blocks most membranes and their molecules comprise of a hydrophobic (acyl chain) and a hydrophilic (polar) head group. The relative size of the hydrophobic tails and hydrophilic head of the molecule characterizes the molecular shape and determines the structure of the molecular assemblies in contact with w ater. Molecules with polar and non-polar regions (PC, PS, PI, Sphm) of equal size have a cylindrical shape and form lipid bilayers. Molecules that have a larger non-polar region are cone-shaped (PE, PA, Choi, Car), and form reversed micelles, in contact to water. When the polar region is larger (lysophospholipids) the molecule assembles an inverted cone and form micelles. Fig. (8). 

A significant amount of work has demonstrated the feasibility and the interest of reversed micelles for the separation of proteins and for the enhancement or inhibition of specific reactions. The number of micellar systems presently available and studied in the presence of proteins is still limited. An effort should be made to increase the number of surfactants used as well as the set of proteins assayed and to characterize the molecular mechanism of solubilization and the microstructure of the laden organic phases in various systems, since they determine the efficiency and selectivity of the separation and are essential to understand the phenomena of bio-activity loss or preservation. As the features of extraction depend on many parameters, particular attention should be paid to controlling all of them in each phase. Simplified thermodynamic models begin to be developed for the representation of partition of simple ions and proteins between aqueous and micellar phases. Relevant experiments and more complete data sets on distribution of salts, cosurfactants, should promote further developments in modelling in relation with current investigations on electrolytes, polymers and proteins. This work could be connected with distribution studies achieved in related areas as microemulsions for oil recovery or supercritical extraction (74). In addition, the contribution of physico-chemical experiments should be taken into account to evaluate the size and structure of the micelles. 

It is of particular interest to be able to correlate solubility and partitioning with the molecular structure of the surfactant and solute. Likes dissolve like is a well-worn phrase that appears applicable, as we see in microemulsion formation where reverse micelles solubilize water and normal 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 structure. 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... 

There are a variety of other types of nonbilayer lipid structures such as reversed micelles sandwiched between monolayers of the lipid bilayers in vivo, while the main structural pattern of biological membranes is the flat bilayer of lipid molecules. These nonbilayer structures can explain many processes occurring in the living cell, such as fusion, and exo- and endo-cytosis. Because the water in the reversed micelle resembles that adjacent to biological membranes or biological reversed micelle-like microcompartments, reversed micelles may be an appropriate model for investigating biological catalysis at the molecular level [3-5]. 

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