Reversed micelle processes

Fig. 6 shows the Raman response of three different samples of gadolinium doped eeria (GDQ nanoparticles produced using reverse micelle processing with different production parameters [65]. The Raman spectrum is dominated by a single intense, well defined Raman peak at about 460cm and... 

Hwang BJ, Hsu KF, Hu SK, Cheng MY, Chou TC (2009) Template-free reverse micelle process for the synthesis of a rod-like LiFeP04/C composite cathode for hthium batteries. J Power Sourc 194 515-519... 

A large fraction of the hazardous waste generated in industry is in the form of dilute aqueous solutions. The special challenges of separation in highly dilute solutions may be met by the development of new, possibly liquid-filled, membranes by processes involving selective concentration of toxic chemicals on the surfaces of particles or by the use of reversed micelles. 

Studies of reversed micelles dispersed in supercritical fluids have shown their ability to solubihze hydrophihc substances, including biomolecules and dyes, opening the door to many new applications [60,61]. In particular, solutions of reversed micelles in liquid and supercritical carbon dioxide have been suggested as novel media for processes generating a minimum amount of waste and with a low energy requirement [62]. 

In the case of water-containing AOT-reversed micelles, less than 1 in 1000 intermi-cellar coUisions leads to micelle coalescence followed by separation and a material exchange process occurring in the microsecond to millisecond time scale [3,79]. 

The importance of the material exchange process can hardly be overemphasized since it is the mechanism whereby the equUibrium miceUar size and polydispersity are reached and maintained, the reversed micelles of ionic surfactants become charged, polar and amphiphilic solubilizates are transported, and hydrophilic reactants can come in... 

The solubilization of water in lecithin-reversed micelles has been found to be an exothermic process. This finding confirms that water interacts with the zwitterionic head group of lecithin, promoting the formation of strong intermolecular H bonds [104]. 

In recent decades, many investigations have been carried out on the solubilization and on the physicochemical characterization of a wide variety of substances confined in water-containing reversed micelles. Even if these studies have not produced a general theory to predict a priori all the effects accompanying the solubihzation process, some general aspects nonetheless have been underhned. In the following, the results of some of these investigations, selected to show the extent of some peculiar behaviors, will be reported. 

The different location of polar and amphiphilic molecules within water-containing reversed micelles is depicted in Figure 6. Polar solutes, by increasing the micellar core matter of spherical micelles, induce an increase in the micellar radius, while amphiphilic molecules, being preferentially solubihzed in the water/surfactant interface and consequently increasing the interfacial surface, lead to a decrease in the miceUar radius [49,136,137], These effects can easily be embodied in Eqs. (3) and (4), aUowing a quantitative evaluation of the mean micellar radius and number density of reversed miceUes in the presence of polar and amphiphilic solubilizates. Moreover it must be pointed out that, as a function of the specific distribution law of the solubihzate molecules and on a time scale shorter than that of the material exchange process, the system appears polydisperse and composed of empty and differently occupied reversed miceUes [136],... 

In addition to the degree of hydrophilicity of the solubilizates, their size and structure, the size of the host microregions, or the occurrence of specific processes must be taken into account in order to rationalize the driving forces of the solubilization process and of the solubilization site within water-containing reversed micelles [25,138,139],... 

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]. 

Taking into account that the state of nanoparticles is thermodynamically unstable against an unlimited growth, the physicochemical processes allowing reversed micelles to lead to stable dispersions and to a size control of nanoparticles are ... 

It follows that in spite of the apolar coat surrounding water-containing AOT-reversed micelles and their dispersion in an apolar medium, some microscopic processes are able to establish intermicellar attractive interactions. These intermicellar interactions between AOT-reversed micelles increase with increasing temperature or the chain length of the hydrocarbon solvent molecule, thus leading to the enhancement of the clustering process [244-246], whereas they are reduced in the presence of inorganic salts [131]. 

Investigation of water motion in AOT reverse micelles determining the solvent correlation function, C i), was first reported by Sarkar et al. [29]. They obtained time-resolved fluorescence measurements of C480 in an AOT reverse micellar solution with time resolution of > 50 ps and observed solvent relaxation rates with time constants ranging from 1.7 to 12 ns. They also attributed these dynamical changes to relaxation processes of water molecules in various environments of the water pool. In a similar study investigating the deuterium isotope effect on solvent motion in AOT reverse micelles. Das et al. [37] reported that the solvation dynamics of D2O is 1.5 times slower than H2O motion. 

Effectiveness of a crude oil demulsifier is correlated with the lowering of shear viscosity and dynamic tension gradient of the oil-water interface. Using the pulsed drop technique, the interfacial dilational modulii with different demulsifiers have been measured. The interfacial tension relaxation occurs faster with an effective demulsifier. Electron spin resonance with labeled demulsifiers indicate that the demulsifiers form reverse micelle like clusters in bulk oil. The slow unclustering of the demulsifier at the interface appears to be the rate determining step in the tension relaxation process. 

Other claimed matter DBT for enrichment, biocatalyst preparation contacting process Enzymes contacting process Pure compounds as feedstock Membrane fragments and extracts Cell-free extract (envelope and its fragments + associated enzyme) reversible emulsion microemulsion reverse micelles Cell-free enzyme preparation microemulsified process RR and derivatives and other biocatalyst concepts + any known microorganism active for C—S bond cleavage... 

Figure 14.23 Silica nanoparticles containing fluorescent dye molecules can be prepared using a reverse micelle suspension process (a) The water-in-oil emulsion is formed with the aqueous phase droplets containing TEOS and dye molecules in detergent, (b) The final particles contain entrapped dye within the silica particle matrix, creating highly fluorescent particles.

M.T. Perez Pita, A.J. Reviejo, F.J.M. de Villena, and J.M. Pingarron, Amperometric selective biosensing of dimethyl- and diethyldithiocarbamates based on inhibition processes in a medium of reversed micelles. Anal. Chim. Acta 340, 89-97 (1997). 

For a while there was some confusion in the literature the NMR studies indicated a rapid process was occurring while the flow studies indicated something slower. We now understand that they were looking at different events. Reversed micelles behave differently and fusion of the micelle is an important factor in solute exchange [Atik, S. S. Thomas, J. K. J. Am.Chem. Soc. 1981, 103, 3543]. ... 

The reactant does not form reverse micelles under the conditions of the process, in which case a surfactant, and sometimes also a cosurfactant, must be added to the organic phase in order to produce a reverse micellar phase. In this case the reverse micelles are usually mixed, i.e., they include in the micellar shell the reactant and the additives. 

Counterion extraction Due to the relative slowness of back extraction based on the methods above, the back-extraction of proteins encapsulated in AOT reverse micelles was evaluated by adding a counterionic surfactant, either TOMAC or DTAB, to the reverse micelles [33]. This novel backward transfer method gave higher backward extraction yields compared to the conventional method. The back-extraction process with TOMAC was found to be 100 times faster than back-extraction with the conventional method, and as much as three times faster than forward extraction. The 1 1 complexes of AOT and TOMAC in the solvent phase could be efficiently removed using adsorption onto montmorillonite so that the organic solvent could be reused. 

For the scale-up of reverse micelle extractions, it is important to know which factors determine the mass transfer rate to or from the reverse micelle phase. So far most work has concentrated on the kinetics of solubilization of water molecules [34,35], protons [36], metal ions [20,35,37,38 0], amino acids [41], and proteins [8,35,42,43]. There are two separate processes forward transfer, which is transfer of solute from the aqueous to the reverse micelle phase, and back transfer, which is the antithesis of the first one. 

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