Microemulsions reversed

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... 

These are transparent or translucent systems covering the size range from 5 to 50nm. Unlike emulsions and nanoemulsions (which are only kinetically stable), microemulsions are thermodynamically stable as the free energy of their formation is either zero or negative. Microemulsions are better considered as swollen micelles normal micelles can be swollen by some oil in the core of the micelle to form O/W microemulsions. Reverse micelles can be swollen by water in the core to form W/O microemulsions. 

Oldfield, C., Enzymes in water-in-oil microemulsions ( reversed micelles ) principles and appbcations, in Biotechnology and Genetic Engineering Reviews, Tombs, M.P., Ed., Vol. 12, Intercept Ltd., Andover, U.K., 155-ill, 1994. 

Figure 9.10. Schematic representations of the possible effects of the presence of a solute on the observed radius of water in oil microemulsions (reversed-micelles). Since the radius is imposed by the surface-to-volume ratio, localization in surfactant layers shrinks the radius, while localization in the core increases the radius. Separate micellization may induce polydispersity, while localization in the bulk oil has no effect on the reversed-micelle...

A reverse microemulsion method is applied for the preparation of composite nanoparticles [96]. By controlling the amount of surfactant and water, fabrication of particles in water-in-oil microemulsions (reverse micelles) affords great control over the size and shape of the particles [15]. This procedure takes advantage of two selforganizing processes. First, the reverse micelles are used to synthesize metallic... 

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). 

Micelles are mainly important because they solubilize immiscible solvents in their cores. Nonnal micelles solubilize relatively large quantities of oil or hydrocarbon and reverse micelles solubilize large quantities of water. This is because the headgroups are water loving and the tailgroups are oil loving. These simple solubilization trends produce microemulsions (see section C2.3.11). 

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... 

Figure C2.3.10. Ternary phase diagram of surfactant, oil and water illustrating tire (regular) and (reverse) L2 microemulsion domains.

Microemulsions or reverse micelles are composed of enzyme-containing, surfactant-stabiHzed aqueous microdroplets in a continuous organic phase. Such systems may be considered as a kind of immobilization in enzymatic synthesis reactions. 

Cosolvents ana Surfactants Many nonvolatile polar substances cannot be dissolved at moderate temperatures in nonpolar fluids such as CO9. Cosolvents (also called entrainers, modifiers, moderators) such as alcohols and acetone have been added to fluids to raise the solvent strength. The addition of only 2 mol % of the complexing agent tri-/i-butyl phosphate (TBP) to CO9 increases the solubility ofnydro-quinone by a factor of 250 due to Lewis acid-base interactions. Veiy recently, surfac tants have been used to form reverse micelles, microemulsions, and polymeric latexes in SCFs including CO9. These organized molecular assemblies can dissolve hydrophilic solutes and ionic species such as amino acids and even proteins. Examples of surfactant tails which interact favorably with CO9 include fluoroethers, fluoroacrylates, fluoroalkanes, propylene oxides, and siloxanes. 

The main supramolecular self-assembled species involved in analytical chemistry are micelles (direct and reversed), microemulsions (oil/water and water/oil), liposomes, and vesicles, Langmuir-Blodgett films composed of diphilic surfactant molecules or ions. They can form in aqueous, nonaqueous liquid media and on the surface. The other species involved in supramolecular analytical chemistry are molecules-receptors such as calixarenes, cyclodextrins, cyclophanes, cyclopeptides, crown ethers etc. Furthermore, new supramolecular host-guest systems arise due to analytical reaction or process. 

Microemulsion and miniemulsion polymerization processes differ from emulsion polymerization in that the particle sizes are smaller (10-30 and 30-100 nm respectively vs 50-300 ran)77 and there is no discrete monomer droplet phase. All monomer is in solution or in the particle phase. Initiation usually takes place by the same process as conventional emulsion polymerization. As particle sizes reduce, the probability of particle entry is lowered and so is the probability of radical-radical termination. This knowledge has been used to advantage in designing living polymerizations based on reversible chain transfer (e.g. RAFT, Section 9.5.2)." 2... 

On a microscopic scale, a microemulsion is a heterogeneous system and, depending on the relative amounts of the constituents, three main types of structures can be distinguished [69] oil in water (OAV, direct micellar structure), water in oil (W/O, reverse micellar structure) and a bicontinuous structure (B) (Figure 6.1). By adding oil in water, OAV dispersion evolves smoothly to a W/O dispersion via bicontinuous phases. 

Generation of nanoparticles under Langmuir monolayers and within LB films arose from earlier efforts to form nanoparticles within reverse micelles, microemulsions, and vesicles [89]. Semiconductor nanoparticles formed in surfactant media have been explored as photocatalytic systems [90]. One motivation for placing nanoparticles within the organic matrix of a LB film is to construct a superlattice of nanoparticles such that the optical properties of the nanoparticles associated with quantum confinement are preserved. If mono-layers of capped nanoparticles are transferred, a nanoparticle superlattice can be con-... 

As a result of the micellar environment, enzymes and proteins acquire novel conformational and/or dynamic properties, which has led to an interesting research perspective from both the biophysical and the biotechnological points of view [173-175], From the comparison of some properties of catalase and horseradish peroxidase solubilized in wa-ter/AOT/n-heptane microemulsions with those in an aqueous solution of AOT it was ascertained that the secondary structure of catalase significantly changes in the presence of an aqueous micellar solution of AOT, whereas in AOT/n-heptane reverse micelles it does not change. On the other hand, AOT has no effect on horseradish peroxidase in aqueous solution, whereas slight changes in the secondary structure of horseradish peroxidase in AOT/n-heptane reverse micelles occur [176],... 

Even entrapment of entire cells within reversed micelles without loss of their functionality has been achieved. For example, mitochondria and bacteria (Actinobacter cal-coaceticus, Escherichia coli, Corynebacterium equi) have been successfully solubilized in a microemulsion consisting of isopropyl pahnitate, polyoxyethylene sorbitan trioleate [162], Enhanced hydrogen photoproduction by the bacterium Rhodopseudomonas sphaeroides or by the coupled system Halobacterium halobium and chloroplasts organelles entrapped inside the aqueous core of reversed micelles with respect to the same cells suspended in normal aqueous medium has been reported [183,184],... 

Moreover, stable liquid systems made up of nanoparticles coated with a surfactant monolayer and dispersed in an apolar medium could be employed to catalyze reactions involving both apolar substrates (solubilized in the bulk solvent) and polar and amphiphilic substrates (preferentially encapsulated within the reversed micelles or located at the surfactant palisade layer) or could be used as antiwear additives for lubricants. For example, monodisperse nickel boride catalysts were prepared in water/CTAB/hexanol microemulsions and used directly as the catalysts of styrene hydrogenation [215]. 

It must be pointed out that formation and stabihzation of nanoparticles in reversed micelles are the result of a delicate equilibrium among many factors. In addition, lacking a general theory enabling the selection a priori of the optimal conditions for the synthesis of nanoparticles of a given material with the wanted properties, stable nanoparticles containing w/o microemulsions can be achieved only in some system-specific and experimentally selected conditions. 

Another mechanism postulated to explain the conductometric behavior of these microemulsions attributes it to the transfer of sodium counterions from a reversed micelle to another through water channels opened by intermicellar coalescence [255-258],... 

By dynamic light scattering it was found that, in surfactant stabilized dispersions of nonaqueous polar solvents (glycerol, ethylene glycol, formamide) in iso-octane, the interactions between reversed micelles are more attractive than the ones observed in w/o microemulsions, Evidence of intermicellar clusters was obtained in all of these systems [262], Attractive intermicellar interactions become larger by increasing the urea concentration in water/AOT/ -hexane microemulsions at/ = 10 [263],... 

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