Micelle supported

The rapid development of biotechnology during the 1980s provided new opportunities for the application of reaction engineering principles. In biochemical systems, reactions are catalyzed by enzymes. These biocatalysts may be dispersed in an aqueous phase or in a reverse micelle, supported on a polymeric carrier, or contained within whole cells. The reactors used are most often stirred tanks, bubble columns, or hollow fibers. If the kinetics for the enzymatic process is known, then the effects of reaction conditions and mass transfer phenomena can be analyzed quite successfully using classical reactor models. Where living cells are present, the growth of the cell mass as well as the kinetics of the desired reaction must be modeled [16, 17]. 

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]. 

The energetics and kinetics of film formation appear to be especially important when two or more solutes are present, since now the matter of monolayer penetration or complex formation enters the picture (see Section IV-7). Schul-man and co-workers [77, 78], in particular, noted that especially stable emulsions result when the adsorbed film of surfactant material forms strong penetration complexes with a species present in the oil phase. The stabilizing effect of such mixed films may lie in their slow desorption or elevated viscosity. The dynamic effects of surfactant transport have been investigated by Shah and coworkers [22] who show the correlation between micellar lifetime and droplet size. More stable micelles are unable to rapidly transport surfactant from the bulk to the surface, and hence they support emulsions containing larger droplets. 

The majority of practical micellar systems of Tionnal micelles use water as tire main solvent. Reverse micelles use water immiscible organic solvents, altlrough tire cores of reverse micelles are usually hydrated and may contain considerable quantities of water. Polar solvents such as glycerol, etlrylene glycol, fonnamide and hydrazine are now being used instead of water to support regular micelles [10]. Critical fluids such as critical carbon dioxide are... 

The fonnation of surface aggregates of surfactants and adsorbed micelles is a challenging area of experimental research. A relatively recent summary has been edited by Shanna [51]. The details of how surfactants pack when aggregated on surfaces, with respect to the atomic level and with respect to mesoscale stmcture (geometry, shape etc.), are less well understood than for micelles free in solution. Various models have been considered for surface surfactant aggregates, but most of these models have been adopted without finn experimental support. 

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. 

Amorphous silica, with pore sizes in the range 1-10 nm is a common support for base catalysts, whilst more structured pore sizes can be made by what is known as the sol-gel method. In this method a micelle is... 

An effect similar to that of cetyltrimethylammonium bromide micelles can be realized through the use of microgels with trimethylamino side-chain function and this may then allow solid supported microgels to be used in a continuous reaction. Evans et al. (1995) have utilized microgels incorporating 2-tetradecyl dimethyl amino/ethyl methacrylate bromide, which solubilizes aryl laurate esters in an aquous solution and catalyses the alkaline hydrolysis. 

The solvation dynamics of the three different micelle solutions, TX, CTAB, and SDS, exhibit time constants of 550, 285, 180 ps, respectively. The time constants show that solvent motion in these solutions is significantly slower than bulk water. The authors attribute the observed time constants to water motion in the Stern layer of the micelles. This conclusion is supported by the steady-state fluorescence spectra of the C480 probe in these solutions. The spectra exhibit a significant blue shift with respect the spectrum of the dye in bulk water. This spectral blue shift is attributed to the probe being solvated in the Stern layer and experiencing an environment with a polarity much lower than that of bulk water. 

This work also shows that the time constants for the ionic surfactant micelle solutions are twice as fast as the TX solution time constant. Differences between the Stern layers of the micelles appear to be the charge of the surfactant polar headgroups and the presence of counterions. However, these differences do not account for the observed dynamics. Since the polar headgroups and counterions should interfact more strongly with the water molecules, the water motion at the interface should be slower. This view is supported by recent investigations where systematic variation of surfactant counter-... 

The observation of slow, confined water motion in AOT reverse micelles is also supported by measured dielectric relaxation of the water pool. Using terahertz time-domain spectroscopy, the dielectric properties of water in the reverse micelles have been investigated by Mittleman et al. [36]. They found that both the time scale and amplitude of the relaxation was smaller than those of bulk water. They attributed these results to the reduction of long-range collective motion due to the confinement of the water in the nanometer-sized micelles. These results suggested that free water motion in the reverse micelles are not equivalent to bulk solvation dynamics. 

We have been developing methods to prepare and characterize supported attune catalysts nsing readily available commercial snpports. One potential means of depositing amines on oxide surfaces is shown in Scheme 38.1, in which the micelle s role is to space the amines on the snrface. Cnrrent work is directed towards characterizing these samples, particularly applying flnorescence resonance energy transfer (FRET) techniques. 

One of the most promising applications of enzyme-immobilized mesoporous materials is as microscopic reactors. Galameau et al. investigated the effect of mesoporous silica structures and their surface natures on the activity of immobilized lipases [199]. Too hydrophilic (pure silica) or too hydrophobic (butyl-grafted silica) supports are not appropriate for the development of high activity for lipases. An adequate hydrophobic/hydrophilic balance of the support, such as a supported-micelle, provides the best route to enhance lipase activity. They also encapsulated the lipases in sponge mesoporous silicates, a new procedure based on the addition of a mixture of lecithin and amines to a sol-gel synthesis to provide pore-size control. 

Fig. 5 Membrane models for NMR structure analysis, (a) An isotropic detergent micelle (left) is compared to the dimensions of lipid bilayers (right), (b) Macroscopically oriented membrane samples can be prepared on solid support, as nanodiscs, or as magnetically oriented bicelles. (c) Nomenclature and variability of liposomes small (SUV, 20-40 nm), intermediate (IUV, 40-60 nm), large (LUV, 100-400 nm), and giant unilamellar vesicles (GUV, 1 pm) multi-lamellar (MLV), oligo-lamellar (OLV) and highly heterogeneous multi-oligo-lamellar vesicles (MOLV)...

Most examples discussed so far made use of amorphous inorganic supports or sol-gel processed hybrid polymers. Highly disperse materials have recently become accessible via standard processes and, as a result, materials with various controlled particle size, pore diameter are now available. Micelle-templated synthesis of inorganic materials leads to mesoporous materials such as MCM-41, MCM-48, MSU, and these have been extensively used as solid supports for catalysis [52]. Modifications of the polarity of the material can increase the reactivity of the embedded centre, or can decrease its susceptibility to deactivation. In rare cases, enhanced stereo- or even... 

Water is highly dispersable it has a high tendency to support micelle and/or microemulsion formation. These tendencies may be enhanced by additives such as surfactants... 

By combining (1), (3) and (4), expressions (5) and (6) are obtained. These, or similar, equations readily explain why first-order rate constants of micelle-assisted bimolecular reactions typically go through maxima with increasing surfactant concentration if the overall reactant concentration is kept constant. Addition of surfactant leads to binding of both reactants to micelles, and this increased concentration increases the reaction rate. Eventually, however, increase in surfactant concentration dilutes the reactants in the micellar pseudophase and the rate falls. This behavior supports the original assumption that substrate in one micelle does not react with reactant in another, and that equilibrium is maintained between aqueous and micellar pseudophases. 

The similarity for many reactions of second-order rate constants in aqueous and micellar pseudophases, and the observation that substrate hydrophobicity usually affects binding and not inherent reactivity in the micelle, suggests that substrate location or orientation is relatively unimportant. This conclusion is strongly supported by a quantitative analysis of the effects of CTABr micelles on the reaction of OH- and arylsulfonylalkyl arenesulfonates (16) (van der Langkruis and Engberts, 1984). 

All the evidence suggests that in solvents of high water content the microemulsion droplets are very similar to micelles in their ability to promote bimolecular reactions, and other probes support this view. 

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