Organized media micelles

Crooks et al. reported the transfer of amine-functionalized poly(amidoamine) dendrimers into toluene containing dodecanoic acid [198], The method is based on the formation of ion pairs between the fatty acids and the terminal amine-groups. These dendrimer-fatty acid complexes resemble unimolecular inverted micelles and could be used as phase transfer vehicles for the transport of Methyl Orange, an anionic dye molecule, into an organic medium. 

Unlike isotropic media, where molecules have equal mobility and conformational flexibility in all dimensions, in an organized medium their mobility and flexibility are restricted or constrained in at least one dimension. For example, the reaction cavities of a micelle and cyclodextrins are made up of a hydrophobic core and a hydrophilic exterior (Fig. 11). A highly polar boundary separates the hydrophobic core from the aqueous exterior. Such a boundary provides unique features to these media that are absent in isotropic solution. Translational motion of a guest present within the reaction cavity is hindered by the well-defined boundary. 

Finally, it should be mentioned that a series of enzymes have been trapped in reverse micelles as a method of dispersing the hydrophilic biocatalysts in a very unpolar organic medium [31]. 

Since the dynamics of the twisted intramolecular charge transfer (TICT) process is very sensitive to the polarity of the medium, the local polarity of an organized medium may also be determined from the rate of the HCT process. For TNS, which is nearly nonfluorescent in water ((j)f = 10 and Xf = 60 ps), the emission quantum yield and lifetime increases nearly 50 times on binding to cyclodextrins and more than 500 times on binding to a neutral micelle, TX -100 [86]. Such a dramatic increase in the emission intensity and lifetime arises because of the marked reduction of the nonradiative HCT process inside the less polar microenvironment of the cyclodextrins and the micelle. Determination of the micropolarities of various organized assemblies using TICT probes has been surveyed quite extensively in several recent reviews [5b-d,f,86]. Therefore, in this chapter we will focus only on some selected works not covered in the earlier reviews. 

Reverse micelles are formed by association of polar headgroups of amphiphiles with colloidal drops of water in an organic medium. A favored surfactant seems to be AOT (sodium-di[2-ethylhexyl]sulfosuccinnate) but SDS and tetraalkylammoni-um salts have also proved to be useful. Like aqueous micelles, reverse micelles exist in highly diluted systems. 

As displayed in Table 1, the highest incorporation of starch nanopartides within reverse micelles was found by using the AOT/isooctane microemulsion system. Based on these results, the AOT/isooctane system was used to prepare surfactant coated starch nanopartides. To isolate the AOT-coated starch nanopartides, the isooctane was removed under reduced pressure. Previous studies in our laboratory showed that toluene was a preferred organic medium in which to perform Novozyme 435 catalyzed transesterification reactions(29). Hence, the AOT-coated starch nanospheres were solubilized in toluene and evaluated for modification reactions. 

In consideration of the thermodynamic aspects, and from the early results of Price [5] and Quintana et al. [ 135], it is now well established that the micellization of block copolymers in organic medium is an enthalpic driven process, the micellar core formation being the main contribution to the exothermic process. 

A micelle-bound substrate will experience a reaction environment different from bulk water, leading to a kinetic medium effect. Hence, micelles are able to catalyse or inhibit organic reactions. Research on micellar catalysis has focused on the kinetics of the organic reactions involved. An overview of the multitude of transformations that have been studied in micellar media is beyond the scope of this chapter. Instead, the reader is referred to an extensive set of review articles and monographs" ... 

Different type of reaction system containing organic solvent can be classified in a simple way. To accomplish this we first distinguished between microaqueous organic systems with a continuous organic phase, then reversed micelles stabilized with surfactant and a liquid-liquid biphasic system in which distinct organic and aqueous phase are mixed. The latter medium is discussed in this paper. 

Most of the applications of the micelles in aqueous medium are based on the association or solubilization of solutes. The interactions between both can be electrostatic, hydrophobic, or, more normally, a combination of both effects [23, 24], It was thought initially that hydrophobic solutes dissolve in the core of the micelle in the same way in which they would do so in an organic solvent, but... 

It is easy to understand the lower reactivity of non-ionic nucleophiles in micelles as compared with water. Micelles have a lower polarity than water and reactions of non-ionic nucleophiles are typically inhibited by solvents of low polarity. Thus, micelles behave as a submicroscopic solvent which has less ability than water, or a polar organic solvent, to interact with a polar transition state. Micellar medium effects on reaction rate, like kinetic solvent effects, depend on differences in free energy between initial and transition states, and a favorable distribution of reactants from water into a micellar pseudophase means that reactants have a lower free energy in micelles than in water. This factor, of itself, will inhibit reaction, but it may be offset by favorable interactions with the transition state and, for bimolecular reactions, by the concentration of reactants into the small volume of the micellar pseudophase. 

Micelles are capable of self-replication if an appropriate chemical reaction occurs within the micelle itself that produces more of the same amphiphile that forms the micelle. Such self-replication has been demonstrated for both ordinary micelles in an aqueous medium [139] as well as for reverse micelles, [140] which are spherules of water stabilized by an amphiphile in an organic solvent. Some of the prebiotic potentialities of replicating membranous vesicles have been investigated, [141] and they have been characterized as "minimum protocells. [142]... 

The rate constants and k represent rate constants for a surface reaction and have units m mol s and s respectively. The accelerative effects are about 10 -10 fold. They indicate that both reactants are bound at the surface layer of the micelle (surfactant-water interface) and the enhanced rates are caused by enhanced reactant concentration here and there are no other significant effects. Similar behavior is observed in an inverse micelle, where the water phase is now dispersed as micro-droplets in the organic phase. With this arrangement, it is possible to study anion interchange in the tetrahedral complexes C0CI4 or CoCl2(SCN)2 by temperature-jump. A dissociative mechanism is favored, but the interpretation is complicated by uncertainty in the nature of the species present in the water-surfactant boundary, a general problem in this medium. 

The catalytic principle of micelles as depicted in Fig. 6.2, is based on the ability to solubilize hydrophobic compounds in the miceUar interior so the micelles can act as reaction vessels on a nanometer scale, as so-called nanoreactors [14, 15]. The catalytic complex is also solubihzed in the hydrophobic part of the micellar core or even bound to it Thus, the substrate (S) and the catalyst (C) are enclosed in an appropriate environment In contrast to biphasic catalysis no transport of the organic starting material to the active catalyst species is necessary and therefore no transport limitation of the reaction wiU be observed. As a consequence, the conversion of very hydrophobic substrates in pure water is feasible and aU the advantages mentioned above, which are associated with the use of water as medium, are given. Often there is an even higher reaction rate observed in miceUar catalysis than in conventional monophasic catalytic systems because of the smaller reaction volume of the miceUar reactor and the higher reactant concentration, respectively. This enhanced reactivity of encapsulated substrates is generally described as micellar catalysis [16, 17]. Due to the similarity to enzyme catalysis, micelle and enzyme catalysis have sometimes been correlated in literature [18]. 

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