Exchange between surfactant reaction

Photoredox reactions at organized assemblies such as micelles and microemulsions provide a convenient approach for modeling life-sustaining processes. Micelles are spontaneously formed in solutions in the presence of surfactants above a certain critical concentration. In aqueous solutions, the hydrophobic tails of the surfactant form aggregates with the polar head facing toward the aqueous environment, as depicted in Fig. 9. The hydrophobic core in micelles is amorphous and exhibits properties similar to a liquid hydrocarbon. The polar heads are also randomly oriented, generating an electrical double layer around the micelle structure. In this respect, surface properties of micelles can be somewhat correlated with the polarized ITIES. The structure of micelles is in dynamic equilibrium, in which monomers are exchanged between bulk solution and the assembly. 

To overcome most of solubilization problems, colloidal surfactant systems (e.g. micelles, liquid crystals, microemulsions, vesicles, emulsions, etc.) are attracting a great deal of attention as alternative reaction media (Walde 1996 Holmberg 1997 Antonietti 2001). Their advantages are they possess micro- and nanostmctures consisting of well-defined hydrophilic and lipophilic domains separated by surfactant films with very large interfacial area, the exchange between chemical species... 

Micelles are not frozen objects. They are in dynamic equilibrium with the free (nomnicellized) surfactant. Surfactants are constantly exchanged between micelles and the intermicellar solution (exchange process), and the residence time of a surfactant in a micelle is fmite. Besides, micelles have a finite lifetime. They constantly form and break up via two identified pathways by a series of stepwise entry/exit of one surfactant A at a time into/from a micelle (Reaction 1) or by a series of frag-mentation/coagulation reactions involving aggregates A, and Aj (Reaction... 

As already mentioned in the beginning, triplet-triplet annihilation reactions as well as delayed fluorescence of amphiphilic pyrene derivatives were used to probe the microemulsion dynamics. [68]. The fact that the interacting species were associated with the surfactant monolayer made it possible to probe the dynamics in an unusual way. It was found that at low occupation numbers, the annihilation between triplets associated with different droplets occurred at a rate close to diffusion-controlled. Evidently, this reaction did not require a fusion or exchange between the aqueous compartments of the droplets, which is the process we discussed above and which would be slower than diffusion-controlled by two or three orders of magnitude. 

The kinetics of surfactant exchange between gemini surfactant micelles and intermicellar solution was investigated. Gemini surfactants with short alkyl chains, 8-6-8, 2Br" and 8-3-8, 2Br", were found to behave similarly to their monomeric counterparts [35]. Gemini surfactants associate to, and dissociate from, their micelles in a single step (the two chains at a time). The association reaction is nearly diffusion controlled, whereas the rate of dissociation (exit) depends strongly on the surfactant hydrophobicity. 

This reaction can also be considered as that by which one surfactant is exchanged between the two micelles A and An-1. It is often referred to as surfactant exchange. 

Specific-ion electrodes are expensive, temperamental and seem to have a depressingly short life when exposed to aqueous surfactants. They are also not sensitive to some mechanistically interesting ions. Other methods do not have these shortcomings, but they too are not applicable to all ions. Most workers have followed the approach developed by Romsted who noted that counterions bind specifically to ionic micelles, and that qualitatively the binding parallels that to ion exchange resins (Romsted 1977, 1984). In considering the development of Romsted s ideas it will be useful to note that many micellar reactions involving hydrophilic ions are carried out in solutions which contain a mixture of anions for example, there will be the chemically inert counterion of the surfactant plus the added reactive ion. Competition between these ions for the micelle is of key importance and merits detailed consideration. In some cases the solution also contains buffers and the effect of buffer ions has to be considered (Quina et al., 1980). 

Interactions between cationic micelles and uni- and divalent anions have been treated quantitatively by solving the Poisson-Boltzmann equation in spherical symmetry and considering both Coulombic and specific attractive forces. Predicted rate-surfactant profiles are similar to those based on the ion-exchange and mass-action models (Section 3), but fit the data better for reactions in solutions containing divalent anions (Bunton, C. A. and Moffatt, J. R. (1985) J. Phys. Chem. 1985, 89, 4166 1986,90, 538). 

A pseudophase ion exchange model has been applied to reactions in micellar systems with varying success (1-7). According to this model, the distribution of nucleophile is considered to depend on the ion-exchange equilibrium between the nucleophile and the surfactant counterion at the micelle surface. This leads to a dependence on the ion-exchange constant (K g) as well as on the degree of dissociation (a) of the surfactant counterion. The ion exchange (IE) model has recently been extended to oil in water microemulsions (8). 

For a surface active betaine ester the rate of alkaline hydrolysis shows significant concentration dependence. Due to a locally elevated concentration of hydroxyl ions at the cationic micellar surface, i.e., a locally increased pH in the micellar pseudophase, the reaction rate can be substantially higher when the substance is present at a concentration above the critical micelle concentration compared to the rate observed for a unimeric surfactant or a non-surface active betaine ester under the same conditions. This behavior, which is illustrated in Fig. 10, is an example of micellar catalysis. The decrease in reaction rate observed at higher concentrations for the C12-C18 1 compounds is a consequence of competition between the reactive hydroxyl ions and the inert surfactant counterions at the micellar surface. This effect is in line with the essential features of the pseudophase ion-exchange model of micellar catalysis [29,31]. 

Figure 8. (A) Schematic illustration of surfactant exchange reaction (B) TEM image of 8 nm nanoparticle superlattice with each particle being surrounded by oleate molecules and interparticle spacing at 4 nm (C) TEM images of 8 nm nanoparticle superlattice after surfactant exchange with dicyanobenzene. The spacing between two particles is at lnm.

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