Micelles interfacial potentials

The common method of estimation of the interfacial potential in microheteroge-neous systems is to use pH indicators adsorbed at for instance charged micelles. The local interfacial proton activity is related to the bulk activity and to an interfacial potential by Boltzmann s law according to the equation [17,70-72]... 

All three methods give similar values of interfacial potentials typical results for some of micelles and vesicles are listed in Table 3. Also listed are estimates of interfacial dielectric constants (e), determined by comparing the position of absorption bands of solvatochromic indicators in the surfactant assemblies with that of reference 1,4-dioxane water mixtures with known e values. More generally, luminescence probe analysis [49], thermal leasing [50] and absorption spectroscopy [47, 51] are techniques that have all been utilized to measure local polarities in micelles and vesicles. It is important to note that these methods presume knowledge of the loca-... 

These examples should serve to underscore the difficulty in predicting the effects that interfacial potentials, membrane structure and microphase organization will have on electron-transfer reactions across the membrane interface and within the bilayer itself. The principles involved are common to micelles and vesicles, but the more anisotropic and highly ordered vesicles provide a more complex reaction environment for solubilized or adsorbed reactants. 

It is now believed from studies on the natural photosynthetic systems that microenvironments for the photoinduced ET reaction play an important role in the suppression of the back ET [1-3]. As such reaction environments, molecular assembly systems such as micelles [4], liposomes [5], microemulsions [6-8] and colloids [9] have been extensively investigated. In them, the presence of microscopically heterogeneous phases and interfacial electrostatic potential is the key to the ET rate control. 

Functionalized polyelectrolytes are promising candidates for photoinduced ET reaction systems. In recent years, much attention has been focused on modifying the photophysical and photochemical processes by use of polyelectrolyte systems, because dramatic effects are often brought about by the interfacial electrostatic potential and/or the existence of microphase structures in such systems [10, 11], A characteristic feature of polymers as reaction media, in general, lies in the potential that they make a wider variety of molecular designs possible than the conventional organized molecular assemblies such as surfactant micelles and vesicles. From a practical point of view, polymer systems have a potential advantage in that polymers per se can form film and may be assembled into a variety of devices and systems with ease. 

As mentioned earlier, a great deal of literature has dealt with the properties of heterogeneous liquid systems such as microemulsions, micelles, vesicles, and lipid bilayers in photosynthetic processes [114,115,119]. At externally polarizable ITIES, the control on the Galvani potential difference offers an extra variable, which allows tuning reaction paths and rates. For instance, the rather high interfacial reactivity of photoexcited porphyrin species has proved to be able to promote processes such as the one shown in Fig. 3(b). The inhibition of back ET upon addition of hexacyanoferrate in the photoreaction of Fig. 17 is an example of a photosynthetic reaction at polarizable ITIES [87,166]. At Galvani potential differences close to 0 V, a direct redox reaction involving an equimolar ratio of the hexacyanoferrate couple and TCNQ features an uphill ET of approximately 0.10 eV (see Fig. 4). However, the excited state of the porphyrin heterodimer can readily inject an electron into TCNQ and subsequently receive an electron from ferrocyanide. For illumination at 543 nm (2.3 eV), the overall photoprocess corresponds to a 4% conversion efficiency. 

This transition may j-.e. reducing the specific surface energy, f. The reduction of f to sufficiently small values was accounted for by Ruckenstein (15) in terms of the so called dilution effect". Accumulation of surfactant and cosurfactant at the interface not only causes significant reduction in the interfacial tension, but also results in reduction of the chemical potential of surfactant and cosurfactant in bulk solution. The latter reduction may exceed the positive free energy caused by the total interfacial tension and hence the overall Ag of the system may become negative. Further analysis by Ruckenstein and Krishnan (16) have showed that micelle formation encountered with water soluble surfactants reduces the dilution effect as a result of the association of the the surfactants molecules. However, if a cosurfactant is added, it can reduce the interfacial tension by further adsorption and introduces a dilution effect. The treatment of Ruckenstein and Krishnan (16) also highlighted the role of interfacial tension in the formation of microemulsions. When the contribution of surfactant and cosurfactant adsorption is taken into account, the entropy of the drops becomes negligible and the interfacial tension does not need to attain ultralow values before stable microemulsions form. 

Bioaccumulation All classes of surfactant are active surface tension depressants. At the critical micelle concentration (CMC) abrupt changes occur in the characteristic properties of surfactants such that surface and interfacial tensions in an aqueous system are at their minimum while osmotic pressure and surface detergent properties are significantly increased. The CMC for most surfactants is reached around 0.01% (18, 19). These effects have an impact on the potential for bioaccumulation of the pesticide, and in the organisms monitored the presence of Dowanol and nonylphenol increased the accumulation of fenitrothion and aminocarb at least 20-300% respectively, over the accumulation obtained in their absence (20). In effect, these adjuvants... 

The stability of inverse micelles has been treated by Eicke (8,9) and by Muller (10) for nonaqueous systems, while Adamson (1) and later Levine (11) calculated the electric field gradient in an inverse micelle for a solution in equilibrium with an aqueous solution. Ruckenstein (5) later gave a more complete treatment of the stability of such systems taking both enthalpic (Van der Waals (VdW) interparticle potential, the first component of the interfacial free energy and the interparticle contribution of the repulsion energy from the compression of the diffuse part of the electric double layer) and entropic contributions into consideration. His calculations also were performed for the equilibrium between two liquid solutions—one aqueous, the other hydrocarbon. 

In previous papers, the experimental values of B for several (jj/o microemulsions have been measured. As already pointed out, these values are function of both the radius of the micelles and the alcohol chain length (9-10). The attractive interactions between micelles increase as the micellar radius increases and as the alcohol chain length is shorter. We have proposed an interaction potential between w/o micelles which allows to account for the scattering results (10). This potential V(r) results from the possibility of penetration of the micelles. V(r) is proportional to the volume of interpenetration of micelles. The penetration is limited by the molecules of alcohol located inside the interfacial film, r is the distance between two micelles. 

Figure 2 presents a schematic of one scenario in which nonionic surfactant may assist biomineralization. In this situation micellar nonionic surfactant has solubilized HOC from soil. As microorganisms deplete aqueous-phase HOC via mineralization, the micelle releases HOC to solution. HOC exit rates from micelles may be significantly faster than HOC desorption rates from soil, and this condition thereby potentially enhances the availability of HOC to the microorganism. Other researchers (25, 28) suggested that surfactants may make HOCs more available for microbial attack in soil by decreasing the interfacial tension between the compound and water. 

The main purpose of the model was to relate the ion concentration and the local electrostatic parameters. The first step towards this relation was to assume that thermodynamic equilibrium was achieved between the water pools of the reversed micelles and the excess aqueous phase. This hypothesis differs from classical thermodynamics in that the equilibrium does not take place between two macroscopic phases. Biais et already suggested in a microemulsion pseudophase model (60) that, due to the low interfacial tension, chemical potentials of any constituents depend on the composition, even in microscopic domains, but not on the geometric parameters of the structure. 

More quantitively, Fernandez and Fromheiz investigated the interfacial region of SDS, CTAB, and Triton X-100 micelles (194). They used fluorescent pH indicators, hydroxycoumarin and aminocoumarin dyes substituted by alkane chains, and measured shifts of the pK-values. The authors attributed these shifts partly to the dielectric constant at the micelle-water interface and pardy to the electrical potential at the surface of charged micelles. In this way they calculated... 

Figure 12. Plots of C vs, A predicted by the model when a surface aggregation process occurs. Curves were calculated from Eqs. (43) using the parameters given in text at the following In p.. x values, (1) -3, (2) -2, (3) -I, (4) 0, (5) 1, Inset Experimental C vs, E plots of the interface between an HME and a 0.1 M Na2S04 solution of lO" M Tween 80", recorded using 2 mV s" potential scan rate. Experimental data were reprinted from J. Electroaml. Chem., 356, S. Sotiropoulos el ai. Interfacial Micellization of Cetyl-Dimethyl-Benzylammonium Chloride and Tween-80" at the Hg/Electrolyte Solution Interface, p, 225, Copyright 1993, with permission from of Elsevier Science.

The relationship between adsorption and interfacial properties such as contact angle, zeta-potential and flotation recovery is illustrated in Figure 39.2 for cationic surfactant dodecylammonium acetate/quartz system (5). The increase in adsorption due to association of surfactants adsorbed at the solid-liquid interface into two dimensional aggregates called solloids (surface colloids) or hemi-micelles occurs at about 10 M DA A. This marked increase in adsorption density is accompanied by concomitant sharp changes in contact angle, zeta-potential and flotation recovery. Thus these interfacial phenomena depend primarily on the adsorption of the surfactant at the solid-liquid interface. The surface phenomena that reflect the conditions at the solid-liquid interface (adsorption density and zeta-potential) can in many cases be correlated directly with the phenomena that reflect the... 

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