Micelle vesicular

In many cases, under changing experimental conditions, water-containing reversed micelles evolve, exhibiting a wide range of shapes such as disks, rods, lamellas, and reverse-vesicular aggregates [15,107,108], Nickel and copper bis(2-ethylhexyl) sulfosucci-nate and sodium bis(2-ethylhexyl) phosphate, for example, form rod-shaped droplets at low water contents that convert to more spherical aggregates as the water content is increased [23,92,109,110],... 

This limited amount of kinetic evidence suggests that the kinetic models developed for reactivity in aqueous micelles are directly applicable to reactions in vesicles, and that the rate enchancements have similar origins. There is uncertainty as to the appropriate volume element of reaction, especially if the vesicular wall is sufficiently permeable for reaction to occur on both the inner and outer surfaces, because these surfaces will have different radii of curvature and one will be concave and the other convex. Thus binding, exchange and rate constants may be different at the two surfaces. 

Fig. 12 Spherical (a), rodlike (b), and vesicular (c) morphologies for crew-cut micelles (images downloaded from http //ottomaass.chem.mcgill.ca/groups/eisenberg/). Adapted from [35]...

Experiments have shown that, in most cases, such as for SDS, the initially spherical-shaped micelles may be influenced to grow under into larger aggregates (disclike, cylindrical, lamellar, vesicular) (Figure 3.11). 

To understand the effects of micelles and vesicles on (organic) reactions, it is important to know where reactants are located in the micellar and vesicular pseudophase and what this region looks like in terms of a reaction medium. As mentioned above, micelles (but similar arguments are valid for vesicles) can be thought of as offering... 

Micelles offer a variety of highly dynamic binding sites, which makes their description as a reaction medium an intricate affair. Whereas vesicular dynamics are slower than micellar dynamics, this by no means results in more straightforward descriptions of the... 

Most of the characteristics invoked to explain rate accelerations and rate retardations by micelles are valid for vesicles as well. For example, the alkaline hydrolysis of A-methyl-A-nitroso-p-toluenesulfonamide is accelerated by cationic vesicles (dioctade-cyldimethylammonium chloride). This rate acceleration is the result of a higher local OH concentration which more than compensates for the decreased polarity of the vesicular pseudophase (compared to both water and micelles) resulting in a lower local second-order rate constant. Similar to effects found for micelles, the partial dehydration of OH and the lower local polarity are considered to contribute significantly to the catalysis of the Kemp elimination " by DODAB vesicles. Even the different... 

Similarly, vesicular reactivity is dependent on bilayer fluidity and Arrhenius (or Eyring) plots for the decarboxylation of 6-NBIC show a break around Tm. " For the Kemp elimination in different bilayers, it was found that the bilayer for which kinetic data had been gathered below its was least effective as a catalyst. Ester hydrolysis has also been found to be faster above r. For the decarboxylation of 6-NBIC, the increase in catalytic efficiency was attributed to different aggregate surface dynamics based on the observation that vesicles above showed intermediate activation parameters between vesicles below and micelles. One could, of course, discuss causality here considering the fact that many of the bilayer... 

Hydrolysis of acetals yields aldehydes, which are intermediates in the biochemical /3-oxidation of hydrocarbon chains. Acid catalyzed hydrolysis of unsubstituted acetals is generally facile and occurs at a reasonable rate at pH 4-5 at room temperature. Electron-withdrawing substituents, such as hydroxyl, ether oxygen, and halogens, reduce the hydrolysis rate, however [50]. Anionic acetal surfactants are more labile than cationic [40], a fact that can be ascribed to the locally high oxonium ion activity around such micelles. The same effect can also be seen for surfactants forming vesicular aggregates. 

Micellar theory has developed in a somewhat uncertain fashion and is still in many respects open to discussion. Possible micelle structures include the spherical, laminar and cylindrical arrangements illustrated schematically in Figure 4.14. Living cells can be considered as micellar-type arrangements with a vesicular structure. 

Keenan, 1975 Neville et al., 1981 Watters, 1984 Virk et al., 1985), the presumption is that the formation of casein micelles is orchestrated with the transport of ions, the phosphorylation and glycosy-lation of the caseins, and lactose synthesis, such that the intravesicular ionic environment and casein concentration change continuously during the 20 min or so required for micelle assembly. Patton and Jensen (1975) observed, in electron micrographs, the same density of micellar particles in the alveolus as in mature vesicles, suggesting that, by this stage, the vesicular concentrations are virtually identical to those in the aqueous phase of milk. 

Figure 7 Plot of the change in the product of the coupling and maximum saturation factors as a function of macromolecular structure. At lower pH values, the spin-labelled lipids are present as vesicles and vesicular aggregates, while at higher pH values, micelles are formed. The higher psmax values for the micelles imply greater water accessibility to the radical site. The solid circles represent 16-DS (16-doxyl stearic acid, spin-labelled at the end of the lipid tail) while the open circles represent 5-DS (5-doxyl stearic acid, spin-labelled near the polar head group). Reproduced with permission from Ref. [70].

Considerations of the packing parameter concept of Israelachvili et al. [1] suggest that double-chain surfactants, which form the basis of measurements described in this article, cannot readily form spherical micelles. With double-chain surfactants, a more likely aggregate structure is the formation of bilayer vesicles, which can be also thought of as a dispersed lamellar phase (La) as such the vesicular dispersed form is likely to be preferentially formed at low concentrations ( 1 mmol dm-3) of surfactant. Furthermore, it is necessary to consider the possibility, unlike in the case of micelles, that such vesicles, formed by self-assembly of surfactant monomers, will not be thermodynamically stable. The instability is then likely to be in the direction of growth to a thermodynamically-stable lamellar phase from the vesicles. This process will be driven, at least initially, by fusion of two vesicles. 

Fig. 2 Cross-sectional view of chain packing in diblock copolymer spherical, cylindrical, vesicular, and tubular micelles [18]. Copyright 2006 Wiley-VCH Verlag GmbH Co. KGaA. Reproduced with permission...

---