Quaternary water-in-oil microemulsion of a cationic surfactant (cetyltrimethylammonium bromide, CTAB), n-hexane, water, and n-pentanol has been investigated using conductivity, quasi-elastic light scattering, nearinfrared absorption spectroscopy, and pulsed field gradient spin-echo NMR measurements. The conductivity behavior shows features characteristic of the migration of charged droplets. Consequently, using the charge fluctuation model, the conductivity data were correlated with the droplet radius obtained from self-diffusion coefficients for different obstruction factors. Conductivity and self-diffusion measurements were found to be self-consistent for spherical droplets with hard-sphere interactions. Comparison between collective diffusion and self-diffusion coefficients fully supports this conclusion. The average head-group area of CTAB, the amount of water free in the organic bulk, and the fraction of alcohol present into the aggregates were evaluated together with the thickness of both the interfacial film and the bound water layer providing a full microscopic picture of the system. IntroductionMicroemulsions are transparent, isotropic, thermodynamically stable dispersions of oil and water, stabilized by surfactant molecules. 1-3 Four-component systems of surfactant, cosurfactant (generally a short chain linear alcohol), oil, and water have many important features and are the most studied microemulsion systems. The reason for the significance of these systems is that the introduction of cosurfactant greatly extends the isotropic solution region, especially with single-chain ionic surfactants. Microemulsions based on the cationic surfactant cetyltrimethylammonium bromide (CTAB) have been extensively used as host for different enzymes. 4 These systems offer the possibility to compare the enzymatic activities performed in a cationic microemulsion with those performed in the wellknown systems AOT/hydrocarbon/water. 5 Furthermore, the system CTAB/n-pentanol/n-hexane/water can be a useful tool to investigate the properties of anionic polyelectrolytes such as nucleic acids, 6 since the system is cationic, is transparent in the UV region (avoiding the limitation imposed by the use of chloroform which is often employed as cosolvent for CTABbased microemulsions 7 ), and can solubilize high quantities of water, up to 80 molecules of water per surfactant molecule. These characteristics are at the basis of two recent papers, where this microemulsion was used as a microreactor to perform the self-replication of oligonucleotides. 8,9 Despite such widespread interest in CTAB water-in-oil (w/ o) microemulsions, little is known about their microstructure. This prevents one from completely understanding the basic mechanism of the phenomena taking place inside them. The problem of the structure of a quaternary microemulsion is not an easy task to afford, as can be deduced by the fact that several studies, making use of a wide range of experimental techniques, gave a small contribution toward a reliable picture of these syst...

The microstructure of the quaternary water-in-oil microemulsion CTAB/water/n-pentanol/n-hexane has been investigated by means of the pulsed gradient spin-echo NMR technique over a wide range of composition. The composition of the continuous organic phase and of the interfacial phase has been determined through the analysis of the n-pentanol self-diffusion coefficient. The size of the reverse aggregates has been evaluated from the CTAB self-diffusion coefficient. The correlation of the reverse micellar size with interfacial composition has therefore been possible. Results coming from both water dilution lines and interface dilution lines have been analyzed according to suitable models. A "master plot", i.e., a graphical representation that allows us to display the data collected at all the possible compositions of the four components system, is also proposed.

The isothermal quasi-ternary-phase diagram of the lecithin-cyclohexane-water system was determined at 25 °C using a combination of polarizing microscopy, small-angle X-ray diffraction, and NMR techniques. The system contains four lyotropic liquid-crystalline phases and two isotropic liquid phases. Apart from the lamellar (LR) phase, there are only reverse-type aggregates with a water interior, in addition to an essentially pure water phase, whose relative locations in the phase diagram follow the sequence (from the oil corner to the surfactant corner): reverse micellar solution (L2), reverse anisotropic nematic (N2), reverse micellar cubic (I2), reverse hexagonal (H2), and finally, the lamellar phase. The aggregates have a finite swelling with water, and coexistence with excess water is found at higher water contents. The area per lecithin molecule was determined in the H2 and LR phases. This area varies with the mole ratio [H2O]/[Lec] ) W0 at lower W0 values, but saturates at an area of 90 Å 2 / molecule for W0 J 15. The phase diagram is discussed in relation to the known formation of giant wormlike reverse micelles in the liquid L2 phase. Of particular interest here is the transition from liquid (L2) to nematic (N2) as the wormlike aggregate concentration is increased.