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Unique liquid crystal behavior in water of anionic fluorocarbon–hydrocarbon hybrid surfactants containing oxyethylene units

Sagisaka, Masanobu, Fujita, Yoshie, Shimizu, Yusuke, Osanai, Chie, Yoshizawa, Atsushi
Journal of colloid and interface science 2011 v.357 no.2 pp. 400-406
droplets, fluorescence, hydrophilicity, liquid crystals, micelles, solubilization, surfactants, temperature
This study reports the unique aqueous lyotropic liquid crystal behavior of an anionic hybrid surfactant, 8F-B2ES, which has 2-[2-(butyloxy)ethyloxy]ethyl and 1H,1H,2H,2H-perfluorodecyl tails. An 8F-B2ES-analog hybrid surfactant with no oxyethylene units (8F-DeS) and a symmetric fluorinated double-tail surfactant with two 2-(1H,1H,2H,2H-perfluorohexyloxy)ethyl tails (4FEOS) were used as control surfactants in examining the effects of the oxyethylene units and of the hybrid structure on the liquid crystal behavior. Polarized microscopic observations showed the formation of a lamellar liquid crystal phase for each surfactant/water mixture at surfactant concentrations higher than 10wt.%. In the case of the 30wt.% 8F-B2ES/water mixture, two types of spherical aggregates were observed at temperatures higher than 40°C: one was a typical lamella liquid crystal with a maltese cross-texture, and the other was optically isotropic. Interestingly, when the 8F-B2ES lamellar phase was cooled to below 40°C, the lamellar aggregates were distorted and the isotropic droplets became anisotropic. As this unique liquid crystal behavior was not observed for aqueous mixtures of the control surfactants, the oxyethylene units in the hybridized hydrocarbon tail play an important role in the behavior. This study also examined the effect of the oxyethylene units on microenvironmental polarity in the hybrid surfactant bilayer via fluorescence spectral measurements of pyrene solubilized in each lamellar phase. The polarity of the 8F-B2ES bilayer at 70°C was found to be that of a hydrocarbon surfactant lamellar phase, and increased gradually with decreasing temperature. The polarity became the same as that of hydrophilic spherical micelles below 40°C, despite the presence of the lamellar aggregates. Since the polarity in the 8F-DeS bilayer was independent of temperature, and as low as that of a typical hydrocarbon surfactant bilayer, hydration of the 8F-B2ES oxyethylene units would increase the polarity, and then loosen the 8F-B2ES packing within the bilayer. This probably led to distortion of the lamellar aggregates.