The synthesis, phase behavior, and mixing properties of cationic dimeric (gemini) surfactants having
one or two perfluoroalkyl chains is described and compared to that of analogue hydrocarbon surfactants.
The combination of the dimeric character of the amphiphiles with the high hydrophobicity of the fluorocarbon
chains leads to very low critical micelle concentration values and unusually low characteristic times of
exchange between surfactants in the bulk solution and surfactants in the aggregate. This results in slow
exchange on the NMR time scale, which allows a practical study of micellization and comicellization by
NMR. With respect to the morphology of the aggregates, the fluorocarbon amphiphiles do not simply
behave as more hydrophobic amphiphiles. Instead, they assemble into various structures including very
stable unilamellar and multilamellar vesicles not seen in their hydrocarbon analogues. The hybrid
hydrocarbon−fluorocarbon dimeric surfactant exhibits features of both families. In particular it mixes
with either hydrocarbon or fluorocarbon surfactants, whereas the latter two undergo a macroscopic phase
separation.
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