Abstract
We report the synthesis and aqueous solution properties of a novel redox-active surfactant, Fc(CH2)11SO3-Na+, where Fc is ferrocene. Electrochemical oxidation of Fc to the ferrocenium cation (Fc+) reversibly transforms the anionic surfactant (Fc(CH2)11SO3-) into a zwitterionic species (Fc+(CH2)11SO3-). When dissolved at concentrations between 0.15 and 0.4 mM in aqueous solutions containing 10 mM Li2SO4, oxidation is accompanied by the reversible transformation of a solution of monomeric species of Fc(CH2)11SO3- into vesicle-like (Dh = 70 ± 8 nm, Rg/Rh = 1.0 ± 0.3) surfactant assemblies of Fc+(CH2)11SO3-. In contrast, at concentrations above 0.4 mM, oxidation reversibly transforms a solution of globular (Dh = 6 ± 2 nm) micelles into vesicle-like assemblies of Fc+(CH2)11SO3-. These various oxidation-induced changes in aggregation are reflected in the interfacial properties of this surfactant system, which are substantially different from those of ferrocenyl surfactants with cationic headgroups (Fc(CH2)11N+(...
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