Rotational Diffusion of Coumarin 153 in Nanoscopic Micellar Environments of n-Dodecyl-β-d-maltoside and n-Dodecyl-hexaethylene-glycol Mixtures

Abstract

The microstructure of mixed micelles containing n-dodecyl-β-D-maltoside and n-dodecyl-hexaethylene-glycol, two nonionic surfactants belonging to the alkyl polyglucoside and polyoxyethyelene alkyl ether families, respectively, has been investigated. With the aim of understanding how the micellar composition affects the microenvironmental properties of micelles, we have examined the photophysics and dynamics of the neutral probe coumarin 153 in the binary mixtures of the surfactants across the entire composition range. We present data on the steady-state absorption and emission spectra of the probe, as well as fluorescence lifetimes and both steady-state and time-resolved fluorescence anisotropies. These data indicate that the participation of the ethoxylated surfactant in the mixed micelle induces an increasing hydration in the palisade layer of the micelle, which forces the probe to migrate toward the inner micellar region, where it senses a slightly less polar environment. The time-resolved fluorescence anisotropy data were analyzed on the basis of the two-step and wobbling-in-cone model. The average reorientation time of the probe molecule was found to decrease with the presence of the ethoxylated surfactant, in good agreement with steady-state fluorescence anisotropy data, suggesting a reduction of the microviscosity in the solubilization site of the probe. The behavior of all diffusion reorientation parameters was analyzed on the basis of two factors: the micellar hydration and the headgroup flexibility of both surfactants. It was concluded that the increasing participation of the ethoxylated surfactant induces a greater hydration in the micellar palisade layer, producing the formation of a less compact microenvironment where the probe experiences a faster rotational reorientation.