Photophysics of a cationic biological photosensitizer in anionic micellar environments: combined effect of polarity and rigidity.

A steady-state and time-resolved photophysical study of a cationic phenazinium dye, phenosafranin (PSF), has been investigated in well-characterized biomimetic micellar nanocavities formed by anionic surfactants of varying chain lengths, namely, sodium decyl sulfate (S(10)S), sodium dodecyl sulfate (S(12)S), and sodium tetradecyl sulfate (S(14)S). In all these micellar environments, the charge transfer fluorescence of PSF shows a large hypsochromic shift along with an enhancement in the fluorescence quantum yield as compared to that in aqueous medium. A reduction in the nonradiative deactivation rate within the hydrophobic interior of micelles led to an increase in the fluorescence yield and lifetime. The present work shows the degree of accessibility of the fluorophore toward the ionic quencher in the presence of surfactants of different surfactant chain lengths. The fluorometric and fluorescence quenching studies suggest that the fluorophore resides at the micelle-water interfacial region. The enhancements in the fluorescence anisotropy and rotational relaxation time of the probe in all the micellar environments from the pure aqueous solution suggest that the fluorophore binds in motionally restricted regions introduced by the micelles. Polarity and viscosity of the microenvironments around the probe in the micellar systems have been determined. The work has paid proper attention to the hydrophobic effect of the surfactant chain length on photophysical observations.