Journal of the American Chemical Society p. 5609 - 5617 (1985)
Update date:2022-08-17
Topics:
Suddaby, Brian R.
Brown, Patti E.
Russell, John C.
Whitten, David G.
An investigation of the fluorescence and photoisomerization of several surfactant trans-stilbene derivatives in aqueous micelles and vesicles is reported.The temperature dependence of Φf was determined for several media over the range 5-70 deg C.The results present a picture of similar micellar solubilization sites for the trans-stilbene chromophore in every case; the micelle is "seen" by the stilbene as a moderately viscous fluid medium with slightly higher values for Φf and slightly reduced Φt->c compared to nonviscous homogeneous solutions.For vesicles considerably more complex behavior is observed.Generally Φf is considerably higher than in solution and Φt->c is much lower.Several, but not all, of the surfactant and hydrophobic stilbenes show a sharp sensitivity in Φf as a function of T when passing through Tc, the vesicle phase transition temperature.Arrhenius plots for the process competing with fluorescence as a function of temperature show relatively high values for Ea and log A, above Tc, consistent with the high temperature phase providing a microenvironment for the stilbene chromophore like a viscous solvent.Below Tc, the variation of Φf gives much lower values for EA and log A which suggest escape from the fluorescence state is "order limited" rather than viscosity dominated.These results suggest that the low-temperature phase of vesicles presents an environment for the stilbene chromophore more like an inclusion complex than a fluid medium.The effect of cholesterol addition on DODAC vesicles containing the stilbenes is to increase fluidity below Tc and to effectively increase viscosity above Tc.
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