ABSTRACT
Atomistic simulations of solutions of CS2 in an ionic liquid, [ C 8 ( C 1 im ) 2 ] [ NTf 2 ] 2 , with a divalent cation and in the corresponding ionic liquid with a monovalent cation, [C4C1im][NTf2], were carried out. The low-frequency librational density of states of the CS2 was of particular interest in view of recent optical heterodyne-detected Raman-induced Kerr effect spectroscopy (OHD-RIKES). Compared to the monocation ionic liquid, the maximum shifts to higher frequencies in the dication ionic liquid under ambient conditions, but was found to be significantly pressure-dependent. CS2 molecules lie above and below the plane of the imidazolium rings and found to be close to the butyl tails of the monocation. The diffusion rates and embedding energies of solvent ions and CS2 in the two ionic liquids were measured.
ABSTRACT
The fluorescence lifetime, tau f, of merocyanine 540 (MC540) in small unilamellar vesicles was measured as a function of temperature and cholesterol content by using phase modulation fluorometry. These vesicles were formed by probe sonication of aqueous suspensions of egg phosphatidylcholine (PC) and cholesterol. The fluorescence lifetime of MC540 in these vesicles decreased with increasing temperature, but was independent of cholesterol. The decrease in tau f with temperature is attributed to trans-cis photoisomerization. At low temperatures, the inverse of tau f, or the fluorescence rate constant, kf, approaches a constant value of 0.45 +/- 0.02 ns-1, which corresponds to the value of the radiative rate constant, kr, of the dye. The photoisomerization rate constant, kiso, was obtained by subtracting kr from kf. The temperature dependence of kiso is well described by an Arrhenius equation, with an activation energy of 31.5 +/- 0.9 kJ mol-1. This Arrhenius behavior is rationalized in terms of the Smoluchowski limit for the Kramers theory for activated barrier crossing. The electronic spectra and kiso for MC540 in these vesicles are consistent with the dye being located in the polar headgroup region of the lipid bilayer.
