Dm. Willard et al., DYNAMICS OF POLAR SOLVATION IN LECITHIN WATER/CYCLOHEXANE REVERSE MICELLES/, Journal of the American Chemical Society, 120(17), 1998, pp. 4151-4160
The solvation dynamics of water in lecithin/cyclohexane reverse micell
es have been determined via ultrafast time-resolved fluorescence studi
es. At hydration levels w(o) less than or equal to 4.8, the reverse mi
cellar samples are nonviscous. Here a single relaxation time is observ
ed that is much longer than the response of free or bulk water. In con
trast, small additions of water to the samples produces a viscous gel,
referred to by others as an organogel or ''living polymer''. At hydra
tion levels of w(o) greater than or equal to 5.8, three relaxation tim
es are observed with approximate time constants of 0.5, 15, and 200 ps
, the shortest of which correlates to free water motion. The dynamics
reveal no evidence of micelle crossover or branch points associated wi
th gel formation. In comparison to Aerosol OT reverse micelles of simi
lar hydration, the water in the lecithin reverse micelles is significa
ntly more restricted. It is proposed that lecithin sequesters signific
antly more water than previously predicted precluding formation of dis
tinct core water pools in the micelles. The results are also compared
to models for aqueous structure and dynamics near phospholipid membran
es and to bulk water dynamics.