local pH in the water pool of Aerosol OT reverse micelles in n-heptane was
estimated from the excitation spectra of the pH-sensitive fluorescence prob
e, pyranine, solubilized into the micellar core as a function of pH of the
aqueous solutions to be solubilized. This probe shows two distinct excitati
on bands corresponding to the neutral (nonionized) and basic (ionized) form
s. The intensity ratios of these bands were in advance plotted as a functio
n of the pH of the aqueous solutions to make a calibration curve for local
pH estimation. The probe-containing aqueous solutions ranging from pH 1 to
12, adjusted using NaOH/HCl or buffers, were solubilized into the reverse m
icelles at a constant water content (Rw = [H2O]/[AOT] = 20). When NaOH/HCl
was used for pH adjustment, even if an acidic or alkaline aqueous solution
was solubilized into the micelles, the solubilized probes reported unexpect
edly an almost constant intensity ratio over a wide pH range. This result s
uggests that the water pool of AOT reverse micelles has buffer-like action.
A similar effect was also observed even when various pH values of buffer s
olutions were solubilized. The use of fluorescein, instead of pyranine, led
to the same conclusion. A model experiment suggested that such buffer-like
action is related to a considerably high concentration of the AOT sulfonat
e groups localizing on the water/oil interface. The mechanism can be explai
ned in terms of the restricted electrolytic dissociation of the AOT sulfona
te groups in the reverse micellar aggregation state.