pH dependence of micellar diffusion and dissociation

A simplified model system was used to examine the effect of pH on the diffusion and dissociation of mixed micelles across an interphase. Diffusion of radioactively labeled taurocholate and oleic acid from a micellar solution into a phosphate buffer of varying pH (5.0-8.0) was measured. The proportion of bile salt and fatty acid as monomers and aggregates in both solutions was determined by ultrafiltration. Results indicate that all of the oleic acid existed as aggregates in the micellar solution, whereas taurocholate was in equilibrium between aggregate and monomer forms. Between pH 5.0 and 7.0, oleic acid and taurocholate diffusion was inversely related to pH and due to the differences in aggregate but not monomer diffusion. Fatty acid diffusion across the interface was always less than taurocholate diffusion, because taurocholate monomers could also diffuse across the interphase. Calculation of the proportion of taurocholate diffusion from aggregate and monomers based on micellar composition was similar to measured values at pH greater than or equal to 6.5, indicating a lack of micelle dissociation. However, at pH less than or equal to 6 measured values for bile salt monomers exceeded calculations, indicating that a low pH microclimate favors dissociation of micelles. A hypothesis is advanced to explain these events occurring in a disequilibrium area adjacent to the epithelial cell membrane.