RÉSUMÉ
The system of two parallel planar, arbitrarily charged surfaces immersed in a solution containing only one ionic species, the counterions, is completely analyzed under a mean field Poisson-Boltzmann approach. Results for the pressure, reduced potential, and counterionic concentration are graphically displayed for two dissociating membranes and for a dissociating and an adsorbing membrane. The results indicate that the system of two planar parallel dissociating membranes acts as a buffer for pressure values and for counterionic concentration values in regions interior to and far from the membranes. The results are related to properties of planar or quasiplanar structures in biological cells.
Sujet(s)
Algorithmes , Membrane cellulaire/composition chimique , Double couche lipidique/composition chimique , Fluidité membranaire , Loi de Poisson , Adsorption , Ions , Modèles biologiques , Contrainte mécanique , Propriétés de surfaceRÉSUMÉ
The study of the H+ concentration at the micellar interface is a convenient system for modeling the distribution of H+ at interfaces. We have synthesized salicylic acid derivatives to analyze the proton dissociation of both the carboxylic and phenol groups of the probes, determining spectrophotometrically the apparent pK(a)'s (pK(ap)) in sodium dodecyl sulfate, SDS, micelles with and without added salt. The synthesized probes were 2-hydroxy-5-(2-trimethylammoniumacetyl)benzoate; 2-hydroxy-5-(2-dimethylhexadecylammoniumacetyl)benzoate; 2-hydroxy-5-(2-dimethylhexadecylammoniumhexanoyl)benzoate; 2-hydroxy-5-(2-dimethylhexadecylammoniumundecanoyl)benzoate; 2-hydroxy-5-acetylbenzoic acid; and 2-hydroxy-5-dodecanoylbenzoic acid. Upon incorporation into SDS micelles the pK(ap)'s of both carboxylic and phenol groups increased by ca. 3 pH units and NaCl addition caused a decrease in the probe-incorporated pK(ap). The experimental results were fitted with a cell model Poisson-Boltzmann (P-B) equation taking in consideration the effect of salt on the aggregation number of SDS and using the distance of the dissociating group as a parameter. The conformations of the probes were analyzed theoretically using two dielectric constants, e.g., 2 and 78. Both the P-B analysis and conformation calculations can be interpreted by assuming that the acid groups dissociate very close to, or at, the interface. Our results are consistent with the assumption that the intrinsic pK(a)'s of both carboxylic and phenol groups of the salicylic acid probes used here can be taken as those in water. Using this assumption the micellar and salt effects on the pK(ap)'s of the (trialkylammonium)benzoate probes were described accurately using a cell model P-B analysis.