Kinetic study on solute permeation at the interface of molecular aggregates by partial filling capillary electrophoresis

Abstract

Moment analysis method using partial filling CE was developed for the kinetic study on solute permeation at the interface of spherical molecular aggregates. Moment equations for partial filling CE were developed by classifying CE systems into five categories according to the migration velocities of solute and molecular aggregate. The method was applied to the study on the dissolution of electrically neutral solutes into SDS micelles. Elution peaks were measured by partial filling CE while changing the concentration of SDS and the filling ratio of SDS micellar zone to the capillary (ϕ_M ). Partition equilibrium constants (K_p ) and rate constants of interfacial solute permeation of SDS micelles (k_in and k_out ) were determined from the first absolute and second central moments of the elution peaks by using the moment equations. Their values were comparable irrespective of ϕ_M and were almost the same as those previously measured by complete filling CE. The positive correlation of K_p with the hydrophobicity of the solutes was explained in terms of the change in k_in and k_out . It was demonstrated that the moment analysis method using partial filling CE is effective for studying solute permeation kinetics at the interface of spherical molecular aggregates.

Keywords: Interfacial mass transfer; Moment analysis theory; Partial filling capillary electrophoresis; Permeation rate constant; Spherical molecular aggregate.