Mathematical model describing gradient focusing methods for trace analytes

The problem of gradient focusing for concentrating trace analytes is considered. Variation of buffer viscosity, conductivity, and possibly also the zeta-potential results in a focusing point where the electrophoretic velocity is balanced by the electroosmotic flow (EOF) and where the sample concentrates. The axial inhomogeneity also results in an induced pressure gradient that alters the EOF profile and therefore causes Taylor dispersion. The coupled hydrodynamics and transport problem leading to the achievement of a steady state is studied in the context of the lubrication approximation: all variations in the axial direction take place over a length scale very much larger than the characteristic channel width. A single length scale sigma(m) and a single time scale tau is found to completely determine the dynamics of the evolution close to the focusing point. Using appropriate scaled variables, the time evolution of the concentration profile near equilibrium can be described by an inhomogeneous advection diffusion equation that is free of all parameters. Explicit formulas are deduced for the location of the peak centroid and its width as a function of time. A simple graphical method is proposed for optimizing the performance of the system when some tunable external parameters are available.