Application of the Exact Dispersion Solution to the Analysis of Solutes beyond the Limits of Taylor Dispersion.

Taylor dispersion analysis (TDA) is a fast and simple method for determining hydrodynamic radii. The method is applicable under conditions that allow the solute molecules to diffuse appreciably across the cross section of the flow before its measurement. This mitigates the effects of early stage convection on the dispersion and thus imposes a lower bound on the value of the diffusion coefficient measurable at a given flow speed. In this paper, we use the exact solution to the dispersion problem to analyze solutes outside the limits of TDA. Furthermore, by modeling the early stage convection, we analyze a mixture of two solutes with significantly different sizes that mimics heavily aggregated samples. The results obtained from the fits in both cases were in good agreement to the expected values. This demonstrates the potential of the model to extend dispersion analysis to regimes well outside the TDA limits such as the analysis of large molecules and the use of high flow-rates.