Dynamics of driftless preconcentration using ion concentration polarization leveraged by convection and diffusion

Over the past several decades, separation and preconcentration methods of (bio)molecules have been actively developed for various biomedical and chemical processes such as disease diagnostics, point of care test and environmental monitoring. Among the great developments of the electrokinetic method in a micro/nanofluidic platform is the ion concentration polarization (ICP) phenomenon, in which a target molecule is accumulated near a permselective nanoporous membrane under an applied electric field. ICP method has been actively studied due to its easy implementation and high preconcentration/separation efficiency. However, the dynamic behavior of preconcentrated analytes has not yet been fully studied, especially driftless migration, where the applied electric field is orthogonal to the direction of the drift migration. Here, we demonstrate anomalous shapes of preconcentrated analytes (either plug or dumbbell shape) and the morphologies were analytically modeled by the leverage of convection and diffusion migration. This model was experimentally verified with various lengths of DNA and the limiting cases (convection-free environment in paper-based microfluidic device and extremely low diffusivity of red blood cells) were also shown to confirm the model. Thus, this study not only provides an insight into the fundamental electrokinetic dynamics of molecules in an ICP platform but also plays a guiding role for the design of a nanofluidic preconcentrator for a lab on a chip application.