We present an experimental study of nanoscale electro-kinetic transport in custom-fabricated quartz nanochan-nels using quantitative epifluorescence imaging and current monitoring techniques.One aim is to yield insight into electrical double layer physics and study the applicability of continuum theory to nanoscale electrokinetic systems.A second aim is to explore a new separation modality offered by nanoscale electrophoretic separations.We perform parametric variations of applied electric field,channel depth,background buffer concentration,and species valence to impose variations on delta potential,effective mobility,and Debye length among other parameters.These measurements were used to validate a continuum theory-based analytical model presented in the first of this two-paper series.Our results confirm the usefulness of continuum theory in predicting electrokinetic transport and electrophoretic separations in nano-channels.Our model leverages independent measurements of delta potential performed in a microchannel system at electrolyte concentrations of interest.These data yield a delta potential versus concentration relation that is used as a boundary condition for the nanochannel electrokinetic transport model.The data and model comparisons together show that the effective mobility governing electrophoretic transport of charged species in nanochannels depends not only on ion mobility values but also on the shape of the electric double layer and analyte ion valence.We demonstrate a method we term electrokinetic separation by ion valence,whereby both ion valence and mobility may be determined independently from a comparison of micro- and nanoscale transport measurements.
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