Electroosmotic flow modulation and dispersion of uncharged solutes in soft nanochannel.

We perform a systematic study on the modulation of electroosmotic flow (EOF), tuning the selectivity using electrolyte ions and hydrodynamic dispersion of the solute band across the soft nanochannel. The supporting walls of the channel are considered to be hydrophobic and bear non-zero surface charge. For such a channel, the inner side of the supporting rigid walls of the channel are coated with a soft polyelectrolyte layer (PEL). The inhomogeneous distribution of monomers and accompanying volume charge within the PEL is modelled soft-step function. The dielectric permittivity of the PEL and electrolyte solution are in general different, which in turn leads to the ion partitioning effect. The impact of ion steric effects due to finite sized ions is further accounted through the modified ion activity coefficient. To model the EOF modulation considering the combined impact of the ion steric and ion partitioning effects as well as inhomogeneous distribution of monomers across the PEL, we adopt the modified Poisson-Boltzmann equation as the governing equation for electrostatic potential. The Debye-Bueche model is adopted to study the flow field across the PEL and the Stokes equation governs the EOF outside the PEL. In order to study the impact of the modulated EOF field on the dispersion of uncharged solution, we adopt three different models, , a general 2D convective-diffusion model as well as cross-sectional averaged dispersion models due to Gill and late-time Taylor and Aris. Going beyond the widely employed Debye-Hückel approximation and uniform distribution of the monomer as well as accompanying volume charge, we find the results for the electric double layer (EDL) potential, EOF field and averaged throughput, by tuning the ion selectivity, , which is sufficient to analyze the transport of ionized liquid across the channel. The numerical results are supplemented with analytical results for the EDL potential as well as the EOF field under various limiting situations. Besides, we have further shown the impact of the modulated EOF field on the solute dispersion process. We have presented results that highlight the impact of parameters related to EOF field modulation, on solute dispersion governed by a convective-diffusive process, as well as obtaining the results for an effective dispersion coefficient. The dispersion models under the modulated EOF field adopted in the present study can thus be applied to study the dispersion process in engineered microdevices.