Molecular transport in nanofluidic systems exhibits properties
that are unique to the nanoscale. Here, the electrostatic and steric
interactions between particle and surfaces become dominant in determining
particle transport. At the solid–liquid interface of charged
surfaces an electric double layer (EDL) forms due to electrostatic
interactions between surfaces and charged particles. In these systems,
tunable charge-selective nanochannels can be generated by manipulating
electrostatic gating via co-ions exclusion and counterions enrichment
of the EDL at the solid–liquid interface. In this context,
electrostatic gating has been used to modulate the selectivity of
nanofluidic membranes for drug delivery, nanofluidic transistors,
and FlowFET, among other applications. While an extensive body of
literature investigating nanofluidic systems exists, there is a lack
of a comprehensive analysis accounting for all major parameters involved
in these systems. Here we performed an all-encompassing modeling investigation
corroborated by experimental analysis to assess the influence of nanochannel
size, electrolyte properties, surface chemistry, gate voltage, dielectric
properties, and molecular charge and size on the exclusion and enrichment
of charged analytes in nanochannels. We found that the leakage current
in electrostatic gating, often overlooked, plays a dominant role in
molecular exclusion. Importantly, by independently considering all
ionic species, we found that counterions compete for EDL formation
at the surface proximity, resulting in concentration distributions
that are nearly impossible to predict with analytical models. Achieving
a deeper understanding of these nanofluidic phenomena will help the
development of innovative miniaturized systems for both medical and
industrial applications.