Emergence of Transport Regimes from the Axial Field-Induced Interfacial Gradients in Uniform Surface Potential Nanopores

Abstract

Gate-modulated nanopores have emerged as a promising platform for achieving ion selectivity and ionic current rectification (ICR) with the advantage of active field-based control. However, the mechanistic origin of these experimentally reported phenomena, arising from electrostatic coupling between the prescribed radial pore surface potential and the axial transmembrane electric field, remains insufficiently understood. Here, using coupled Poisson--Nernst--Planck and Navier--Stokes simulations supported by asymptotic analysis, we show that a uniform surface potential inherently interacts with the axial driving field to generate a three-dimensional, axially nonuniform electric double layer (EDL). This field-induced EDL heterogeneity effectively mimics a linear axial variation in zeta potential, breaking translational symmetry within an otherwise uniform pore. As a result, the system exhibits coupled electrokinetic responses, including ion selectivity, ionic current rectification, and non-canonical electroosmotic flow, all governed by a single asymmetry parameter $α$ derived from the EDL structure. Critical transitions occur at specific values of $α$; in particular, at $α=0$, the EDL becomes axially antisymmetric, leading to reversal of ion selectivity, significant ICR and the emergence of a peculiar negative electroosmotic flow rectification accompanied by internal vortical structures. These findings establish the electrostatic mechanism for axial symmetry breaking as the underlying principle for transport in voltage-gated nanopores, enabling a unified framework for designing tunable electrokinetic functionalities beyond geometry- and chemistry-based strategies.