An asymptotic model of Poisson--Nernst--Planck--Stokes systems in narrow channels

TL;DR

This paper develops an asymptotic model for ion transport in narrow channels described by coupled Poisson--Nernst--Planck--Stokes equations, enabling efficient analysis of electrokinetic phenomena with broader validity than existing models.

Contribution

The authors derive a new asymptotic reduction of the PNPS system that accounts for channels where Debye length is comparable to channel width, extending the applicability of previous models.

Findings

Ion current exhibits multiple flow transitions.

Finite-size effects can enhance ion selectivity.

Model successfully predicts ion transport behaviors in protein channels.

Abstract

Ion transport through narrow channels is described by the coupled Poisson--Nernst--Planck--Stokes equations (PNPS) on a continuum scale. However, direct numerical simulations in two or three dimensions of boundary value problems for small aspect ratio geometries, a crucial characteristic of nanopores, can quickly become computationally intensive and thus limit the insights into the underlying mechanisms that control electrokinetic phenomena. Taking advantage of the small aspect ratio, we derive a systematic asymptotic reduction of the PNPS system. In contrast to existing one-dimensional reductions, which assume a Debye length much smaller than the channel radius, our analysis identifies a distinguished asymptotic regime in which the Debye length is allowed to be comparable to the channel width. Our approach has a significantly larger range of validity and contains existing approximations such as the Helmholtz--Smoluchowski approximation as limiting cases. The derived asymptotic model extends also to a generalized PNPS system, where finite-size constraints and solvation effects are taken into account and thus applies to other well-known models such as the Bikerman--Freise model. Using our asymptotic model we demonstrate that the ion current can undergo a number of different flow transitions and in particular predict that positively charged ions can be pushed against their electrostatic gradient. Furthermore, we show how finite-size effects can influence the ion current and enhance ion selectivity. Finally, we revisit case studies of protein-based channels from the literature to illustrate the predictive potential of our asymptotic model.