▎ 摘　　要

Biological protein channels have many remarkable properties such as gating, high permeability, and selectivity, which have motivated researchers to mimic their functions for practical applications. Herein, using molecular dynamics simulations, we design bioinspired nanopores in graphene sheets that can discriminate between Na+ and K+, two ions with very similar properties. The simulation results show that, under transmembrane voltage bias, a nanopore containing four carbonyl groups to mimic the selectivity filter of the KcsA K+ channel preferentially conducts K+ over Na+. A nanopore functionalized by four negatively charged carboxylate groups to mimic the selectivity filter of the NavAb Na+ channel selectively binds Na+ but transports K+ over Na+. Surprisingly, the ion selectivity of the smaller diameter pore containing three carboxylate groups can be tuned by changing the magnitude of the applied voltage bias. Under lower voltage bias, it transports ions in a single-file manner and exhibits Na+ selectivity, dictated by the knock-on ion conduction and selective blockage by Na+. Under higher voltage bias, the nanopore is K+-selective, as the blockage by Na+ is destabilized and the stronger affinity for carboxylate groups slows the passage of Na+ compared with K+. The computational design of biomimetic ion-selective nanopores helps to understand the mechanisms of selectivity in biological ion channels and may also lead to a wide range of potential applications such as sensitive ion sensors, nanofiltration membranes for Na+/K+ separation, and voltage-tunable nanofluidic devices.