Tunable Current Rectification and Selectivity Demonstrated in Nanofluidic Diodes through Kinetic Functionalization.

The possibility of tuning the current rectification and selectivity in nanofluidic diodes is demonstrated both experimentally and theoretically through dynamically functionalizing a conical nanopore with poly-l-lysine. We identified an optimum functionalization time equivalent to optimum modification depth that assures the highest rectification degrees. Results showed that the functionalization time-dependent rectification behavior of nanofluidic diodes is dominated by the properties of current at positive voltages that in our electrode configuration indicate the "on" state of the diode and accumulation of ions in the nanopore. The functionalization time also tunes the ion selectivity of the diode. If the functionalization time is sufficiently short, an unusual depletion of counterions near the bipolar interface results in a cation-selective nanopore. However, a further increase in the duration of functionalization renders a nanopore that is an anion-selective nanopore. The dynamic functionalization presented in this Letter enables tuning ion selectivity of nanopores.