Gated Molecular Transport in Highly Ordered Heterogeneous Nanochannel Array Electrode.

In biology, all protein channels share a common feature of containing narrow pore regions with hydrophobic functional groups and selectivity filter regions abundant with charged residues, which work together to account for fast and selective mass transport in and out of cells. In this work, an ultrathin layer of polydimethylsiloxane (PDMS) was evaporated on the top orifices of charged silica nanochannels (2-3 nm in diameter and 60 nm in length) vertically attached to the electrode surface, and the resulting structure is designated as heterogeneous silica nanochannels (HSNs). As evidenced by voltammetric studies, the transport of ionic species in these HSNs was controlled by both hydrophobic rejection and electrostatic force arising from the top PDMS layer and from the bottom silica nanochannels, respectively. Anionic species encountered both hydrophobic rejection and electrostatic repulsion forces, and thus, their transport was strongly prohibited, while the transport of cationic species was permitted once the electrostatic attraction exceeded the hydrophobic rejection. Moreover, the magnitude of hydrophobic force could be regulated by the PDMS layer thickness, and that of the electrostatic force can be modulated by the salt concentration, solution pH, or applied voltage. It was demonstrated that the HSNs could be activated from an OFF state (no ion can transport) to an ON state (only cation transport occurs) by decreasing the salt concentration, increasing the solution pH, or applying negative voltages.