Sequential Recognition of Zinc and Pyrophosphate Ions in a Terpyridine-Functionalized Single Nanochannel

A highly selective recognition system for zinc(II) and pyrophosphate ions is constructed using a single conical nanochannel covalently functionalized with N-{4-[(2,2:6,2-terpyridine)-4-yl]benzyl}ethane-1,2-diamine (TPYD). The immobilized TPYD acts as a specific coordination site for Zn2+ to form TPYD-Zn2+ complexes in preference over other metal ions, and subsequently, the resulting Zn2+-coordinated nanochannel can be used as a selective recognition element for the pyrophosphate ion based on the coordination reaction between hydroxyl oxygen atoms of pyrophosphate and Zn2+. Ion recognition is monitored by measuring the current-voltage curves of the solutions. The ionic current of the TPYD-functionalized system at -2.0V undergoes a clear decrease after exposure to Zn2+ ions and is followed with an obvious increase after subsequent treatment with a pyrophosphate solution. The change of ionic current can be primarily attributed to the variation of charge density of the nanochannel. This functionalized single nanochannel might provide a simple and universal means to recognize other targets by modifying different functional molecules onto the inner surfaces of nanochannels.