Voltammetric ion-channel sensing of ammonium ion using self-assembled monolayers modified with ionophoric receptors

Thiazole benzo-crown ether ethylamine-thioctic acid (TBCEAT) was evaluated as an ammonium (NH4+) ionophore for the preparation of ion-channel sensors (ICSs) based on self-assembled monolayers (SAMs) on a gold electrode. A SAM film based on TBCEAT on a gold electrode was assessed as a NH4+-selective sensor, particularly the voltammetric response. The working principle of this voltammetric sensor conceptually mimicked that of the ligand gated ion-channel proteins with regard to the chemically stimulated changes in the membrane permeability. The response to various analytes is based on the change in the electron transfer rates of a redox reaction of the reporter ion [Ru(NH3)6]3+/2+ before and after the binding of NH4+ to TBCEAT on the electrode surface, where electrostatic repulsion between the NH4+-TBCEAT complex and [Ru(NH3)6]3+/2+ induced a decrease in the rate constant. The selective ion-recognition properties of TBCEAT were characterized fully in the conventional ion-selective electrode (ISE) configuration using plasticized polymeric membranes. The mixed monolayer formed with alkylthiol and TBCEAT could bind ammonium ion selectively, and effectively control the flux of the reporter ion [Ru(NH3)6]3+/2+, resulting in ammonium selective ICS with comparable performance (in terms of selectivity and detection limits) to conventional ISE.

The binding of the analyte to TBCEAT/DCT (or TBCEAT/MCH) coated on the surface of the electrode suppresses (or facilitates) the access of a positively charged redox couple, leading to a change in the extent of the electrostatic blocking of SAMs.Figure optionsDownload as PowerPoint slide