Sensitive determination of triacetone triperoxide explosives using electrogenerated chemiluminescence.

Sensitive and selective detection and quantification of high explosive triacetone triperoxide (TATP) with electrogenerated chemiluminescence (ECL) at a glassy carbon electrode in water-acetonitrile solvent mixture were reported. In the presence of ruthenium(II) tris(bipyridine), TATP or hydrogen peroxide derived from TATP via UV irradiation or acid treatment produced ECL emissions upon cathodic potential scanning. Interference from hydrogen peroxide on TATP detection was eliminated by pretreatment of the analyte with catalase enzyme. Selective detection of TATP from hexamethylene triperoxide diamine (HMTD, another common peroxide-based explosive) was realized by comparing ECL responses obtained from the anodic and the cathodic potential scanning; TATP produced ECL upon cathodic potential scanning only, whereas HMTD produced ECL upon both cathodic and anodic potential scanning. The hydroxyl radical formed after the electrochemical reduction of TATP was believed to be the key intermediate for ECL production, and its stability was strongly dependent on the solution composition, which was verified with electron paramagnetic resonance spectroscopy. A detection limit of 2.5 μM TATP was obtained from direct electrochemical reduction of the explosive or hydrogen peroxide derived from TATP in 70/30% (v/v) water-acetonitrile solutions, which was ~400 times lower than that reported previously based on liquid chromatography separation and Fourier transform infrared detection.