Electroanalysis and Spectroelectrochemistry of Nonaromatic Explosives in Acetonitrile Containing Dissolved Oxygen

In search of a rapid, low-cost, and solution-phase detection technique for explosives, the (spectro-)electrochemistry of compounds from two major nonaromatic classes, namely nitramines (RDX and HMX) and nitrate esters (pentaerythritol tetranitrate (PETN) and the plastic explosive composite Semtex 1A) in acetonitrile (AN) is reported. In electrochemical screening, 5 μg of explosive material was detectable in 10 s by multicomponent cyclic voltammetric (CV) analysis on unmodified glassy carbon under ubiquitous environmental influences (i.e., trace water and dissolved oxygen). The explosives were identified with high recoveries under a battery of proof-of-concept testing scenarios in various matrices. In AN containing naturally dissolved oxygen (approx. 2 mM), the superoxide radical is co-electrogenerated during analyte reduction. Free superoxide yields prominent signals that the explosives attenuate quantitatively. To gain further insight into the electrochemical transformation mechanism, spectroelectrochemistry was employed to monitor changes in ultraviolet (UV) absorbance during CV and identify transient intermediates and product species, which could be targeted by future chemical sensors. Overlapping UV spectra of multiple species are deconvoluted using a new strategy, spectral regional baselining, for time- and potential-resolved spectroelectrochemical (SEC) analysis. This study shows that dissolved oxygen, hitherto an interferent purposefully removed from the solution, can be exploited advantageously in electrochemical sensing. The work expands our understanding of high-explosive solution-phase chemistry and offers a novel route to signal transduction for the sensing of energetic materials.