Direct Determination of Peroxide Explosives on Polycarbazole/Gold Nanoparticle-Modified Glassy Carbon Sensor Electrodes Imprinted for Molecular Recognition of TATP and HMTD.

Since peroxide-based explosives (PBEs) lack reactive functional groups, they cannot be determined directly by most detection methods and are often detected indirectly by converting them to HO. However, HO may originate from many sources, causing false positives in PBE detection. Here, we developed a novel electrochemical sensor for the direct sensitive and selective determination of PBEs such as triacetone triperoxide (TATP) and hexamethylene triperoxide diamine (HMTD) using electrochemical modification of the glassy carbon (GC) electrode with PBE-memory polycarbazole (PCz) films decorated with gold nanoparticles (AuNPs) by cyclic voltammetry (CV). The prepared electrodes were named TATP-memory-GC/PCz/AuNPs (used for TATP determination) and HMTD-memory-GC/PCz/AuNPs (used for HMTD detection). The calibration lines of TATP and HMTD were found in the concentration range of 0.1-1.0 mg L using the net current intensities of differential pulse voltammetry (DPV) analyte concentrations. The limit of detection (LOD) commonly found was 15 μg L for TATP and HMTD. The sensor electrodes could separately determine intact TATP and HMTD in the presence of nitro-aromatic, nitramine, and nitrate ester energetic materials. The proposed electrochemical sensing method was not interfered by electroactive substances such as paracetamol, caffeine, acetylsalicylic acid, aspartame, d-glucose, and detergent (containing perborate and percarbonate) used as camouflage materials for PBEs. This is the first molecularly imprinted polymeric electrode for PBEs accomplishing such low LODs, and the DPV method was statistically validated in contaminated clay soil samples against the GC-MS method for TATP and a spectrophotometric method for HMTD using - and -tests.