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 H2O2. However, H2O2 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–1 using the net current intensities of differential pulse voltammetry
(DPV) versus analyte concentrations. The limit of
detection (LOD) commonly found was 15 μg L–1 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 t- and F-tests.