Rapid and selective screening of organic peroxide explosives using acid-hydrolysis induced chemiluminescence

Parvez Mahbub; Chowdhury Kamrul Hasan; David Rudd; Nicolas Hans Voelcker; John Orbell; Ivan Cole; Mirek Macka

doi:10.1016/j.aca.2023.341156

Rapid and selective screening of organic peroxide explosives using acid-hydrolysis induced chemiluminescence

Anal Chim Acta. 2023 May 15:1255:341156. doi: 10.1016/j.aca.2023.341156. Epub 2023 Mar 28.

Authors

Parvez Mahbub¹, Chowdhury Kamrul Hasan², David Rudd³, Nicolas Hans Voelcker⁴, John Orbell², Ivan Cole⁵, Mirek Macka⁶

Affiliations

¹ Institute for Sustainable Industries and Liveable Cities (ISILC), Victoria University, Werribee, Victoria, 3030, Australia. Electronic address: parvez.mahbub@vu.edu.au.
² Institute for Sustainable Industries and Liveable Cities (ISILC), Victoria University, Werribee, Victoria, 3030, Australia.
³ Melbourne Centre for Nanofabrication, Victorian Node of the Australian Fabrication Facility, Clayton, Victoria, 3168, Australia; Drug Delivery, Disposition and Dynamics, Monash Institute of Pharmaceutical Sciences, Faculty of Pharmacy and Pharmaceutical Sciences, Monash University, Melbourne, Australia.
⁴ Melbourne Centre for Nanofabrication, Victorian Node of the Australian Fabrication Facility, Clayton, Victoria, 3168, Australia; Drug Delivery, Disposition and Dynamics, Monash Institute of Pharmaceutical Sciences, Faculty of Pharmacy and Pharmaceutical Sciences, Monash University, Melbourne, Australia; Commonwealth Scientific and Industrial Research Organization (CSIRO), Clayton, Victoria, 3168, Australia.
⁵ Research & Innovation Portfolio, RMIT University, Melbourne, Australia.
⁶ Australian Centre for Research on Separation Science (ACROSS), University of Tasmania, Hobart, Australia; Central European Institute of Technology, Brno University of Technology, Purkynova 123, CZ-612 00, Brno, Czech Republic; Department of Chemistry and Biochemistry, Mendel University in Brno, Zemedelska 1, CZ-613 00, Brno, Czech Republic.

PMID: 37032060
DOI: 10.1016/j.aca.2023.341156

Abstract

Organic peroxide explosives (OPEs) are unstable, non-military, contemporary security threats often found in improvised explosive devices. Chemiluminescence (CL) can be used to detect OPEs, via radical formation consisting of peroxide moieties (-O-O-) under acidic conditions. However, selectivity for specific OPEs is hampered by the ubiquitous background of H₂O₂. Herein, we report the differentiation of hexamethylene triperoxide diamine (HMTD), triacetone triperoxide (TATP), and methyl ethyl ketone peroxide (MEKP) by specific flow injection analysis-CL (FIA-CL) signal profiles, after H₂SO₄ treatment. The radical degradation pathway of each structure, and its corresponding FIA-CL profile, was explored using mass spectrometry to reveal the rapid loss of -O-O- from TATP and HMTD structures, while MEKP formed CL signal-sustaining oligomers, as opposed to the immediate attenuation of H₂O₂. The CL response for OPEs in an aqueous media, measured via the described FIA-CL method, enabled ultra-trace limits of detection down to 0.40 μM for MEKP, 0.43 μM for HMTD, and 0.40 μM for TATP (combined linear range 1-83 μM with 95% confidence limit, n = 12). Expanded uncertainties of measurement (UM) of MEKP = ±0.98, HMTD = ±1.03, and TATP = ±1.1 (UM included probabilities of false positive and false negative as well as standard deviations of % recoveries and limit of detections of OPEs). Direct aqueous sample introduction via FIA-CL thus offers the prospect of rapid and selective screening of OPEs in security-heightened settings (e.g., airports), averting false positives from more ubiquitous H₂O₂.

Keywords: Acid hydrolysis; Direct flow injection analysis-chemiluminescence; Hydrogen peroxide; Organic peroxide explosives; Rapid screening; Selectivity.