Tomasz Krawczyk1. 1. Department of Chemical Organic Technology and Petrochemistry, Faculty of Chemistry, Silesian University of Technology, ul. Krzywoustego 4, 44-100, Gliwice, Poland.
Abstract
RATIONALE: Hexamethylene triperoxide diamine (HMTD) is one of the peroxide-based explosives that are difficult to detect using standard analytical methodologies. METHODS: It was analyzed by electrospray ionization mass spectrometry (ESI-MS) on a UPLC-TOF instrument. Alkali metal salts were used to promote the formation of ions. RESULTS: In the full scan positive ion mode a 3 ng (13 pmol) limit of detection was achieved if [HMTD + Me](+) ions (Me = Li, Na, K) were detected. It was found that HMTD easily undergoes oxidation to tetramethylene diperoxide diamine dialdehyde (TMDDD) in the source as well as in the samples. TMDDD can be detected as [TMDDD + Me](+) ions, but better ionization efficiency leads to the detection limit of TMDDD at the 2 pg (0.01 pmol) level. In butyl acetate the yield of oxidation of HMTD to TMDDD reaches 25% within 20 min at 120 °C, which offers a simple way of improving the detection limit of HMTD by two orders of magnitude. CONCLUSIONS: A simple procedure of detection of HMTD that matches the most sensitive methods available was developed. It uses standard equipment available in many laboratories. It was shown that the frequently reported [HMTD-H](+) cation observed by various authors was in fact a misinterpretation of the results, and should be attributed to [TMDDD + H](+).
RATIONALE: Hexamethylene triperoxide diamine (HMTD) is one of the peroxide-based explosives that are difficult to detect using standard analytical methodologies. METHODS: It was analyzed by electrospray ionization mass spectrometry (ESI-MS) on a UPLC-TOF instrument. Alkali metal salts were used to promote the formation of ions. RESULTS: In the full scan positive ion mode a 3 ng (13 pmol) limit of detection was achieved if [HMTD + Me](+) ions (Me = Li, Na, K) were detected. It was found that HMTD easily undergoes oxidation to tetramethylene diperoxide diamine dialdehyde (TMDDD) in the source as well as in the samples. TMDDD can be detected as [TMDDD + Me](+) ions, but better ionization efficiency leads to the detection limit of TMDDD at the 2 pg (0.01 pmol) level. In butyl acetate the yield of oxidation of HMTD to TMDDD reaches 25% within 20 min at 120 °C, which offers a simple way of improving the detection limit of HMTD by two orders of magnitude. CONCLUSIONS: A simple procedure of detection of HMTD that matches the most sensitive methods available was developed. It uses standard equipment available in many laboratories. It was shown that the frequently reported [HMTD-H](+) cation observed by various authors was in fact a misinterpretation of the results, and should be attributed to [TMDDD + H](+).
Authors: Michelle D Gonsalves; Alexander Yevdokimov; Audreyana Brown-Nash; James L Smith; Jimmie C Oxley Journal: Anal Bioanal Chem Date: 2021-03-15 Impact factor: 4.142
Authors: Kevin Colizza; Alexander Yevdokimov; Lindsay McLennan; James L Smith; Jimmie C Oxley Journal: J Am Soc Mass Spectrom Date: 2017-11-07 Impact factor: 3.109
Authors: Kevin Colizza; Alexander Yevdokimov; Lindsay McLennan; James L Smith; Jimmie C Oxley Journal: J Am Soc Mass Spectrom Date: 2018-01-25 Impact factor: 3.109