Mass spectrometry analysis of hexamethylene triperoxide diamine by its decomposition products

Peña-Quevedo, Alvaro J.; Hernández‐Rivera, Samuel P.

doi:10.1117/12.819080

Cited by 9 publications

(7 citation statements)

References 16 publications

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“…In Figure , the [M + H] + ion for HMTD is observed at m / z 209.0764, and this ion is accompanied by HMTD associated fragments at m / z 179.0660, 145.0604, 88.0400, 74.0608, and 60.0453. These fragments correspond to those previously observed in the mass spectrum of HMTD using the DART (direct analysis in real time) ionization source. − The ion at m / z 179 corresponds to a loss of formaldehyde from the [M + H] + ion, and that at m / z 229 is a water/methanol adduct of m / z 179. The ion at m / z 145 is a loss of hydrogen peroxide from m / z 179.…”

Section: Resultssupporting

confidence: 76%

Vapor Pressure of Hexamethylene Triperoxide Diamine (HMTD) Estimated Using Secondary Electrospray Ionization Mass Spectrometry

et al. 2015

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A rapid method for vapor pressure measurement was developed and used to derive the vapor pressure curve of the thermally labile peroxide-based explosive hexamethylene triperoxide diamine (HMTD) over the temperature range from 28 to 80 °C. This method uses a controlled flow of vapor from a solid-phase HMTD source that is presented to an ambient-pressure-ionization mass spectrometer equipped with a secondary-electrospray-ionization (SESI) source. The subpart-per-trillion sensitivity of this system enables direct detection of HMTD vapor through an intact [M + H](+) ion in real time at temperatures near 20 °C. By calibrating this method using vapor sources of cocaine and heroin, which have known pressure-temperature (P-T) curves, the temperature dependence of HMTD vapor was determined, and a Clausius-Clapeyron plot of ln[P (Pa)] vs 1/[T (K)] yielded a straight line with the expression ln[P (Pa)] = {(-11091 ± 356) × 1/[T (K)]} + 25 ± 1 (error limits are the standard error of the regression analysis). From this equation, the sublimation enthalpy of HMTD was estimated to be 92 ± 3 kJ/mol, which compares well with the theoretical estimate of 95 kJ/mol, and the vapor pressure at 20 °C was estimated to be ∼60 parts per trillion by volume, which is within a factor of 2 of previous theoretical estimates. Thus, this method provides not only the first direct experimental determination of HMTD vapor pressure but also a rapid, near-real-time capability to quantitatively measure low-vapor-pressure compounds, which will be useful for aiding in the development of training aids for bomb-sniffing canines.

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Section: Resultssupporting

confidence: 76%

Vapor Pressure of Hexamethylene Triperoxide Diamine (HMTD) Estimated Using Secondary Electrospray Ionization Mass Spectrometry

et al. 2015

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“…The molecular ion of HMTD (m/z 209.0779) was observed with an intensity of only 7% relative to the base peak at m/z 84.0817. The peak at m/z 145.0615 represents the loss of hydrogen peroxide from this [C 5 H 11 N 2 O 5 ] + ion, as reported elsewhere [58,60]. At m/z 229.0446 and m/z 245.0194, the loss of two hydrogen atoms from [M + Na] + and [M + K] + , respectively, are seen with similar intensities as observed with laser electrospray [61].…”

Section: Sawn-ms Analysis Of Organic Peroxide Explosivessupporting

confidence: 75%

“…IPA with the addition of 15 v% of an aqueous solution of 0.1 wt% of formic acid was found to be the optimal solvent mixture. Despite the limited sensitivity observed, all ions that have been previously reported with ESI and DART [15,59,60] are also seen in the SAWN MS spectrum depicted in Figure 3. This spectrum was recorded for a 30 μg/mL solution of HMTD, and this concentration also corresponded to the detection limit as at lower levels, the key adduct ions could not be consistently differentiated from the background noise.…”

Section: Sawn-ms Analysis Of Organic Peroxide Explosivesmentioning

confidence: 81%

Utilizing Surface Acoustic Wave Nebulization (SAWN) for the Rapid and Sensitive Ambient Ionization Mass Spectrometric Analysis of Organic Explosives

Pintabona

Astefanei

Corthals

et al. 2019

J. Am. Soc. Mass Spectrom.

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When considering incident investigations and security checks focused on energetic materials, there is an ongoing need for rapid, onscene chemical identification. Currently applied methods are not capable of meeting all requirements, and hence, portable mass spectrometry is an interesting alternative although many instrumental challenges still exist. To be able to analyze explosives with mass spectrometry outside the traditional laboratory, suitable ambient ionization methods need to be developed. Ideally such methods are also easily implemented in the field requiring limited to no power sources, gas supplies, flow controllers, and heating devices. For this reason, the potential of SAWN (surface acoustic wave nebulization) for the ambient ionization and subsequent mass spectrometric (MS) analysis of organic explosives was investigated in this study. Excellent sensitivity was observed for nitrate-based organic explosives when operating the MS in negative mode. No dominant adduct peaks were observed for the peroxides TATP and HMTD with SAWN-MS in positive mode. The MS spectra indicate extensive fragmentation of the peroxide explosives even under the mild ionization conditions provided by SAWN. The potential of SAWN-MS was demonstrated with the correct identification of nitrate-based organic explosives in pre-and post-explosion case samples in only a fraction of the time and effort required for the regular laboratory analysis. Results show that SAWN-MS can convincingly identify intact organic energetic compounds and mixtures but that sensitivity is not always sufficient to detect traces of explosives in post-explosion residues.

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“…The molecular ion for HMTD was observed in positive ion mode in the form of the protonated molecule ion [M + H] + at m/z 209. The 2 most dominant products for HMTD were observed at m/z 145 for [M − CH 4 O 3 ] + (due to a loss of formaldehyde and hydrogen peroxide) and at m/z 88 for [C 2 H 6 O 2 N] + …”

Section: Resultsmentioning

confidence: 99%

Explosive detection using a novel dielectric barrier discharge ionisation source for mass spectrometry

et al. 2018

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The detection of explosives is of great importance, as is the need for sensitive, reliable techniques that require little or no sample preparation and short run times for high throughput analysis. In this work, a novel ionisation source is presented based on a dielectric barrier discharge (DBD). This not only affects desorption and ionisation but also forms an ionic wind, providing mass transportation of ions towards the mass spectrometer. Furthermore, the design incorporates 2 asymmetric alumina sheets, each containing 3 DBDs, so that a large surface area can be analysed. The DBD operates in ambient air, overcoming the limitation of other plasma-based techniques which typically analyse smaller surface areas and require solvents or gases. A range of explosives across 4 different functional groups was analysed using the DBD with low limits of detection for cyclotrimethylene trinitramine (RDX) (100 pg), pentaerythritol trinitrate (PETN) (100 pg), hexamethylene triperoxide diamide (HMTD) (1 ng), and trinitrotoluene (TNT) (5 ng). Detection was achieved without any sample preparation or the addition of reagents to facilitate adduct formation.

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Mass spectrometry analysis of hexamethylene triperoxide diamine by its decomposition products

Cited by 9 publications

References 16 publications

Vapor Pressure of Hexamethylene Triperoxide Diamine (HMTD) Estimated Using Secondary Electrospray Ionization Mass Spectrometry

Vapor Pressure of Hexamethylene Triperoxide Diamine (HMTD) Estimated Using Secondary Electrospray Ionization Mass Spectrometry

Utilizing Surface Acoustic Wave Nebulization (SAWN) for the Rapid and Sensitive Ambient Ionization Mass Spectrometric Analysis of Organic Explosives

Explosive detection using a novel dielectric barrier discharge ionisation source for mass spectrometry

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