Using Gas Phase Reactions of Hexamethylene Triperoxide Diamine (HMTD) to Improve Detection in Mass Spectrometry

Abstract

Our efforts to lower the detection limits of hexamethylene triperoxide diamine (HMTD) have uncovered previously unreported gas-phase reactions of primary and secondary amines with one of the six methylene carbons. The reaction occurs primarily in the atmospheric pressure chemical ionization (APCI) source and is similar to the behavior of alcohols with HMTD [1]. However, unlike alcohols, the amine reaction conserves the hydrogen peroxide on the intact product. Furthermore, with or without amines, HMTD is oxidized to tetramethylene diperoxide diamine dialdehyde (TMDDD) in a temperature-dependent fashion in the APCI source. Synthesized TMDDD forms very strong adducts (not products) to ammonium and amine ions in the electrospray ionization (ESI) source. Attempts to improve HMTD detection by generating TMDDD in the APCI source with post-column addition of amines were not successful. Signal intensity of the solvent related HMTD product in methanol, [HMTD+MeOH-HO] (m/z 207.0975), was understandably related to the amount of methanol in the HMTD environment as it elutes into the source. With conditions optimized for this product, the detection of 100 pg on column was accomplished with a robust analysis of 300 pg (1.44 pmol) routinely performed on the Orbitrap mass spectrometers. Graphical Abstract ᅟ.

n-Butylamine for Improving the Efficiency of Untargeted Mass Spectrometry Analysis of Plasma Metabolite Composition

“…We assumed that the proposed decontamination procedure would also be effective for the elimination other alkylamines, for instance, N,N,N -triethylamine (TEA). After using TEA as an additive for MS analysis and the ordinary washing procedure (direct infusion of 50% aqueous acetonitrile by a syringe pump for 20 min, flow rate of 180 µL/h), the polarity was switched from negative to positive and a highly intense peak corresponding to TEA (102.1277 m / z for TEA [M + H] + ) [31]) was observed in the positive ion mass spectra (Figure 5A). There was no significant alteration in signal intensity after flushing with a high volume of ordinary cleaning solution (direct infusion of 50% aqueous acetonitrile by syringe pump) for a long time.…”

Silica Nanoparticle/Fluorescent Dye Assembly Capable of Ultrasensitively Detecting Airborne Triacetone Triperoxide: Proof-of-Concept Detection of Improvised Explosive Devices in the Workroom

“…Common explosives containing nitro groups, such as trinitrotoluene (TNT), have a large variety of fluorescent methods for their detection, including our contribution to the field and from other groups. − Another explosive employed in IEDs which is also important, hexamethylene triperoxide diamine (HMTD), has a much lower vapor pressure than TATP. Unfortunately, the detection of HMTD in the vapor phase is not possible . For the detection of TATP, the most common methods are mass spectrometry, ion mobility spectrometry or related technologies, − and multiphoton spectroscopy .…”

“…Unfortunately, the detection of HMTD in the vapor phase is not possible. 24 For the detection of TATP, the most common methods are mass spectrometry, 25 ion mobility spectrometry or related technologies, 26−28 and multiphoton spectroscopy. 29 Optional complementary methods are chemically modified nanosensor arrays, 30 or portable optical methods based on colorimetric sensor arrays, in this case to detect the hydrogen peroxide (H 2 O 2 ) produced by decomposition of the TATP.…”

Dye-modified silica–anatase nanoparticles for the ultrasensitive fluorogenic detection of the improvised explosive TATP in an air microfluidic device

“…Albeit TATP sublimes at room temperature, its presence in the vapor phase is not usually detected by the use of common methods for explosives because of the lack of aromatic nitro groups. 18 In contrast, other important explosive, hexamethylene triperoxide diamine (HMTD) also employed in IEDs has a much lower vapor pressure than TATP therefore its detection in the vapor phase 19 is not possible. Usual methods for the detection of TATP are mass spectrometry, 20 ion mobility spectrometry or related technologies [21][22][23] and multiphoton spectroscopy.…”