Using Gas Phase Reactions of Hexamethylene Triperoxide Diamine (HMTD) to Improve Detection in Mass Spectrometry
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 . 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+MeOH2–H2O2]+ (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.
KeywordsHMTD Hexamethylene triperoxide diamine TMDDD Tetramethylene diperoxide diamine dialdehyde Gas-phase reactions Smines APCI
This material is based upon work supported by US Department of Homeland Security (DHS), Science and Technology Directorate, Office of University Programs, under Grant 2013-ST-061-ED0001. Views and conclusions are those of the authors and should not be interpreted as necessarily representing the official policies, either expressed or implied, of DHS.
- 2.Bradley J. Fikes: REGION: Escondido “bomb house” controlled burn a model for nation, expert says. San Diego Union-Tribune. http://www, (2012)Google Scholar
- 3.Don Van Natta, J., Sciolino, E., Grey, S.: Details emerge in British terror case. New York Times (2006)Google Scholar
- 4.Johnson, K.: New sentence imposed in Bomb Plot from 1999. New York Times (2012)Google Scholar
- 5.Morris, S.: Terror suspect student “had suicide vest and explosives”. The Gaurdian (2009)Google Scholar
- 7.Colizza, K., Yevdokimov, A., McLennan, L., Smith, J.L., Oxley, J.C.: Reactions of organic peroxides with alcohols in atmospheric pressure chemical ionization—the pitfalls of quantifying triacetone triperoxide (TATP). J. Am. Soc. Mass Spectrom. In rress, (2017)Google Scholar
- 10.Kinghorn, R., Milner, C., Zweigenbaum, J.: Analysis of trace residues of explosive materials by time-of-flight LC/MS. Agil. Technol. Appl. Note 1–18 (2006)Google Scholar
- 14.Jeanville, P., Colizza, K., Kamel, A.: Mechanisms of ion formation for famotidine and azithromycin using hydrogen/deuterium exchange and high resolution mass measurements. ThermoFisher Sci. Appl. Note 1–6 (2007)Google Scholar
- 15.Jeanville, P., Kamel, A., Colizza, K.: Collisionally-induced dissociation of methimazole and acetylsalicylic acid : proposed mechanisms of ion formation using hydrogen / deuterium exchange. Thermo Fish. Sci. Appl. Note 375, 1–6 (2007)Google Scholar
- 17.Marr, A.J., Groves, D.M.: Ion mobility spectrometry of peroxide explosives tatp and HMTD. Int. J. Ion Mobil. Spectrom. 6, 59 (2003)Google Scholar