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

  • Kevin Colizza
  • Alexander Yevdokimov
  • Lindsay McLennan
  • James L. Smith
  • Jimmie C. Oxley
Research Article


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+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.

Graphical Abstract


HMTD 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.

Supplementary material

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Copyright information

© American Society for Mass Spectrometry 2018

Authors and Affiliations

  • Kevin Colizza
    • 1
  • Alexander Yevdokimov
    • 1
  • Lindsay McLennan
    • 1
  • James L. Smith
    • 1
  • Jimmie C. Oxley
    • 1
  1. 1.Department of ChemistryUniversity of Rhode IslandKingstonUSA

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