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Title: 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{sub 2}–H{sub 2}O{sub 2}]{sup +} (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. .

Authors:
; ; ; ;  [1]
  1. University of Rhode Island, Department of Chemistry (United States)
Publication Date:
OSTI Identifier:
22776930
Resource Type:
Journal Article
Journal Name:
Journal of the American Society for Mass Spectrometry
Additional Journal Information:
Journal Volume: 29; Journal Issue: 4; Other Information: Copyright (c) 2018 American Society for Mass Spectrometry; http://www.springer-ny.com; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 1044-0305
Country of Publication:
United States
Language:
English
Subject:
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND TECHNOLOGY; CARBON; DETECTION; IONIZATION; MASS SPECTROMETERS; MASS SPECTROSCOPY; SENSITIVITY; TEMPERATURE DEPENDENCE

Citation Formats

Colizza, Kevin, Yevdokimov, Alexander, McLennan, Lindsay, Smith, James L., and Oxley, Jimmie C., E-mail: joxley@chm.uri.edu. Using Gas Phase Reactions of Hexamethylene Triperoxide Diamine (HMTD) to Improve Detection in Mass Spectrometry. United States: N. p., 2018. Web. doi:10.1007/S13361-017-1879-5.
Colizza, Kevin, Yevdokimov, Alexander, McLennan, Lindsay, Smith, James L., & Oxley, Jimmie C., E-mail: joxley@chm.uri.edu. Using Gas Phase Reactions of Hexamethylene Triperoxide Diamine (HMTD) to Improve Detection in Mass Spectrometry. United States. doi:10.1007/S13361-017-1879-5.
Colizza, Kevin, Yevdokimov, Alexander, McLennan, Lindsay, Smith, James L., and Oxley, Jimmie C., E-mail: joxley@chm.uri.edu. Sun . "Using Gas Phase Reactions of Hexamethylene Triperoxide Diamine (HMTD) to Improve Detection in Mass Spectrometry". United States. doi:10.1007/S13361-017-1879-5.
@article{osti_22776930,
title = {Using Gas Phase Reactions of Hexamethylene Triperoxide Diamine (HMTD) to Improve Detection in Mass Spectrometry},
author = {Colizza, Kevin and Yevdokimov, Alexander and McLennan, Lindsay and Smith, James L. and Oxley, Jimmie C., E-mail: joxley@chm.uri.edu},
abstractNote = {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{sub 2}–H{sub 2}O{sub 2}]{sup +} (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. .},
doi = {10.1007/S13361-017-1879-5},
journal = {Journal of the American Society for Mass Spectrometry},
issn = {1044-0305},
number = 4,
volume = 29,
place = {United States},
year = {2018},
month = {4}
}