Mass spectral fragmentation of perfluoroacyl derivatives of half nitrogen mustards for their detection by Gas Chromatography - Mass Spectrometry

Rapid Communications in Mass Spectrometry : RCM
Buddhadeb ChandraMeehir Palit

Abstract

Analytical methods for the detection and identification of half nitrogen mustards (halfNMs), i.e., partial hydrolyzed product of nitrogen mustards (pHpNMs), using silyl derivatives are often associated with low sensitivity and selectivity. In order to overcome these limitations, the derivatization of halfNMs was performed using perfluoroacylation. Two efficient derivatization techniques using trifluroacetyl (TFA) and heptaflurobutyryl (HFB) groups were developed for the unambiguous identification of halfNMs. A mass spectral database was generated by performing gas chromatography electron ionization mass spectrometry (GC/EI-MS) and gas chromatography positive chemical ionization mass spectrometry (GC/PCI-MS). The fragmentation pathways were studied by tandem mass spectrometry (MS/MS) in both EI and PCI modes. The EI-MS spectra of the TFA and HFB derivatives of halfNMs contain intense molecular ions and fragment ions, thus making perfluoroacylation preferable to silylation. In addition, the background-free chromatogram obtained using these derivatives provides unambiguous identification of these compounds in blind samples. The structures of the fragment ions were postulated, and the sources of significant ions were traced by perf...Continue Reading

References

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Sep 1, 2008·Environmental Toxicology and Pharmacology·S ChauhanV Karthik
Nov 1, 2011·Journal of the American Chemical Society·Yunyan KuangXiaohua Peng
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