Mass spectrometric identification of the N‐monosubstituted N‐hydroxylamino functionality in protonated analytes via ion/molecule reactions in tandem mass spectrometry. (16th March 2015)

• Record Type: Journal Article
• Authors: Sheng, Huaming; Tang, Weijuan; Yerabolu, Ravikiran; Kong, John Y.; Williams, Peggy E.; Zhang, Minli; Kenttämaa, Hilkka I.
• Is Part Of: Rapid communications in mass spectrometry. Volume 29:Number 8(2015)
• Page Start: 730
• Page End: 734
• Publication Date: 2015-03-16
• Subjects: Mass spectrometry -- Periodicals; 543.65
• DOI: 10.1002/rcm.7154
• Languages: English
• ISSNs: 0951-4198

Abstract

Abstract : Rationale: N ‐Monosubstituted hydroxylamines correspond to an important class of metabolites for many bioactive molecules. In this study, a tandem mass spectrometric method based on ion/molecule reactions was developed for the identification of compounds with the N ‐monosubstituted hydroxylamino functionality. Methods: The diagnostic ion/molecule reaction occurs between protonated analytes with 2‐methoxypropene (MOP) inside a linear quadrupole ion trap mass spectrometer. Results: Most protonated compounds with N ‐monosubstituted and disubstituted hydroxylamino and oxime functional groups react with MOP via proton transfer and formation of a stable adduct in a linear quadrupole ion trap mass spectrometer. However, only protonated compounds with N ‐monosubstituted hydroxylamino groups form the characteristic MOP adduct–MeOH product. Possible mechanisms of this reaction are discussed. Conclusions: A method based on functional group‐selective ion/molecule reactions in a linear quadrupole ion trap mass spectrometer has been demonstrated to allow the identification of protonated compounds with the N ‐monosubstituted hydroxylamino functionality. Only N ‐monosubstituted hydroxylamines react with MOP via formation of an adduct that has eliminated methanol. Copyright © 2015 John Wiley & Sons, Ltd.