title: Mass spectrometric identification of the N-monosubstituted N-hydroxylamino functionality in protonated analytes via ion/molecule reactions in tandem mass spectrometry.
abstract: BACKGROUND
  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.
authors.affiliation: Purdue University, Department of Chemistry, West Lafayette, IN, 47907, USA.
authors.forename: Huaming
authors.initials: H
authors.lastname: Sheng
authors.affiliation: Purdue University, Department of Chemistry, West Lafayette, IN, 47907, USA.
authors.forename: Weijuan
authors.initials: W
authors.lastname: Tang
authors.affiliation: Purdue University, Department of Chemistry, West Lafayette, IN, 47907, USA.
authors.forename: Ravikiran
authors.initials: R
authors.lastname: Yerabolu
authors.affiliation: Purdue University, Department of Chemistry, West Lafayette, IN, 47907, USA.
authors.forename: John Y
authors.initials: JY
authors.lastname: Kong
authors.affiliation: Purdue University, Department of Chemistry, West Lafayette, IN, 47907, USA.
authors.forename: Peggy E
authors.initials: PE
authors.lastname: Williams
authors.affiliation: AstraZeneca, Boston, MA, 02130, USA.
authors.forename: Minli
authors.initials: M
authors.lastname: Zhang
authors.affiliation: Purdue University, Department of Chemistry, West Lafayette, IN, 47907, USA.
authors.forename: Hilkka I
authors.initials: HI
authors.lastname: Kenttämaa
mesh_terms: D019811:Hydroxylamine / Q000737:chemistry*; D007211:Indoles / Q000737:chemistry; D000432:Methanol / Q000737:chemistry; D008738:Methyl Ethers / Q000737:chemistry; D010091:Oximes / Q000737:chemistry; D011522:Protons; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods; D053719:Tandem Mass Spectrometry / Q000379:methods; D014753:Vinyl Compounds / Q000737:chemistry
chemical_list: D007211:Indoles; D008738:Methyl Ethers; D010091:Oximes; D011522:Protons; D014753:Vinyl Compounds; C534882:2-methoxypropene; D019811:Hydroxylamine; D000432:Methanol