Electrospray tandem mass spectrometric investigations of morphinans.
In this study positive ESI tandem mass spectra of the [M + H]+ ions of morphinan alkaloids obtained using an ion trap MS were compared with those from a triple quadrupole MS. This allows to assess the differences of the tandem-in-time versus the tandem-in-space principle, often hampering the development of ESI MS/MS libraries. Fragmentation pathways and possible fragment ion structures were discussed. In order to obtain elemental composition, accurate mass measurements were performed. According to the MS/MS fragmentation pathway, the investigated compounds can be grouped into 4 subsets: (1) morphine and codeine, (2) morphinone, codeinone, and neopinone, (3) thebaine and oripavine, (4) salutaridine and salutaridinol. Salutaridinol-7-O-acetate shows a different fragmentation behavior because of the favored loss of acetic acid. Although most fragment ions occur in both ion trap and triple quad tandem mass spectra, some are exclusively seen in either type. For triple quad, quadrupole time-of-flight and FT-ICR MS/MS, the base peak of morphine results from an ion at m/z 165 that contains neither nitrogen nor oxygen. This ion is not found in ion trap MS/MS, but in subsequential MS3 and MS4.
Institute of Pharmaceutics and Biopharmaceutics, Martin Luther University, Halle, Germany. raith@pharmazie.uni-halle.de
Klaus
K
Raith
Reinhard
R
Neubert
Chotima
C
Poeaknapo
Christian
C
Boettcher
Meinhart H
MH
Zenk
Jürgen
J
Schmidt
D005583:Fourier Analysis; D007202:Indicators and Reagents; D009019:Morphinans / Q000737:chemistry*; D009022:Morphine Derivatives / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization
D007202:Indicators and Reagents; D009019:Morphinans; D009022:Morphine Derivatives