Identification of isobaric product ions in electrospray ionization mass spectra of fentanyl using multistage mass spectrometry and deuterium labeling

Isobaric product ions cannot be differentiated by exact mass determinations, although in some cases deuterium labeling can provide useful structural information for identifying isobaric ions. Proposed fragmentation pathways of fentanyl were investigated by electrospray ionization ion trap mass spect...

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Bibliographic Details
Published in:Rapid communications in mass spectrometry 2010-09, Vol.24 (17), p.2547-2553
Main Authors: Wichitnithad, Wisut, McManus, Terence J., Callery, Patrick S.
Format: Article
Language:English
Subjects:
Deuterium
Deuterium Exchange Measurement - methods
Fentanyl - chemistry
Fragmentation
Ionization
Isobars
Isomerism
Marking
Mass spectrometry
Multistage
Pressure
Spectra
Spectrometry, Mass, Electrospray Ionization - methods
Tandem Mass Spectrometry - methods
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Summary:Isobaric product ions cannot be differentiated by exact mass determinations, although in some cases deuterium labeling can provide useful structural information for identifying isobaric ions. Proposed fragmentation pathways of fentanyl were investigated by electrospray ionization ion trap mass spectrometry coupled with deuterium labeling experiments and spectra of regiospecific deuterium labeled analogs. The major product ion of fentanyl under tandem mass spectrometry (MS/MS) conditions (m/z 188) was accounted for by a neutral loss of N‐phenylpropanamide. 1‐(2‐Phenylethyl)‐1,2,3,6‐tetrahydropyridine (1) was proposed as the structure of the product ion. However, further fragmentation (MS3) of the fentanyl m/z 188 ion gave product ions that were different from the product ion in the MS/MS fragmentation of synthesized 1, suggesting that the m/z 188 product ion from fentanyl includes an isobaric structure different from the structure of 1. MS/MS fragmentation of fentanyl in deuterium oxide moved one of the isobars to 1 Da higher mass, and left the other isobar unchanged in mass. Multistage mass spectral data from deuterium‐labeled proposed isobaric structures provided support for two fragmentation pathways. The results illustrate the utility of multistage mass spectrometry and deuterium labeling in structural assignment of isobaric product ions. Copyright © 2010 John Wiley & Sons, Ltd.
ISSN:0951-4198
1097-0231
1097-0231
DOI:10.1002/rcm.4673