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- Title
Re-investigation of the fragmentation of protonated carotenoids by electrospray ionization and nanospray tandem mass spectrometry.
- Authors
Neto, Fausto Carnevale; Guaratini, Thais; Costa‐Lotufo, Letícia; Colepicolo, Pio; Gates, Paul J.; Lopes, Norberto Peporine
- Abstract
RATIONALE: Carotenoids are polyene isoprenoids with an important role in photosynthesis and photoprotection. Their characterization in biological matrices is a crucial subject for biochemical research. In this work we report the full fragmentation of 16 polyenes (carotenes and xanthophylls) by electrospray ionization tandem mass spectrometry (ESI-CID-MS/MS) and nanospray tandem mass spectrometry (nanoESI-CID-MS/MS). METHODS: Analyses were carried out on a quadrupole time-of-flight (QTOF) mass spectrometer coupled with a nanoESI source and on a Fourier transform ion cyclotron resonance (FTICR) mass spectrometer with an ESI source. The formulae of the product ions were determined by accurate-mass measurements. RESULTS: It is demonstrated that the fragmentation routes observed for the protonated carotenoids derive essentially from charge-remote fragmentations and pericyclic rearrangements, such as electrocyclic and retro-ene eliminations (assisted or not by a sigmatropic hydrogen shift). All mechanisms are dependent on cis-trans isomerization through the formation of several conjugated polyene carbocation intermediates. Some specific ions for the carotenoid epoxides were justified through formation of cyclic oxonium ions. CONCLUSIONS: Complete fragmentation pathways of protonated carotenoids by ESI- and nanoESI-CID-MS/MS provided structural information about functional groups, polyene chain and double bonds, and contribute to identification of carotenoids based on MS/MS fragmentation patterns.
- Subjects
POLYENES; CAROTENES; XANTHOPHYLLS; ELECTROSPRAY ionization mass spectrometry; TIME-of-flight mass spectrometry; ION cyclotron resonance spectrometry
- Publication
Rapid Communications in Mass Spectrometry: RCM, 2016, Vol 30, Issue 13, p1540
- ISSN
0951-4198
- Publication type
Article
- DOI
10.1002/rcm.7589