| Full text | |
| Author(s): |
Carnevale Neto, Fausto
;
Guaratini, Thais
;
Costa-Lotufo, Leticia
;
Colepicolo, Pio
;
Gates, Paul J.
;
Lopes, Norberto Peporine
Total Authors: 6
|
| Document type: | Journal article |
| Source: | RAPID COMMUNICATIONS IN MASS SPECTROMETRY; v. 30, n. 13, p. 9-pg., 2016-07-15. |
| 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. Copyright (C) 2016 John Wiley & Sons, Ltd. (AU) | |
| FAPESP's process: | 14/50265-3 - Distribution and metabolism of natural and synthetic xenobiotics: from the comprehension of reactional process to tissue imaging generation |
| Grantee: | Norberto Peporine Lopes |
| Support Opportunities: | BIOTA-FAPESP Program - Thematic Grants |
| FAPESP's process: | 14/12343-2 - Method development and prospection studies of marine biological resources with citotoxic potential based on systems biology |
| Grantee: | Fausto Carnevale Neto |
| Support Opportunities: | Scholarships in Brazil - Post-Doctoral |