EFFECT OF CHARGE GENERATION IN ESI SOURCE ON THE NEUTRAL AROMATIC ELIMINATION MECHANISM IN XANTHOPHYLLS

Resumo

Carotenes and xanthophylls are natural pigments with high economic relevance in chemical, cosmetics, food and pharmaceutical industries. Systematic studies of carotenoid fragmentation pathways have demonstrated that the neutral elimination of aromatic ring from the polyene chain by electrocyclization reaction produced diagnostic ions to rapidly identify their presence in mixture. However, carotenes and xanthophylls also showed the ability to produce both protonated and radical molecular species, opening up multiple acid-base and/or redox fragmentation, which hamper carotenoids elucidation. Here we investigate the ionization and fragmentation of the radical/protonated and sodiated parent masses [M]^+•/[M+H]⁺ and [M+Na]⁺ of two natural xanthophylls (canthaxanthin and fucoxanthin) and the synthetic apo-b-carotene using a Fourier-transform ion-cyclotron resonance mass spectrometer (FTICR MS). The MS/MS analysis showed that sodium adduct yielded better fragmentation of the diagnostic aromatic ring elimination in a simpler MS/MS spectra, whereas molecular ion and protonated molecule resulted in a multitude of fragments involving additional charge-remote fragmentations and direct cleavages of the conjugated π-system by retro-ene and vinyl-allyl reactions. The results suggested that Na⁺ promoted electrocyclic aromatic ring elimination by assisting the correct orbital conformation of the polyene chain, giving clearly fragments to the unambiguous determination of carotenoids in biological samples.

Keywords: carotenoids, xanthophylls, pericyclic rearrangement, electrocyclization, aromatic ring elimination, FTICR MS