Electrospray ionization tandem mass spectrometry analysis of isopimarane diterpenes from Velloziaceae

Angelo da Cunha Pinto, Ricardo Vessecchi, Carmelita Gomes da Silva, Ana Carolina Lourenço Amorim, Helvécio Martins Dos Santos Júnior, Michelle Jakeline Cunha Rezende, Paul J Gates, Claudia Moraes Rezende, Norberto Peporine Lopes

Research output: Contribution to journalArticle (Academic Journal)peer-review

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Abstract

RATIONALE: The study of natural products by electrospray ionization tandem mass spectrometry (ESI-MS/MS) is an important strategy for the characterization of the major fragmentation reactions which can then help to determine the composition of complex mixtures. Application of ESI-MS/MS to a series of isopimarane diterpenes from Velloziaceae allowed the rationalization of their fragmentation mechanisms.

METHODS: Velloziaceae diterpenes were isolated by silica gel column chromatography and investigated by ESI-MS/MS analysis. The fragmentation studies were performed on a quadrupole-time-of-flight instrument using N2 as the collision gas. To help rationalize the fragmentation pathways observed, the geometry and sites of reactivity of the diterpenes were obtained by theoretical calculations using the B3LYP/6-31 + G(d,p) model. Fragmentation mechanisms were proposed on the basis of the calculated protonation sites and product ions energies using density functional theory (DFT) methods.

RESULTS: The presence of hydroxyl and carbonyl groups on the terpene core influences the protonation site observed. One compound showed a radical cation as the base peak. MS/MS spectra exhibit water elimination as the major fragmentation pathway (via two ways), either when protonation takes place on the oxygen atom, or through elimination after activation from hydrogen migration. After the elimination of water, the formation of an endocyclic double bond induces a sequential retro-Diels-Alder (RDA) reaction as the major fragmentation step.

CONCLUSIONS: A thorough rational analysis of the fragmentation mechanisms of protonated Velloziaceae diterpenes was used to propose the dissociation mechanisms in ESI-MS/MS. The presence of esters in the side chain also influenced the intensity or occurrence of the observed protonated or cationized molecules in ESI-MS. These results will aid the identification of analogues in sample extracts in future metabolomics studies. Copyright © 2015 John Wiley & Sons, Ltd.

Original languageEnglish
Pages (from-to)61-68
Number of pages8
JournalRapid Communications in Mass Spectrometry
Volume30
Issue number1
Early online date2 Dec 2015
DOIs
Publication statusPublished - 15 Jan 2016

Keywords

  • fragmentation mechanism
  • Velloziaceae
  • natural products
  • terpene

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