Gas-phase fragmentation reactions of protonated benzofuran- and dihydrobenzofuran-type neolignans investigated by accurate-mass electrospray ionization tandem mass spectrometry

Herbert J. Dias, Manon Baguenard, Eduardo J. Crevelin, Vinicius Palaretti, Paul J. Gates, Ricardo Vessecchi, Antônio E.M. Crotti*

*Corresponding author for this work

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

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Abstract

We have investigated gas‐phase fragmentation reactions of protonated benzofuran neolignans (BNs) and dihydrobenzofuran neolignans (DBNs) by accurate‐mass electrospray ionization tandem and multiple‐stage (MSn) mass spectrometry combined with thermochemical data estimated by Computational Chemistry. Most of the protonated compounds fragment into product ions B ([M + H–MeOH]+), C ([B–MeOH]+), D ([C–CO]+), and E ([D–CO]+) upon collision‐induced dissociation (CID). However, we identified a series of diagnostic ions and associated them with specific structural features. In the case of compounds displaying an acetoxy group at C‐4, product ion C produces diagnostic ions K ([C–C2H2O]+), L ([K–CO]+), and P ([L–CO]+). Formation of product ions H ([D–H2O]+) and M ([H–CO]+) is associated with the hydroxyl group at C‐3 and C‐3′, whereas product ions N ([D–MeOH]+) and O ([N–MeOH]+) indicate a methoxyl group at the same positions. Finally, product ions F ([A–C2H2O]+), Q ([A–C3H6O2]+), I ([A–C6H6O]+), and J ([I–MeOH]+) for DBNs and product ion G ([B–C2H2O]+) for BNs diagnose a saturated bond between C‐7′ and C‐8′. We used these structure‐fragmentation relationships in combination with deuterium exchange experiments, MSn data, and Computational Chemistry to elucidate the gas‐phase fragmentation pathways of these compounds. These results could help to elucidate DBN and BN metabolites in in vivo and in vitro studies on the basis of electrospray ionization ESI‐CID‐MS/MS data only.
Original languageEnglish
Pages (from-to)35-46
Number of pages12
JournalJournal of Mass Spectrometry
Volume54
Issue number1
Early online date18 Dec 2018
DOIs
Publication statusPublished - Jan 2019

Keywords

  • benzofuran
  • computational chemistry
  • dihydrobenzofuran
  • fragmentation mechanisms
  • neolignans

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