Mass spectral similarity networking and gas-phase fragmentation reactions in the structural analysis of flavonoid glycoconjugates

Alan Cesar Pilon, Haiwei Gu, Daniel Raftery, Vanderlan Da Silva Bolzani, Norberto Peporine Lopes, Ian Castro-Gamboa, Fausto Carnevale Neto

Research output: Contribution to journalArticle

Abstract

Flavonoids represent an important class of natural products with a central role in plant physiology and human health. Their accurate annotation using untargeted mass spectrometry analysis still relies on differentiating similar chemical scaffolds through spectral matching to reference library spectra. In this work, we combined molecular network analysis with rules for fragment reactions and chemotaxonomy to enhance the annotation of similar flavonoid glyconjugates. Molecular network topology progressively propagated the flavonoid chemical functionalization according to collision-induced dissociation (CID) reactions, as the following chemical attributes: aglycone nature, saccharide type and number, and presence of methoxy substituents. This structure-based distribution across the spectral networks revealed the chemical composition of flavonoids across intra- and interspecies and guided the putatively assignment of 64 isomers and isobars in the Chrysobalanaceae plant species, most of which are not accurately annotated by automated untargeted MS2 matching. These proof of concept results demonstrate how molecular networking progressively grouped structurally related molecules according to their product ion scans, abundances, and ratios. The approach can be extrapolated to other classes of metabolites sharing similar structures and diagnostic fragments from tandem mass spectrometry.

Original languageEnglish (US)
Pages (from-to)10458-10466
Number of pages9
JournalAnalytical chemistry
Volume91
Issue number16
DOIs
StatePublished - Aug 20 2019
Externally publishedYes

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Glycoconjugates
Flavonoids
Structural analysis
Gases
Mass spectrometry
Physiology
Electric network analysis
Metabolites
Biological Products
Scaffolds
Isomers
Topology
Health
Ions
Molecules
Chemical analysis

ASJC Scopus subject areas

  • Analytical Chemistry

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Mass spectral similarity networking and gas-phase fragmentation reactions in the structural analysis of flavonoid glycoconjugates. / Pilon, Alan Cesar; Gu, Haiwei; Raftery, Daniel; Bolzani, Vanderlan Da Silva; Lopes, Norberto Peporine; Castro-Gamboa, Ian; Carnevale Neto, Fausto.

In: Analytical chemistry, Vol. 91, No. 16, 20.08.2019, p. 10458-10466.

Research output: Contribution to journalArticle

Pilon, Alan Cesar ; Gu, Haiwei ; Raftery, Daniel ; Bolzani, Vanderlan Da Silva ; Lopes, Norberto Peporine ; Castro-Gamboa, Ian ; Carnevale Neto, Fausto. / Mass spectral similarity networking and gas-phase fragmentation reactions in the structural analysis of flavonoid glycoconjugates. In: Analytical chemistry. 2019 ; Vol. 91, No. 16. pp. 10458-10466.
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