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 language | English (US) |
|---|---|
| Pages (from-to) | 10458-10466 |
| Number of pages | 9 |
| Journal | Analytical chemistry |
| Volume | 91 |
| Issue number | 16 |
| DOIs | |
| State | Published - Aug 20 2019 |
| Externally published | Yes |
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ASJC Scopus subject areas
- Analytical Chemistry
Cite this
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 journal › Article
}
TY - JOUR
T1 - Mass spectral similarity networking and gas-phase fragmentation reactions in the structural analysis of flavonoid glycoconjugates
AU - Pilon, Alan Cesar
AU - Gu, Haiwei
AU - Raftery, Daniel
AU - Bolzani, Vanderlan Da Silva
AU - Lopes, Norberto Peporine
AU - Castro-Gamboa, Ian
AU - Carnevale Neto, Fausto
PY - 2019/8/20
Y1 - 2019/8/20
N2 - 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.
AB - 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.
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U2 - 10.1021/acs.analchem.9b01261
DO - 10.1021/acs.analchem.9b01261
M3 - Article
C2 - 31373797
AN - SCOPUS:85072058262
VL - 91
SP - 10458
EP - 10466
JO - Analytical Chemistry
JF - Analytical Chemistry
SN - 0003-2700
IS - 16
ER -