Mass Spectral Similarity Networking and Gas-Phase Fragmentation Reactions in the Structural Analysis of Flavonoid Glycoconjugates

Author(s)

Pilon, Alan Cesar ^{[1, 2]} ; Gu, Haiwei ^{[3, 4]} ; Raftery, Daniel ^{[4, 5]} ; Bolzani, Vanderlan da Silva ^[2] ; Lopes, Norberto Peporine ^[1] ; Castro-Gamboa, Ian ^[2] ; Carnevale Neto, Fausto ^{[1, 4, 2]}

Affiliation

^[1] Univ Sao Paulo, Fac Ciencias Farmaceut Ribeirao Preto, Dept Fis & Quim, NPPNS, BR-14040903 Ribeirao Preto, SP - Brazil

^[2] Univ Estadual Paulista, UNESP, Dept Quim Organ, Inst Quim, Nucleo Bioensaios Biossintese & Ecofisiol Prod Na, BR-14800900 Araraquara, SP - Brazil

^[3] East China Inst Technol, Jiangxi Key Lab Mass Spectrometry & Instrumentat, Nanchang, Jiangxi - Peoples R China

^[4] Univ Washington, Northwest Metabol Res Ctr, Dept Anesthesiol & Pain Med, 850 Republican St, Seattle, WA 98109 - USA

^[5] Fred Hutchinson Canc Res Ctr, Publ Hlth Sci Div, Seattle, WA 98109 - USA

• Document type: Journal article
• Source: Analytical Chemistry; v. 91, n. 16, p. 10413-10423, AUG 20 2019.
• Web of Science Citations: 2

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. (AU)

• FAPESP's process: 16/13292-8 - Analysis of nitrogen content in antropic influenced areas in Amazon and Atlantic Forest using a metabolomic tools
• Grantee: Alan Cesar Pilon
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 10/17935-4 - Development of analytical methods of dereplication by NMR and multivaried analysis of metabolomic profile from Solanaceae species with bioactive potential
• Grantee: Alan Cesar Pilon
• Support Opportunities: Scholarships in Brazil - Doctorate
• FAPESP's process: 03/02176-7 - Conservation and sustainable use of the diversity from Cerrado and Atlantic Forest: chemical diversity and prospecting for potential drugs - phase II
• Grantee: Vanderlan da Silva Bolzani
• Support Opportunities: BIOTA-FAPESP Program - Thematic Grants
• FAPESP's process: 14/12343-2 - Method development and prospection studies of marine biological resources with citotoxic potential based on systems biology
• Grantee: Fausto Carnevale Neto
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 10/07564-9 - Study of Chrysobalanaceae species with cytotoxic activities: Metabolomic analysis for the understanding of sinergistic associations and their micromolecular complexity
• Grantee: Fausto Carnevale Neto
• Support Opportunities: Scholarships in Brazil - Doctorate
• FAPESP's process: 14/50265-3 - Distribution and metabolism of natural and synthetic xenobiotics: from the comprehension of reactional process to tissue imaging generation
• Grantee: Norberto Peporine Lopes
• Support Opportunities: BIOTA-FAPESP Program - Thematic Grants