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Anthocyanidins structural study using positive electrospray ionization triple quadrupole mass spectrometry and H/D exchange
Author(s) -
Poliseli Camila B.,
Ribeiro Marcos,
Tonin Angelica P.P.,
Vagula Julianna M.,
Santos Oscar O.,
Visentainer Jesuí V.,
Pontes Rodrigo M.,
Moraes Luiz A.B.,
Meurer Eduardo C.
Publication year - 2018
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/jms.4293
Subject(s) - chemistry , anthocyanidins , fragmentation (computing) , tandem mass spectrometry , triple quadrupole mass spectrometer , mass spectrometry , electrospray ionization , collision induced dissociation , computational chemistry , analytical chemistry (journal) , thermochemistry , selected reaction monitoring , chromatography , organic chemistry , flavonoid , computer science , antioxidant , operating system
We report herein a detailed structural study by collision‐induced dissociation (CID) of nonglycosylated anthocyanins (anthocyanidins) using electrospray ionization triple quadrupole mass spectrometry (ESI‐QqQ) and isotope labeling experiments to understand the fragmentation process often used in mass spectrometry analysis of this class of compounds. Tandem mass spectrometric product ion spectra for three anthocyanidins (cyanidin, delphynidin, and pelargonin) were evaluated to propose fragmentation mechanisms to this natural colorant class of organic compounds. The proposed rearrangements, retro Diels‐Alder reaction, water loss, CO losses, and stable acylium ion formation, were evaluated based on tandem mass spectrometric experiments of normal and labeled precursor ions together to computational thermochemistry. B3LYP/6‐311 + G** ab initio calculations studies were carried out to obtain energy diagrams to show the viability of the proposed mechanisms. The CO losses fragmentation channels have lower energies when compared with water losses and the other proposed fragmentations. The isotope labeling experiments indicate the H/D exchange of the hydroxyl protons and corroborate the proposed general fragmentation mechanism for anthocyanidins.