Characterisation of anthocyanidins by electrospray ionisation and collision‐induced dissociation tandem mass spectrometry

Abstract

The present study describes the use of electrospray ionisation mass spectrometry, in combination with collision-induced dissociation (CID) and tandem mass spectrometry, for the structural characterisation of anthocyanidins and their O-glycosides. The high-energy CID spectra of [M-Cl](+) ions of the free aglycones show characteristic fragmentation pathways, which provide useful information about the substitution pattern in the A- and B-rings of each compound. The major fragmentation observed in the high-energy CID spectra of [M-Cl](+) ions of anthocyanins involves loss of the mono- or disaccharide units resulting in ions containing only the aglycone moiety. From the spectral data, the identity of the aglycone can be established as well as the number and the class of monosaccharide units in the O-glycosides.

Anthocyanin content and antioxidant capacity in bran extracts of some Thai black rice varieties

“…Regardless of their different relative intensities, a series of these product ions was in accordance with those in the report of Oliveira et al . () on the characterisation of peonidin‐3‐ O ‐glucoside.…”

“…The confirmation of the chemical structure of the black rice anthocyanin aglycones was done by elucidating the fragmentation patterns of their full scan daughter ion mass spectra obtained by LC-ESI-MS/ MS. The MS/MS spectra were also compared with those reported previously (Oliveira et al, 2001;Montoro et al, 2006). The product ion mass spectrum of the parent aglycone ion, [M-glucose] + , having m/z 287 is shown in Fig.…”

Liquid chromatography–mass spectrometry identification of anthocyanins of isla oca (Oxalis tuberosa, Mol.) tubers

“…When an anthocyanidin is substituted with two sugars in positions 3 and 5, respectively, the fragmentation of the molecular ion leads to the formation of three fragment ions, one corresponding to the aglycone, another corresponding to the 3-O-glycoside and the last corresponding to the 5-O-glycoside. If both sugars were the same, only two signals would appear in the MS 2 spectrum: one corresponding to the aglycone and the other corresponding to the two possible monoglycosides [24,25]. Taking into account the analytical data and this fact, peak 3 was identified as malvidin 3,5-O-diglucoside.…”

Identification of dimeric anthocyanins and new oligomeric pigments in red wine by means of HPLC‐DAD‐ESI/MSn

“…API techniques and especially ESI/MS have been largely employed over the last decade as interfaces coupled to HPLC. In addition, collision induced dissociation (CID) tandem mass (MS/MS) spectrometry and MS n analyses, which allow the sequential fragmentation of a given molecular ion, provide information for the identification of anthocyanins based on their fragmentation patterns 12. This information is very useful to differentiate compounds with similar chromatographic and UV‐vis spectral features and possess the same m / z ratios.…”