Determination of the glycosylation site of flavonoid monoglucosides by metal complexation and tandem mass spectrometry

Metal complexation and tandem mass spectrometry were used to differentiate C- and O-bonded flavonoid monoglucoside isomers. Electrospray ionization of solutions containing a flavonoid glycoside and a metal salt led to the generation of the key [M(II) (L) (L-H)](+) complexes, where M is the metal ion...

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Bibliographic Details
Published in:Journal of the American Society for Mass Spectrometry 2004-09, Vol.15 (9), p.1287-1299
Main Authors: DAVIS, Barry D, BRODBELT, Jennifer S
Format: Article
Language:English
Subjects:
Binding Sites
Calcium
Calcium - chemistry
Chemical bonds
Chemistry
Cobalt
Complexation
Coordination compounds
Copper
Diagnostic systems
Exact sciences and technology
Flavonoids
Flavonoids - chemistry
Glucosides
Glucosides - chemistry
Glycosylation
Ionization
Ions
Isomers
Magnesium - chemistry
Mass spectra
Mass spectrometry
Mass spectroscopy
Metals - chemistry
Molecular Structure
Nickel
Organic chemistry
Reactivity and mechanisms
Scientific imaging
Spectrometry, Mass, Electrospray Ionization
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Summary:Metal complexation and tandem mass spectrometry were used to differentiate C- and O-bonded flavonoid monoglucoside isomers. Electrospray ionization of solutions containing a flavonoid glycoside and a metal salt led to the generation of the key [M(II) (L) (L-H)](+) complexes, where M is the metal ion and L is the flavonoid glycoside. Thirteen flavonoid monoglucosides were examined in combination with Ca(II), Mg(II), Co(II), Ni(II), and Cu(II). Collisional activated dissociation (CAD) of the [M(II) (L) (L-H)](+) complexes resulted in diagnostic mass spectra, in contrast to the CAD mass spectra of the protonated, deprotonated, and sodium-cationized flavonoid glucosides. Five common sites of glycosylation could be predicted based on the fragmentation patterns of the flavonoid glucoside/magnesium complexes, while flavonoid glucoside/calcium complexes also were effective for location of the glycosylation site when MS(3) was employed. Cobalt, nickel and copper complexation had only limited success in this application. The metal complexation methods were also applied for characterization of a flavonoid rhamnoside, and the dissociation pathways of the metal complexes indicate that flavonoid rhamnosides have distinctive dissociation features from flavonoid glucosides.
ISSN:1044-0305
1879-1123
DOI:10.1016/j.jasms.2004.06.003