Peculiarities of the Mass Spectrometric Detection of Anthocyanins in High-Performance Liquid Chromatography
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The dependence of the degree of fragmentation of anthocyanin “molecular” ions on the cone voltage of a mass spectrometric electrospray ionization detector was studied. It was found that the voltage required for the fragmentation of 50% of original “molecular” ions, E f (0.5), increased with the number of glycoside residues. The fragmentation of glycosides proceeds with the removal of the entire residue regardless of their structures. In the case of 3,5-diglycosides, two types of fragment ions formed due to the loss of glycosidic residues from different positions; the ratio of their peak intensities is reciprocal to the ratio of the masses of residues eliminated. The values of E f (0.5) for monoglycosides (190 V), diglycosides (229 V), triglycosides (267 V), and for some acylated cyanidin-3,5-diglycosides are determined. These results were given for the gradient separation of anthocyanins by reversed-phase HPLC in aqueous acetonitrile containing 10 vol % of formic acid using quadrupole mass spectrometric detection.
Keywordsanthocyanins HPLC mass spectrometric detector electrospray voltage of 50% fragmentation
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