Mass spectrometric identification and quantification of glycosyl flavonoids, including dihydrochalcones with neutral loss scan mode.
We developed a strategy for determination and quantification of glycosyl flavonoids using liquid chromatography-triple quadrupole mass spectrometry with neutral loss scan at 15 and 30eV collision energy in the positive ion mode. The fragmentation patterns of glycosyl flavonoids at 15 and 30eV showed that fragmentation of sugar moiety depended on the type of glycosidic bond to aglycone, the site of C-glycosylation, and the type of aglycone. C-Glycosyl dihydrochalcones especially stood out because they produced [M+H-162](+) even at 15eV such as O-glycoside in spite of C-glycoside. C-Glycosides were classified according to (i) the intensity ratio A of [M+H-150](+) to [M+H-120](+) at 30eV and (ii) the intensity ratio B of [M+H-120](+) at 15eV to one at 30eV. The 8-C-glycosides were A<1 and B<1, the 6-C-glycosides were A>1 and B<1, and the C-glycosyl dihydrochalcones were A>1 and B>>1. Therefore, the intensity ratios of the neutral loss scan of 120 and 150Da at 30eV and those of 120, 162, and 308Da at 15eV allowed sequential distinction among these three types of C-glycosides as well as between O- and C-glycosides. Our method was applied for analysis of Rooibos tea, and the identified glycosides could be quantified specifically by the selected reaction monitoring method.
Kazuno
Saiko
S
Division of Proteomics and Biomolecular Science, BioMedical Research Center, Juntendo University Graduate School of Medicine, Tokyo 113-8421, Japan. kazuno@med.juntendo.ac.jp
Yanagida
Mitsuaki
M
Shindo
Noriko
N
Murayama
Kimie
K
D036903:Aspalathus / Q000737:chemistry; D001628:Beverages / Q000032:analysis; D002599:Chalcone / Q000031:analogs & derivatives* / Q000032:analysis / Q000737:chemistry; D047188:Chalcones / Q000032:analysis / Q000737:chemistry; D002623:Chemistry Techniques, Analytical; D002851:Chromatography, High Pressure Liquid; D005419:Flavonoids / Q000032:analysis* / Q000737:chemistry; D008401:Gas Chromatography-Mass Spectrometry; D006031:Glycosylation; D013058:Mass Spectrometry / Q000379:methods* / Q000706:statistics & numerical data; D015394:Molecular Structure
D047188:Chalcones; D005419:Flavonoids; D002599:Chalcone; C015812:dihydrochalcone