Characterization and differentiation of diglycosyl flavonoids by positive ion fast atom bombardment and tandem mass spectrometry

Abstract

This study shows that fast atom bombardment (FAB) in combination with collisional activation and tandem mass spectrometric techniques is useful for the characterization of, and the differentiation between, O-diglycosyl, O-C-diglycosyl and di-C-glycosyl flavonoids. A quick differentiation between the three types of glycosyl flavonoids is possible by simply examining FAB mass spectra. Low-energy product ion spectra of [M+H]+ ions have been used for determining the carbohydrate sequence in O-diglycosyl flavonoids and characterizing the terminal monosaccharide in O-C-diglycosyl flavonoids. The data obtained for per-O-deuterated precursor ion species of O-diglycosyl flavonoids indicate that O-linked hydrogen atoms are involved in the formation of Yn+ ions. High-energy product ion spectra of [M+H]+ ions enable further characterization and differentiation of isomeric di-6,8-C-glycosides.

Tandem mass spectral strategies for the structural characterization of flavonoid glycosides

“…With regard to collisional-induced dissociation, both high-and low-energy CID has been evaluated on instruments (1) and (2). For details about the experimental conditions reference is made to our original articles [5][6][7][8][9][10]. Experimental conditions are only given below for experiments in the negative ion mode, which were performed on instrument (3).…”

“…During the last several years our research at the University of Antwerp has focused on the structural analysis of O-, C-and O,C-diglycosides isolated from medicinal plants using fast atom bombardment (FAB) or electrospray (ES) ionization in combination with collision-induced dissociation (CID) and tandem mass spectrometry (MS/MS) [5][6][7][8][9][10]. In this article we will review various tandem mass spectral approaches to the structural characterization of flavonoid glycosides.…”

Study of C- and O-glycosylflavones in sugarcane extracts using liquid chromatography: exact mass measurement mass spectrometry

“…MS/MS in the negative ion mode using an ion trap instrument, 11 and CID using ion trap, 12 triple quadrupole 13 or magnetic sector 14 spectrometers all revealed differences in the fragmentation patterns between schaftoside and isoschaftoside sufficient to allow their differentiation and a positive ion method using FAB-CID has also been described. 15 According to such reports, 11 preferential fragmentation is of the sugar moiety at the 6-C rather than the 8-C position. In the present study it was observed that the unequivocal distinction of schaftoside and isoschaftoside was possible through comparison of the differences in the relative abundance of fragments at m/z 475 ( .…”

Characterization of the Rutin-Metal Complex by Electrospray Ionization Tandem Mass Spectrometry

“…With the development of mass spectrometry, many ionization methods have been used to characterize flavonoid compounds, such as EI, 17,18 CI, 19 and FAB. [20][21][22][23] Since the discovery of soft ionization, matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) 24 and electrospray ionization (ESI) [25][26][27][28][29][30] have also been applied to the analysis of flavonoids. Because ESI-MS has a potential to generate ions directly from the liquid phase, which means that it is possible to provide molecule structure information in a solution environment, it has become a very popular analytical method to analyze the compound structure in solution.…”