Structural characterization of flavonol di-O-glycosides from Farsetia aegyptia by electrospray ionization and collision-induced dissociation mass spectrometry.
This study reports the application of mass spectrometric methods to characterize unknown flavonoids of the herb Farsetia aegyptia Turra (Crucifereae). High-performance liquid chromatography was performed in combination with UV-photodiode array detection (LC/UV-DAD) and electrospray ionization mass spectrometry (LC/ESI-MS) in both positive and negative ion modes. Collision-induced dissociation (CID) mass spectral data were obtained off-line by nanospray (nano-ESI) analysis, which provided a wealth of information and led to the structural proposal of the flavonol di-O-glycosides present in the herb extract. In addition to the mass spectral data, we also report NMR data for the major compound which allowed the completion of its structural elucidation. The Farsetia aegyptia Turra herb extract was found to contain three flavonol di-O-glycosides containing a monosaccharidic residue linked to the 3-O position and a disaccharidic residue linked to the 7-O position; the major compound was characterized as the new flavonoid, isorhamnetin 3-O-alpha-L-arabinoside 7-O-[beta-D-glucosyl-1 --> 2]-alpha(L)rhamnoside. Different types of CID spectra, i.e., low-energy [M+H]+, [M+Na]+ and [M--H]- spectra as well as high-energy [M+Na]+ spectra, were evaluated with respect to their utility to locate the O-linked saccharidic residues in flavonol di-O-glycosides and to determine the sequence in the disaccharidic part. In agreement with previously published data, the 3-O-glycosyl residue was more readily lost from the protonated molecule than the 7-O-glycosyl residue. The opposite behavior was noted for the fragmentation of the deprotonated and sodiated molecules. Radical ions were observed in the high-energy [M+Na]+ CID spectra which provided supporting information on the glycosylation positions.
Shahat
Abdelaaty A
AA
Department of Pharmaceutical Sciences, University of Antwerp, B-2610 Antwerp, Belgium.
Cuyckens
Filip
F
Wang
Wu
W
Abdel-Shafeek
Khaled A
KA
Husseiny
Husseiny A
HA
Apers
Sandra
S
Van Miert
Sabine
S
Pieters
Luc
L
Vlietinck
Arnold J
AJ
Claeys
Magda
M
D019607:Brassicaceae / Q000737:chemistry*; D002851:Chromatography, High Pressure Liquid; D044948:Flavonols / Q000032:analysis / Q000737:chemistry*; D006027:Glycosides / Q000032:analysis / Q000737:chemistry*; D008514:Medicine, Arabic; D010936:Plant Extracts / Q000737:chemistry; D010946:Plants, Medicinal / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization
D044948:Flavonols; D006027:Glycosides; D010936:Plant Extracts