Mass spectrometric identification and quantification of glycosyl flavonoids, including dihydrochalcones with neutral loss scan mode
Section snippets
Materials
Aspalathin and nothofagin were provided by the Medical Research Council of South Africa (Tygerberg, South Africa). Vitexin, orientin, isoorientin, isoquercitrin, rutin, hyperoside, luteolin-7-O-glucoside, and phloretin were purchased from Extrasynthese (Genay, France). Isovitexin was obtained from Indofine Chemical (Hillsborough, NJ, USA). Daidzin, acetonitrile (for LC–MS), and methanol (for HPLC) were purchased from Wako Pure Chemical Industries (Osaka, Japan). Formic acid was obtained from
Fragmentation patterns of C- and O-glycosyl flavonoids in the positive mode
The theoretical fragmentation pattern of glycosyl flavonoid is shown in Fig. 1. The cleavage and nomenclature were described according to the system adopted by Waridel et al. [11]. O-Glycosyl flavonoid for rutin, which is a disaccharide composed of rhamnosyl glucose (rutinose), produced the Y0+ and Y1+ ions by fragmentation of the O-glycosidic bond. The Y0+ ion is neutral loss of 308 Da (rutinose), and the Y1+ ion is 146 Da (rhamnose) as loss of terminal sugar moiety. Although both ions appeared
Conclusion
We confirmed that collision-induced dissociation analysis at two levels of collision energy in the positive ion mode could distinguish sequentially not only between O- and C-glycoside but also the C-glycosidic site. In addition, it was remarkable that C-glycosyl dihydrochalcone showed characteristic fragmentation, which occurred even at low collision energy and produced Y0+ ion corresponding to neutral loss of 162 Da in spite of C-glycoside.
These results allowed effective identification of
Acknowledgment
We thank Yoshikazu Ohtsuka, Department of Pediatrics and Adolescent Medicine, Juntendo University School of Medicine, Tokyo, for kindly providing the glycosyl flavonoid standards and Rooibos tea samples.
References (35)
- et al.
Oxidative DNA damage: assessment of the role in carcinogenesis, atherosclerosis, and acquired immunodeficiency syndrome
Free Radic. Biol. Med.
(2002) - et al.
Structural determination of 6-C-diglycosyl-8-C-glycosylflavones and 6-C-glycosyl-8-C-diglycosylflavones by mass spectrometry of their permethyl ethers
Phytochemistry
(1984) Application of mass spectrometry for identification and structural studies of flavonoid glycosides
Phytochemistry
(2000)- et al.
Evaluation of quadrupole time-of-flight tandem mass spectrometry and ion-trap multiple-stage mass spectrometry for the differentiation of C-glycosidic flavonoid isomers
J. Chromatogr. A
(2001) - et al.
Identification and determination of glucuronides and their aglycones in Erigeron breviscapus by liquid chromatography–tandem mass spectrometry
J. Chromatogr. A
(2001) - et al.
Structural characterization of flavonoid glycosides by collisionally activated dissociation of metal complexes
J. Am. Soc. Mass Spectrom.
(2001) - et al.
Differentiation of flavonoid glycoside isomers by using metal complexation and electrospray ionization mass spectrometry
J. Am. Soc. Mass Spectrom.
(2003) - et al.
Determination of the glycosylation site of flavonoid monoglucosides by metal complexation and tandem mass spectrometry
J. Am. Soc. Mass Spectrom.
(2004) - et al.
Threshold dissociation and molecular modeling of transition metal complexes of flavonoids
J. Am. Soc. Mass Spectrom.
(2005) - et al.
Superoxide anion and α,α-diphenyl-β-picrylhydrazyl radical scavenging capacity of Rooibos (Aspalathus linearis) aqueous extracts, crude phenolic fractions, tannin and flavonoids
Food Res. Int.
(2004)
HPLC quantification of the dihydrochalcones, aspalathin and nothofagin, in Rooibos tea (Aspalathus linearis) as affected by processing
Food Chem.
Internal glucose residue loss in protonated O-diglycosyl flavonoids upon low-energy collision-induced dissociation
J. Am. Soc. Mass Spectrom.
Flavonoids as antioxidants
J. Nat. Prod.
Mass spectrometry in the structural analysis of flavonoids
J. Mass Spectrom.
Fast atom bombardment and fast atom bombardment collision-activated dissociation/mass-analysed ion kinetic energy analysis of C-glycosidic flavonoids
Biomed. Environ. Mass Spectrom.
Electron impact mass spectral analysis of flavonoids
J. Agric. Food Chem.
Mass spectrometric methods for the characterisation and differentiation of isomeric O-diglycosyl flavonoids
Phytochem. Anal.
Cited by (97)
Biological importance and therapeutic potential of Trilobatin in the management of human disorders and associated secondary complications
2022, Pharmacological Research - Modern Chinese MedicineCitation Excerpt :Flavonoids, chalcones and chalcone derivatives have been reported to display cytotoxic, anti-tumor, anti-inflammatory, anti-plasmodial, immunosuppressive and antioxidant properties [56]. Flavonoids have attracted a great deal of attention due to their antioxidant activity to scavenge reactive oxygen species (ROS), which cause lipid peroxidation in the cell membrane, protein modification, and DNA damage [57]. Dihydrochalcone is a flavonoid class phytochemical having two aromatic rings and a saturated C3 chain in the basic C6-C3-C6 skeleton structure.
Herbal medicine used to treat andrological problems: Africa
2021, Herbal Medicine in AndrologyStudy of the pharmacokinetics of eriodictyol-6-C-β-D-glucoside, a flavonoid of rooibos (Aspalathus linearis) extract, after its oral administration in mice
2020, Journal of Chromatography B: Analytical Technologies in the Biomedical and Life SciencesThe Structure and Function of Major Plant Metabolite Modifications
2019, Molecular Plant