Structural characterization of flavonol 3,7-di-O-glycosides and determination of the glycosylation position by using negative ion electrospray ionization tandem mass spectrometry

被引:217
作者
Ablajan, K
Abliz, Z [1 ]
Shang, XY
He, JM
Zhang, RP
Shi, JG
机构
[1] Chinese Acad Med Sci, Inst Mat Med, Key Lab Bioact Subst & Resource Utilizat Chinese, Minist Educ, Beijing 100050, Peoples R China
[2] Peking Union Med Coll, Beijing 100050, Peoples R China
来源
JOURNAL OF MASS SPECTROMETRY | 2006年 / 41卷 / 03期
关键词
flavonol 3,7-di-O-glycosides; structural characterization; glycosylation position; negative ion electrospray ionization; tandem mass spectrometry;
D O I
10.1002/jms.995
中图分类号
Q5 [生物化学];
学科分类号
071010 ; 081704 ;
摘要
Flavonol 3,7-di-O-glycosides were investigated by negative ion electrospray ionization tandem mass spectrometry using a quadrupole linear ion trap (LIT) mass spectrometer. The results indicate that the fragmentation behavior of flavonol 3,7-di-O-glycosides is substantially different from that of their isomeric mono-O-diglycosides. In order to characterize a flavonoid as a flavonol 3,7-di-O-glycoside, both [Y-0(3) - H](-center dot)and [Y-0 - 2H](-) ions should be present in [M - H](-) product ion spectrum. The MS3 product ion spectra of Y-0(3)-, [Y-0(3) - H](-center dot) and y(0)(7)(-) ions generated from the [M - H](-) ion provide sufficient structural information for the determination of glycosylation position. Furthermore, the glycosylation positions are determined by comparing the relative abundances of Y-0(3)- and y(0)(7)(-) ions and their specific fragmentation patterns with those of flavonol mono-O-glycosides. In addition, a [Y-0(3) - H](-center dot) ion formed by the homolytic cleavage of 3-O glycosidic bond with high abundance points to 3-O glycosylation, while a [Y-0 - 2H](-) ion formed by the elimination of the two sugar residues is consistent with glycosylation at both the 3-O and 7-O positions. Investigation of negative ion ESI-MS2 and MS3 spectra of flavonol O-glycosides allows their rapid characterization as flavonol 3,7-di-O-glycoside and their differentiation from isomeric mono-O-diglycosides, and also enables their direct analysis in crude plant extracts. Copyright (c) 2006 John Wiley & Sons, Ltd.
引用
收藏
页码:352 / 360
页数:9
相关论文
共 33 条
[1]   Structure-activity relationships for antioxidant activities of a series of flavonoids in a liposomal system [J].
Arora, A ;
Nair, MG ;
Strasburg, GM .
FREE RADICAL BIOLOGY AND MEDICINE, 1998, 24 (09) :1355-1363
[2]   Antioxidant and prooxidant behavior of flavonoids: Structure-activity relationships [J].
Cao, GH ;
Sofic, E ;
Prior, RL .
FREE RADICAL BIOLOGY AND MEDICINE, 1997, 22 (05) :749-760
[3]   Flavonoids - Chemistry, metabolism, cardioprotective effects, and dietary sources [J].
Cook, NC ;
Samman, S .
JOURNAL OF NUTRITIONAL BIOCHEMISTRY, 1996, 7 (02) :66-76
[4]  
CUCYKENS F, 2005, J MASS SPECTROM, V40, P364, DOI DOI 10.1002/JMS.794
[5]  
Cuyckens F, 2004, J MASS SPECTROM, V39, P1, DOI [10.1002/jms.585, 10.1002/jms.622]
[6]   Structure characterization of flavonoid O-diglycosides by positive and negative nano-electrospray ionization ion trap mass spectrometry [J].
Cuyckens, F ;
Rozenberg, R ;
de Hoffmann, E ;
Claeys, M .
JOURNAL OF MASS SPECTROMETRY, 2001, 36 (11) :1203-1210
[7]   Tandem mass spectral strategies for the structural characterization of flavonoid glycosides [J].
Cuyckens, F ;
Ma, YL ;
Pocsfalvi, G ;
Claeys, M .
ANALUSIS, 2000, 28 (10) :888-895A
[8]   Determination of the glycosylation site of flavonoid monoglucosides by metal complexation and tandem mass spectrometry [J].
Davis, BD ;
Brodbelt, JS .
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY, 2004, 15 (09) :1287-1299
[9]   Determination of flavone, flavonol, and flavanone aglycones by negative ion liquid chromatography electrospray ion trap mass spectrometry [J].
Fabre, N ;
Rustan, I ;
de Hoffmann, E ;
Quetin-Leclercq, J .
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY, 2001, 12 (06) :707-715
[10]   Characterization of the interglycosidic linkage in di-, tri-, tetra- and pentaglycosylated flavonoids and differentiation of positional isomers by liquid chromatography/electrospray ionization tandem mass spectrometry [J].
Ferreres, F ;
Llorach, R ;
Gil-Izquierdo, A .
JOURNAL OF MASS SPECTROMETRY, 2004, 39 (03) :312-321