title: Multistage and tandem mass spectrometry of glycosylated triterpenoid saponins isolated from Bacopa monnieri: comparison of the information content provided by different techniques.
abstract: Whereas all state-of-the-art techniques in mass spectrometry (MS) have been extensively applied to oligosaccharides derived from glycoproteins, less effort has been devoted to the analysis of smaller glycoconjugates. In the present study, the application of a variety of MS techniques for the analysis of two dammarane-type triterpenoid saponins isolated from B. monnieri is reported. The structural information provided by ESI-ion trap (IT)-, AP-MALDI-IT-, and MALDI-IT/reflectron time-of-flight (RTOF)-MS, all utilizing low-energy collision-induced dissociation (CID), and MALDI-TOF/RTOF-MS, facilitating postsource decay and high-energy CID analysis, was compared. The applied desorption/ionization technique does not influence the fragmentation of identical precursor ions in low-energy CID. All three fragmentation techniques clearly yield the sequence and branching of the glycan moiety as well as the molecular mass of the intact aglycon. Cross-ring cleavage of the branching sugar, which gives some information about the sugar linkages, was mainly observed in low-energy CID. High-energy CID, on the other hand, yielded some additional diagnostic fragment ions from the aglycon moiety. Internal cleavage ions are formed by alternative mechanisms in high-energy CID and are assumed to be diagnostic for some linkages. However, none of the applied MS techniques facilitates the identification of those saponins that differ only by their aglycon moiety (i.e., jujubogenin or pseudojujubogenin).
authors.affiliation: Institute of Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9/164, A-1060 Vienna, Austria.
authors.forename: Martin
authors.initials: M
authors.lastname: Zehl
authors.forename: Ernst
authors.initials: E
authors.lastname: Pittenauer
authors.forename: Leopold
authors.initials: L
authors.lastname: Jirovetz
authors.forename: Pamita
authors.initials: P
authors.lastname: Bandhari
authors.forename: Bikram
authors.initials: B
authors.lastname: Singh
authors.forename: Vijay K
authors.initials: VK
authors.lastname: Kaul
authors.forename: Andreas
authors.initials: A
authors.lastname: Rizzi
authors.forename: Guenter
authors.initials: G
authors.lastname: Allmaier
mesh_terms: D034681:Bacopa / Q000737:chemistry*; D002851:Chromatography, High Pressure Liquid / Q000379:methods; D006031:Glycosylation; D015394:Molecular Structure; D015203:Reproducibility of Results; D012503:Saponins / Q000032:analysis*; D012680:Sensitivity and Specificity; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods; D013237:Stereoisomerism; D053719:Tandem Mass Spectrometry / Q000379:methods*
chemical_list: D012503:Saponins