Electrospray ionization mass spectrometry for identification and structural characterization of pregnane glycosides.
Pregnane glycosides are a class of naturally occurring substances characterized by some interesting biological activities and widely distributed in the plant kingdom and in some marine organisms. Their toxicity and use in herbal drugs and folk medicines has generated great interest in the chemical characterization of these molecules. In the study reported here the potential of electrospray ionization mass spectrometry (ESI-MS) in the identification and structural characterization of pregnane glycosides was examined. ESI-MS/MS and ESI-MS(n) analyses were performed on 27 different compounds employing two mass spectrometers equipped with a triple-quadrupole or an ion-trap analyzer. The data illustrate the ability of the ESI techniques in the identification of pregnane glycosides, including the nature of the pregnane core, the kind of ester substituents, the types of sugar residues (hexose, deoxyhexose, dideoxyhexose, O-methyldeoxyhexose and O-methyldideoxyhexose), and the primary structure of the saccharide chain. From these data, a generalized fragmentation pathway was proposed by comparing the spectra acquired for all the compounds. Interestingly, similar results were obtained from the two instruments, thus demonstrating that detailed analyses of product ion spectra obtained using a triple-quadrupole mass spectrometer led to structural information comparable to those obtainable in MSn experiments using an ion trap. Different and complementary information was deduced by fragmenting the [M+H]+ or the [M+Na]+ ions, or the protonated aglycone [Agl+H]+ generated by in-source fragmentation. The present evidence clearly suggests that, in order to obtain a complete characterization of pregnane glycosides by MS, all three of these species should be accurately analyzed.
Dal Piaz
Fabrizio
F
Dipartimento di Scienze Farmaceutiche, Università di Salerno, via Ponte Don Melillo 84084, Fisciano (SA), Italy.
De Leo
Marinella
M
Braca
Alessandra
A
De Simone
Francesco
F
Morelli
Ivano
I
De Tommasi
Nunziatina
N
D029062:Apocynaceae / Q000737:chemistry*; D006027:Glycosides / Q000737:chemistry* / Q000302:isolation & purification*; D015394:Molecular Structure; D010936:Plant Extracts / Q000737:chemistry; D011278:Pregnanes / Q000737:chemistry* / Q000302:isolation & purification*; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*
D006027:Glycosides; D010936:Plant Extracts; D011278:Pregnanes