Formation and fragmentation of the [M + Na]<sup>+</sup> ion of glycosides in fast atom bombardment mass spectrometry

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<jats:title>Abstract</jats:title><jats:p>Positive‐ion fast atom bombardment (FAB) mass spectra of flavonol and steroid glycosides with sodium chloride added showed well known characteristic features; of the appearance of [M + Na]<jats:sup>+</jats:sup> peaks, disappearance of [M + H]<jats:sup>+</jats:sup> peaks and a significant decrease in the peak heights of fragment ions. Compared with the features in the FAB mass spectra of crown ethers with addition of salt, and above features suggest a complexation between Na<jats:sup>+</jats:sup> and the glycosides in matrix solution. The <jats:italic>B</jats:italic>/<jats:italic>E</jats:italic>‐constant linked scanning technique was used to obtain structural information of the [M + Na]<jats:sup>+</jats:sup> ion of the glycosides. The <jats:italic>B</jats:italic>/<jats:italic>E</jats:italic> spectra gave the daughter‐ion peaks, suggesting that coordination of Na<jats:sup>+</jats:sup> with the biosides and triosides occurs at the sugar moiety, whereas the coordination with the monoglycosides occurs at the aglycone moiety, except for monoglycosides in which the aglycone moiety does not contain significant oxygen functional groups such as OH and CO.</jats:p>

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