Characterization of cyclodextrins using ion‐evaporation atmospheric‐pressure ionization tandem mass spectrometry

A tandem mass spectrometer equipped with the pneumatically‐assisted electrospray (ion spray) liquid chromatography/mass spectrometry interface and an atmospheric‐pressure ionization source was used for characterization of underivatized cyclic oligosaccharides. Protonated singly charged molecular ions were generated via ion‐evaporation mechanism(s). The formation of doubly charged molecular ions from the model compounds appears to be related to the channel diameter of these cyclic oligosaccharides. Tandem mass spectrometry (MS/MS) was used to study collision‐induced dissociation of the protonated molecule and showed exclusive cleavage of the glycosidic bond. The molecular weights of these oligosaccharides as well as the number of sugar units were confirmed by MS/MS. The potential application of MS/MS for target compound analysis was demonstrated by the parent‐ion scan method with a synthetic mixture.