Analysis of underivatized oligosaccharides by liquid chromatography/electrospray ionization tandem mass spectrometry with post-column addition of formic acid. 2009

Giancarlo Verardo, and Irene Duse, and Alessandro Callea
Department of Chemical Sciences and Technology, University of Udine, I-33100 Udine, Italy. giancarlo.verardo@uniud.it

Underivatized oligosaccharides were analyzed by electrospray ionization (ESI) using a linear ion trap mass spectrometer in the negative ion mode with post-column addition of an aqueous solution of formic acid. Under these conditions all oligosaccharides showed the presence of the corresponding formate adduct [M + HCOO](-) with high intensity and easy subsequent low-energy collision-induced dissociation (CID) fragmentation using successive MS(n) experiments. A careful examination of the mass spectra obtained from these MS(n) experiments pointed out some significant differences useful to identify and quantify the single components in mixtures of coeluted disaccharides. This new sensitive and rapid method was successfully applied to the quantification of oligosaccharides in some juices minimizing sample handling.

UI MeSH Term Description Entries
D009844 Oligosaccharides Carbohydrates consisting of between two (DISACCHARIDES) and ten MONOSACCHARIDES connected by either an alpha- or beta-glycosidic link. They are found throughout nature in both the free and bound form. Oligosaccharide
D002853 Chromatography, Liquid Chromatographic techniques in which the mobile phase is a liquid. Liquid Chromatography
D005561 Formates Derivatives of formic acids. Included under this heading are a broad variety of acid forms, salts, esters, and amides that are formed with a single carbon carboxy group. Formic Acids,Acids, Formic
D013057 Spectrum Analysis The measurement of the amplitude of the components of a complex waveform throughout the frequency range of the waveform. (McGraw-Hill Dictionary of Scientific and Technical Terms, 6th ed) Spectroscopy,Analysis, Spectrum,Spectrometry
D021241 Spectrometry, Mass, Electrospray Ionization A mass spectrometry technique used for analysis of nonvolatile compounds such as proteins and macromolecules. The technique involves preparing electrically charged droplets from analyte molecules dissolved in solvent. The electrically charged droplets enter a vacuum chamber where the solvent is evaporated. Evaporation of solvent reduces the droplet size, thereby increasing the coulombic repulsion within the droplet. As the charged droplets get smaller, the excess charge within them causes them to disintegrate and release analyte molecules. The volatilized analyte molecules are then analyzed by mass spectrometry. ESI Mass Spectrometry,Electrospray Ionization Mass Spectrometry,Mass Spectrometry, ESI,Spectrometry, ESI Mass

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