Gas-phase reactivity of silver and copper coordinated monosaccharide cations studied by electrospray ionization and tandem mass spectrometry.

Abstract

The analytical distinction of the most common isomeric underivatized hexoses was investigated by means of mass spectrometry experiments. Electrospray ionization and tandem mass spectrometry were used in the analysis of silver and copper-coordinated monosaccharides (D-glucose, D-galactose, D-fructose, O-methyl-alpha-D-glucose and O-methyl-beta-D-glucose). The results show that cationization by Ag(+) allows the differentiation of the three first monosaccharides while the complexes formed by association of Cu(+) with these three monosacharides display a similar reactivity that prevents stereoisomer distinction. Unlike copper, silver adduct-ions of both alpha and beta anomeric O-methyl-D-glucoses exhibit specific decomposition patterns (i.e. a loss of methanol for the alpha-anomer and a loss of silver hydride for the beta-anomer), which allow an easy characterization. A theoretical survey of selected complexes, based on the use of DFT calculations were carried out on both anomers in order to rationalize the experimental findings.