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Effect of stereochemistry on the electrospray ionization tandem mass spectra of transition metal chloride complexes of monosaccharides
Author(s) -
Madhusudanan K. P.,
Kanojiya Sanjeev,
Kumar Brijesh
Publication year - 2005
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/jms.879
Subject(s) - chemistry , electrospray ionization , fragmentation (computing) , monosaccharide , dissociation (chemistry) , molecule , chloride , medicinal chemistry , galactose , stereochemistry , tandem mass spectrometry , mass spectrometry , organic chemistry , chromatography , computer science , operating system
The effect of stereochemistry on the complexation of aldohexoses (glucose, mannose, galactose, allose and talose) and ketohexoses (fructose, tagitose and sorbose) with transition metal chlorides (CoCl 2 , NiCl 2 , MnCl 2 and ZnCl 2 ) has been investigated by electrospray ionization tandem mass spectrometry. Electrospray ionization of methanolic solutions of hexoses containing metal chlorides gave abundant ions corresponding to [M + MetCl] + and [2M + MetCl] + which on collision‐induced dissociation gave characteristic fragment ions. The fragmentation pathways have been confirmed by examining methyl glucoside and several isotopically labeled glucoses. Eliminations of H 2 O and HCl, CC cleavages and elimination of metalhydroxychloride are the competing fragmentation pathways observed. All these pathways seem to be influenced by the stereochemistry of the molecule. The fragmentation of the dimeric complexes, [2M + MetCl] + , is also controlled by the stereochemistry of the molecule. The abundance of the product ions corresponding to elimination of HCl is found to increase with increasing number of axial hydroxyl groups in aldohexoses. [2M + MetCl] + dissociates by elimination of HCl followed by C 2 H 4 O 2 in aldohexose complexes and by elimination of HCl followed by C 3 H 6 O 3 in ketohexose complexes. Copyright © 2005 John Wiley & Sons, Ltd.