Formation of sugar radical cations from collision-induced dissociation of non-covalent complexes with S-nitroso thiyl radical precursors

Abstract

Abstract A 'bio-inspired' method has been developed for generating sugar radical cations by multistage mass spectrometry (MS4) experiments involving collision-induced dissociation (CID) of protonated non-covalent complexes between a sugar and an S-nitrosylated thiol amine, [H3NXSNO + M]+ (where X = (CH2)2, (CH2)3, (CH2)4, CH(CO2H)CH2 and CH(CO2CH3)CH2). In the first stage of CID (MS2), homolysis of the S-NO bond unleashes a thiyl radical to give the non-covalent radical cation, [H3NXS + M]+. It was found that complexes containing S-nitroso cysteamine (X = (CH2)2) produced the most abundant radical cations for monosaccharides, while for larger sugars, the most abundant radical cations were ge..