Formation of sugar radical cations from collision-induced dissociation of non-covalent complexes with S-nitroso thiyl radical precursors
Sandra Osburn, Spencer J Williams, Richard AJ O'Hair
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY | ELSEVIER SCIENCE BV | Published : 2015
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..View full abstract
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RAJO thanks the Australian Research Council (ARC) for financial support via the ARC Centre of Excellence in Free Radical Chemistry and Biotechnology. SJW is an ARC Future Fellow and thanks the ARC for financial support.