Gas-Phase Intercluster Thiyl-Radical Induced C-H Bond Homolysis Selectively Forms Sugar C2-Radical Cations of Methyl D-Glucopyranoside: Isotopic Labeling Studies and Cleavage Reactions
Sandra Osburn, Gaetano Speciale, Spencer J Williams, Richard AJ O'Hair
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY | SPRINGER | Published : 2017
A suite of isotopologues of methyl D-glucopyranosides is used in conjunction with multistage mass spectrometry experiments to determine the radical site and cleavage reactions of sugar radical cations formed via a recently developed 'bio-inspired' method. In the first stage of CID (MS2), collision-induced dissociation (CID) of a protonated noncovalent complex between the sugar and S-nitrosocysteamine, [H3NCH2CH2SNO + M]+, unleashes a thiyl radical via bond homolysis to give the noncovalent radical cation, [H3NCH2CH2S• + M]+. CID (MS3) of this radical cation complex results in dissociation of the noncovalent complex to generate the sugar radical cation. Replacement of all exchangeable OH and ..View full abstract
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Awarded by Australian Research Council (ARC) via the ARC Center of Excellence in Free Radical Chemistry and Biotechnology
Awarded by ARC
R.A.J.O. thanks the Australian Research Council (ARC) for financial support via the ARC Center of Excellence in Free Radical Chemistry and Biotechnology (CE0561607). S.J.W. is an ARC Future Fellow (FT130100103) and thanks the ARC for financial support (DP160100597).