NDLI: 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

Content Provider	Springer Nature Link
Author	Osburn, Sandra Speciale, Gaetano Williams, Spencer J. O’Hair, Richard A. J.
Copyright Year	2017
Abstract	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 (MS$^{2}$), collision-induced dissociation (CID) of a protonated noncovalent complex between the sugar and S-nitrosocysteamine, [H$_{3}$NCH$_{2}$CH$_{2}$SNO + M]$^{+}$, unleashes a thiyl radical via bond homolysis to give the noncovalent radical cation, [H$_{3}$NCH$_{2}$CH$_{2}$S$^{•}$ + M]$^{+}$. CID (MS$^{3}$) of this radical cation complex results in dissociation of the noncovalent complex to generate the sugar radical cation. Replacement of all exchangeable OH and NH protons with deuterons reveals that the sugar radical cation is formed in a process involving abstraction of a hydrogen atom from a C–H bond of the sugar coupled with proton transfer to the sugar, to form [M – H$^{•}$ + D$^{+}$]. Investigation of this process using individual C-D labeled sugars reveals that the main site of H/D abstraction is the C2 position, since only the C2-deuterium labeled sugar yields a dominant [M – D$^{•}$ + H$^{+}$] product ion. The fragmentation reactions of the distonic sugar radical cation, [M – H$^{•}$+ H$^{+}$], were studied by another stage of CID (MS$^{4}$). $^{13}$C-labeling studies revealed that a series of three related fragment ions each contain the C1–C3 atoms; these arise from cross-ring cleavage reactions of the sugar. Graphical Abstract ᅟ
Starting Page	1425
Ending Page	1431
Page Count	7
File Format	PDF
ISSN	10440305
Journal	Journal of The American Society for Mass Spectrometry
Volume Number	28
Issue Number	7
e-ISSN	18791123
Language	English
Publisher	Springer US
Publisher Date	2017-05-04
Publisher Institution	The American Society for Mass Spectrometry
Publisher Place	New York
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Noncovalent complex S-nitrosocysteamine Carbohydrate Collision-induced dissociation Radical chemistry Analytical Chemistry Biotechnology Organic Chemistry Proteomics Bioinformatics
Content Type	Text
Resource Type	Article
Subject	Spectroscopy Structural Biology

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