Abstract
Analytical Chemistry Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA Differentiation of the seven isomers of methyl guanine has been accomplished by monitoring gas-phase hydrogen/deuterium (H/D) exchange reactions of the protonated molecular ions with deuterium oxide (D2O) in a Fourier transform mass spectrometer. In each case a distinctive reaction rate for the first H/D exchange was observed, and exchanges of up to three deuterium atoms occurred with characteristic ion abundances that could be used to differentiate the isomers. O6-Methyl guanine, for example, showed only one slow H/D exchange with D2O, whereas l-methyl guanine exchanged two hydrogen atoms at a significantly faster rate. On comparison of the possible resonance structures of each protonated isomer with the experimental information about the number and rate of H/D exchanges observed, a reaction mechanism involving a concerted proton abstraction-deuterium cation donation was proposed.
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Nourse, B.D., Hettich, R.L. & Buchanan, M.V. Methyl guanine isomer distinction by hydrogen / deuterium exchange using a fourier transform mass spectrometer. J Am Soc Mass Spectrom 4, 296–305 (1993). https://doi.org/10.1016/1044-0305(93)85051-X
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DOI: https://doi.org/10.1016/1044-0305(93)85051-X