Gas-phase hydrogen-deuterium (H/D) exchange reactions involving four isomeric cyclopropane derivatives were investigated under chemical ionization (CI) conditions, using D(2)O and CD(3)OD as reagent gases. There are abundant ions at [M + 1](+), [M + 2](+) and [M + 3](+) in the D(2)O and CD(3)OD posi
Gas-phase hydrogen–deuterium exchange in phosphorothioate d(GTCAG) and d(TCGAT)
✍ Scribed by Richard H. Griffey; Michael J. Greig; Jessica M. Robinson; David A. Laude
- Publisher
- John Wiley and Sons
- Year
- 1999
- Tongue
- English
- Weight
- 93 KB
- Volume
- 13
- Category
- Article
- ISSN
- 0951-4198
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✦ Synopsis
The gas-phase hydrogen-deuterium exchange of phosphorothioate d(GTCAG) and d(TCGAT) has been examined using electrospray Fourier transform ion cyclotron resonance (FTICR) mass spectrometry. The exchange has been monitored for the [M-2H] 2À , [M-3H] 3À , and [M-4H] 4À charge states. The mole fractions of each partially exchanged species have been calculated as a function of time. The rates of initial exchange could not be fit to simple exponential functions. The results suggest that each ion can adopt more than one gas-phase conformation, and that these conformers exchange at different rates. Observation of slowly interconverting populations is consistent with a model where initial ion conformations contain internal hydrogen bonds between the bases and charged residues that are disrupted over time.
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