Journal
JOURNAL OF PHYSICAL CHEMISTRY B
Volume 120, Issue 20, Pages 4616-4624Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcb.6b04052
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Funding
- National Science Foundation [OISE-0730072, OISE-1357787, CHE-1409420]
- WSU
- Nederlandse Organisatie voor Wetenschappeklijk Onderzoek
- WSU Cse Organisatie voor Wetenschappeklijk Onderzoek
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1409420] Funding Source: National Science Foundation
- Office Of The Director
- Office Of Internatl Science &Engineering [1357887] Funding Source: National Science Foundation
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Infrared multiple photon dissociation (IRMPD) action spectroscopy experiments combined with theoretical calculations are performed to investigate the stable gas-phase conformations of the protonated adenine mono-nucleotides, [pdAdo+H](+) and [pAdo+H](+). Conformations that are present in the experiments are elucidated via comparative analyses of the experimental IRMPD spectra and the B3LYP/6-311+G(d,p) IR spectra predicted for the conformers optimized at this level of theory. N3 protonation is preferred as it induces base rotation, which allows a strong hydrogen bond to be formed between the excess proton of adenine and the phosphate moiety. In contrast, both N1 and N7 protonation are predicted to be >35 kJ/mol less favorable than N3 protonation. Only N3 protonated conformers are present in the experiments in measurable abundance. Both the low energy conformers computed and the experimental IRMPD spectra of [pdAdo+H](+) and [pAdo+H](+) indicate that the 2'-hydroxyl moiety does not significantly impact the structure of the most stable conformer or the IRMPD spectral profile of [pAdo+H](+) vs that of [pdAdo+H](+). However, the 2'-hydroxyl leads to a 3-fold enhancement in the IRMPD yield of [pAdo+H](+) in the fingerprint region. Comparison of present results to those reported in a previous IRMPD study of the analogous protonated adenine nucleosides allows the effects of the phosphate moiety on the gas-phase conformations to be elucidated.
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