TY - JOUR
T1 - Enol tautomers of Watson-Crick base pair models are metastable because of nuclear quantum effects
AU - Pérez, Alejandro
AU - Tuckerman, Mark E.
AU - Hjalmarson, Harold P.
AU - Von Lilienfeld, O. Anatole
PY - 2010/8/25
Y1 - 2010/8/25
N2 - Intermolecular enol tautomers of Watson-Crick base pairs could emerge spontaneously via interbase double proton transfer. It has been hypothesized that their formation could be facilitated by thermal fluctuations and proton tunneling, and possibly be relevant to DNA damage. Theoretical and computational studies, assuming classical nuclei, have confirmed the dynamic stability of these rare tautomers. However, by accounting for nuclear quantum effects explicitly through Car-Parrinello path integral molecular dynamics calculations, we find the tautomeric enol form to be dynamically metastable, with lifetimes too insignificant to be implicated in DNA damage.
AB - Intermolecular enol tautomers of Watson-Crick base pairs could emerge spontaneously via interbase double proton transfer. It has been hypothesized that their formation could be facilitated by thermal fluctuations and proton tunneling, and possibly be relevant to DNA damage. Theoretical and computational studies, assuming classical nuclei, have confirmed the dynamic stability of these rare tautomers. However, by accounting for nuclear quantum effects explicitly through Car-Parrinello path integral molecular dynamics calculations, we find the tautomeric enol form to be dynamically metastable, with lifetimes too insignificant to be implicated in DNA damage.
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U2 - 10.1021/ja102004b
DO - 10.1021/ja102004b
M3 - Article
C2 - 20681591
AN - SCOPUS:77955824113
SN - 0002-7863
VL - 132
SP - 11510
EP - 11515
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 33
ER -