A novel conception for spontaneous transversions caused by homo-pyrimidine DNA mismatches: a QM/QTAIM highlight

作者:Brovarets Ol' ha O; Hovorun Dmytro M
来源:Physical Chemistry Chemical Physics, 2015, 17(33): 21381-21388.
DOI:10.1039/c5cp03211c

摘要

We have firstly shown that the T center dot T(w) and C center dot C(w) DNA mismatches with wobble (w) geometry stay in slow tautomeric equilibrium with short T center dot T*(WC) and C center dot C*(WC) Watson-Crick (WC) mispairs. These non-dissociative tautomeric rearrangements are controlled by the plane-symmetric, highly stable, highly polar and zwitterionic transition states. The obtained results allow us to understand in what way the T center dot T(w) and C center dot C(w) mismatches acquire enzymatically competent T center dot T*(WC) and C center dot C*(WC) conformations directly in the hydrophobic recognition pocket of a high-fidelity DNA-polymerase, thereby producing thermodynamically non-equilibrium spontaneous transversions. The simplest numerical estimation of the frequency ratio of the TT to CC spontaneous transversions satisfactorily agrees with experimental data.

  • 出版日期2015