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