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Issue 23, 2015
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Tautomeric transition between wobble A·C DNA base mispair and Watson–Crick-like A·C* mismatch: microstructural mechanism and biological significance

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Abstract

Here, we use MP2/DFT quantum-chemical methods combined with Quantum Theory of Atoms in Molecules to study the tautomeric transition between wobble A·C(w) mismatch and Watson–Crick-like A·C*(WC) base mispair, proceeding non-dissociatively via sequential proton transfer between bases through the planar, highly stable and zwitterionic Image ID:c5cp01568e-t1.gif transition state joined by the participation of (A)N6+H⋯N4(C), (A)N1+H⋯N4(C) and (A)C2+H⋯N3(C) H-bonds. Notably, the A·C(w) ↔ A·C*(WC) tautomerization reaction is accompanied by 10 unique patterns of the specific intermolecular interactions that consistently replace each other. Our data suggest that biologically significant A·C(w) → A·C*(WC) tautomerization is a kinetically controlled pathway for formation of the enzymatically competent Watson–Crick-like A·C*(WC) DNA base mispair in the essentially hydrophobic recognition pocket of the high-fidelity DNA-polymerase, responsible for the occurrence of spontaneous point AC/CA incorporation errors during DNA biosynthesis.

Graphical abstract: Tautomeric transition between wobble A·C DNA base mispair and Watson–Crick-like A·C* mismatch: microstructural mechanism and biological significance

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Publication details

The article was received on 17 Mar 2015, accepted on 02 May 2015 and first published on 06 May 2015


Article type: Communication
DOI: 10.1039/C5CP01568E
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Phys. Chem. Chem. Phys., 2015,17, 15103-15110

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    Tautomeric transition between wobble A·C DNA base mispair and Watson–Crick-like A·C* mismatch: microstructural mechanism and biological significance

    O. O. Brovarets' and D. M. Hovorun, Phys. Chem. Chem. Phys., 2015, 17, 15103
    DOI: 10.1039/C5CP01568E

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