DFT calculations on the deprotonation site of the one-electron oxidised guanine–cytosinebase pair

Literature Information

Publication Date 2010-06-08
DOI 10.1039/C002528C
Impact Factor 3.676
Authors

Steen Steenken, Jóhannes Reynisson


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Abstract

As calculated by the density functional theory (DFT), the acidity of cytosine's exocyclic amine group (C–N4H2) in the base pair G–C is considerably increased upon its one-electron oxidation. The proton affinity (PA) of the amine moiety is lowered by ionisation of G–C (which yields G˙+–C) from −348.1 to −269.1 kcal mol−1. The PA is further decreased by 7.6 kcal mol−1 as a result of the ensuing proton transfer from G˙+ to C to yield the spin–charge separated base pair G(−H)˙–C(+H)+. Under these conditions and taking the hydration energy of H+ into account, the overall proton transfer from the C–N4H2 group to the aqueous phase in the major groove is exothermic by −2.4 kcal mol−1. This proton transfer to water from the initially present DNA radical cation constitutes separation of charge from spin and thus reduces positive charge transfer in double stranded DNA.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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