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Department of Chemistry & Auckland Bioengineering Institute, The University of Auckland, Private Bag 92019, New Zealand
; Fax: +64 9-373-7422
; Tel: +64 9-373-7599 Ext. 83746
Phys. Chem. Chem. Phys., 2010,12, 9088-9093
05 Feb 2010,
12 May 2010
First published online
08 Jun 2010
As calculated by the density functional theory (DFT), the acidity of cytosine's exocyclic amine group (C–N4H2) in the base pairG–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 pairG(−H)˙–C(+H)+. Under these conditions and taking the hydration energy of H+ into account, the overall proton transfer from the C–N4H2group 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 strandedDNA.
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