Effects of OH radical addition on proton transfer in the guanine-cytosine base pair

J Phys Chem B. 2007 Jun 14;111(23):6571-6. doi: 10.1021/jp071772l. Epub 2007 May 17.

Abstract

Double proton transfer (PT) reactions in guanine-cytosine OH radical adducts are studied by the hybrid density functional B3LYP approach. Concerted and stepwise proton-transfer processes are explored between N1(H) on guanine (G) and N3 on cytosine (C), and between N4(H) on C and O6 on G. All systems except GC6OH display a concerted mechanism. 8OHGC has the highest dissociation energy and is 1.2 kcal/mol more stable than the nonradical GC base pair. The origin of the interactions are investigated through the estimation of intrinsic acid-basic properties of the *OH-X monomer (X = G or C). Solvent effects play a significant role in reducing the dissociation energy. The reactions including *OH-C adducts have significantly lower PT barriers than both the nonradical GC pair and the *OH-G adducts. All reactions are endothermic, with the GC6OH --> GC6OHPT reaction has the lowest reaction energy (4.6 kcal/mol). In accordance with earlier results, the estimated NBO charges show that the G moiety carries a slight negative charge (and C a corresponding positive one) in each adduct. The formation of a partial ion pair may be a potential factor leading to the PT reactions being thermodynamically unfavored.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Base Pairing*
  • Cytosine / chemistry*
  • Guanine / chemistry*
  • Hydrogen Bonding
  • Hydroxyl Radical / chemistry*
  • Models, Chemical
  • Molecular Structure
  • Nucleic Acid Conformation
  • Protons*
  • Thermodynamics

Substances

  • Protons
  • Hydroxyl Radical
  • Guanine
  • Cytosine