On the aromatic character of the heterocyclic bases of DNA and RNA

J Org Chem. 2003 Oct 31;68(22):8607-13. doi: 10.1021/jo034760e.

Abstract

Studies based on ab initio optimized geometries (at B3LYP/6-311+G** and MP2/6-311+G** levels) and on experimental structures retrieved from the Cambridge Structural Database (CSD) reveal that the nucleobases constituting DNA and RNA differ significantly in their aromatic character, as shown by the geometry-based index of aromaticity HOMA that ranges from 0.466 for thymine to 0.917 for adenine, based on B3LYP/6-311+G** calculations, and 0.495-0.926, respectively, if based on the MP2/6-311+G** level. Aromaticity of the bases decreases markedly with an increase of the number of double-bond C=X (X = N, O) substituents at the rings. H-bonds involving C=O groups in Watson-Crick pairs cause an increase of the aromatic character of the rings.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Adenine / chemistry
  • Base Pairing
  • Cytosine / chemistry
  • DNA / chemistry*
  • Guanine / chemistry
  • Hydrogen Bonding
  • Mathematical Computing
  • Nucleic Acid Conformation
  • Quantum Theory
  • RNA / chemistry*
  • Stereoisomerism
  • Thymine / chemistry
  • Uracil / chemistry

Substances

  • Uracil
  • Guanine
  • RNA
  • Cytosine
  • DNA
  • Adenine
  • Thymine