Estimation of strength in different extra Watson-Crick hydrogen bonds in DNA double helices through quantum chemical studies

It was shown earlier, from database analysis, model building studies, and molecular dynamics simulations that formation of cross-strand bifurcated or Extra Watson-Crick hydrogen (EWC) bonds between successive base pairs may lead to extra rigidity to DNA double helices of certain sequences. The strengths of these hydrogen bonds are debatable, however, as they do not have standard linear geometry criterion. We have therefore carried out detailed ab initio quantum chemical studies using RHF/6-31G(2d,2p) and B3LYP/6-31G(2p,2d) basis sets to determine strengths of several bent hydrogen bonds with different donor and acceptors. Interaction energy calculations, corrected for the basis set superposition errors, suggest that N-H center dot center dot center dot O type bent EWC hydrogen bonds are possible along same strands or across the strands between successive base pairs, leading to significant stability (ca. 4-9 kcal/mol). The N-H center dot center dot center dot N and C-H center dot center dot center dot O type interactions, however, are not so stabilizing. Hence, consideration of EWC N-H center dot center dot center dot O H-bonds can lead to a better understanding of DNA sequence directed structural features. (c) 2006 Wiley Periodicals, Inc.