Influence of the pi-pi interaction on the hydrogen bonding capacity of stacked DNA/RNA bases.

Abstract:

:The interplay between aromatic stacking and hydrogen bonding in nucleobases has been investigated via high-level quantum chemical calculations. The experimentally observed stacking arrangement between consecutive bases in DNA and RNA/DNA double helices is shown to enhance their hydrogen bonding ability as opposed to gas phase optimized complexes. This phenomenon results from more repulsive electrostatic interactions as is demonstrated in a model system of cytosine stacked offset-parallel with substituted benzenes. Therefore, the H-bonding capacity of the N3 and O2 atoms of cytosine increases linearly with the electrostatic repulsion between the stacked rings. The local hardness, a density functional theory-based reactivity descriptor, appears to be a key index associated with the molecular electrostatic potential (MEP) minima around H-bond accepting atoms, and is inversely proportional to the electrostatic interaction between stacked molecules. Finally, the MEP minima on surfaces around the bases in experimental structures of DNA and RNA-DNA double helices show that their hydrogen bonding capacity increases when taking more neighboring (intra-strand) stacking partners into account.

journal_name

Nucleic Acids Res

journal_title

Nucleic acids research

authors

Mignon P,Loverix S,Steyaert J,Geerlings P

doi

10.1093/nar/gki317

keywords:

subject

Has Abstract

pub_date

2005-03-23 00:00:00

pages

1779-89

issue

6

eissn

0305-1048

issn

1362-4962

pii

33/6/1779

journal_volume

33

pub_type

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