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Theoretical Studies on the Intermolecular Interactions of Potentially Primordial Base‐Pair Analogues
Author(s) -
Šponer Judit E.,
VázquezMayagoitia Álvaro,
Sumpter Bobby G.,
Leszczynski Jerzy,
Šponer Jiří,
Otyepka Michal,
Banáš Pavel,
FuentesCabrera Miguel
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200902068
Subject(s) - stacking , pairing , chemistry , base pair , hydrogen bond , intermolecular force , chemical physics , computational chemistry , base (topology) , crystallography , extrapolation , molecule , physics , dna , quantum mechanics , organic chemistry , biochemistry , mathematical analysis , superconductivity , mathematics
Recent experimental studies on the Watson–Crick type base pairing of triazine and aminopyrimidine derivatives suggest that acid/base properties of the constituent bases might be related to the duplex stabilities measured in solution. Herein we use high‐level quantum chemical calculations and molecular dynamics simulations to evaluate the base pairing and stacking interactions of seven selected base pairs, which are common in that they are stabilized by two NH⋅⋅⋅O hydrogen bonds separated by one NH⋅⋅⋅N hydrogen bond. We show that neither the base pairing nor the base stacking interaction energies correlate with the reported p K a data of the bases and the melting points of the duplexes. This suggests that the experimentally observed correlation between the melting point data of the duplexes and the p K a values of the constituent bases is not rooted in the intrinsic base pairing and stacking properties. The physical chemistry origin of the observed experimental correlation thus remains unexplained and requires further investigations. In addition, since our calculations are carried out with extrapolation to the complete basis set of atomic orbitals and with inclusion of higher electron correlation effects, they provide reference data for stacking and base pairing energies of non‐natural bases.