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Guillaumes L, Simon S, Fonseca Guerra C, et al. The Role of Aromaticity, Hybridization, Electrostatics, and Covalency in Resonance-Assisted Hydrogen Bonds of Adenine-Thymine (AT) Base Pairs and Their Mimics. ChemistryOpen. 2015;4(3):318-27doi: 10.1002/open.201402132.
Guillaumes, L., Simon, S., Fonseca Guerra, C., & Bhagavatula, P. (2015). The Role of Aromaticity, Hybridization, Electrostatics, and Covalency in Resonance-Assisted Hydrogen Bonds of Adenine-Thymine (AT) Base Pairs and Their Mimics. ChemistryOpen, 4(3), 318-27. https://doi.org/10.1002/open.201402132
Guillaumes, L, et al. "The Role of Aromaticity, Hybridization, Electrostatics, and Covalency in Resonance-Assisted Hydrogen Bonds of Adenine-Thymine (AT) Base Pairs and Their Mimics." ChemistryOpen vol. 4,3 (2015): 318-27. doi: https://doi.org/10.1002/open.201402132
Guillaumes L, Simon S, Fonseca Guerra C, Bhagavatula P. The Role of Aromaticity, Hybridization, Electrostatics, and Covalency in Resonance-Assisted Hydrogen Bonds of Adenine-Thymine (AT) Base Pairs and Their Mimics. ChemistryOpen. 2015 Jun;4(3):318-27. doi: 10.1002/open.201402132. Epub 2015 Mar 09. PMID: 26246994; PMCID: PMC4522182.
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ChemistryOpen. 2015 Jun;4(3):318-27. doi: 10.1002/open.201402132. Epub 2015 Mar 09.

The Role of Aromaticity, Hybridization, Electrostatics, and Covalency in Resonance-Assisted Hydrogen Bonds of Adenine-Thymine (AT) Base Pairs and Their Mimics.

ChemistryOpen

L Guillaumes, S Simon, C Fonseca Guerra, Bhagavatula

Affiliations

  1. Institut de Química Computacional i Catàlisi, Departament de Química, Universitat de Girona 17071, Girona, Spain).
  2. Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, VU University Amsterdam De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands).

PMID: 26246994 PMCID: PMC4522182 DOI: 10.1002/open.201402132

Abstract

Hydrogen bonds play a crucial role in many biochemical processes and in supramolecular chemistry. In this study, we show quantum chemically that neither aromaticity nor other forms of π assistance are responsible for the enhanced stability of the hydrogen bonds in adenine-thymine (AT) DNA base pairs. This follows from extensive bonding analyses of AT and smaller analogs thereof, based on dispersion-corrected density functional theory (DFT). Removing the aromatic rings of either A or T has no effect on the Watson-Crick bond strength. Only when the smaller mimics become saturated, that is, when the hydrogen-bond acceptor and donor groups go from sp (2) to sp (3), does the stability of the resulting model complexes suddenly drop. Bonding analyses based on quantitative Kohn-Sham molecular orbital theory and corresponding energy decomposition analyses (EDA) show that the stronger hydrogen bonds in the unsaturated model complexes and in AT stem from stronger electrostatic interactions as well as enhanced donor-acceptor interactions in the σ-electron system, with the covalency being responsible for shortening the hydrogen bonds in these dimers.

Keywords: DNA base pairs; aromaticity; density functional calculations; molecular orbital (MO) theory; nucleotides; resonance-assisted hydrogen bonding

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