Why do A·T and G·C self-sort? Hückel aromaticity as a driving force for electronic complementarity in base pairing

Organic & Biomolecular Chemistry
Yu ZhangJudy I Wu

Abstract

Density functional theory computations and block-localized wavefunction analyses for 57 hydrogen-bonded base pairs document excellent linear correlation between the gas-phase association energies and the degree of aromaticity gain of paired bases (r = 0.949), challenging prevailing views of factors that underlie the proposed electronic complementarity of A·T(U) and G·C base pairs. Base pairing interactions can polarize the π-electrons of interacting bases to increase (or decrease) cyclic 4n + 2π electron delocalization, resulting in aromaticity gain (or loss) in the paired bases, and become strengthened (or weakened). The potential implications of this reciprocal relationship for improving nucleic acid force-fields and for designing robust unnatural base pairs are discussed.

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Citations

Mar 4, 2021·Chemical Communications : Chem Comm·Théo P GonçalvesKuo-Wei Huang
May 4, 2021·Wiley Interdisciplinary Reviews. Computational Molecular Science·Lucas J KarasJudy I-Chia Wu

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Software Mentioned

Gaussian09
GAMESS
Multiwfn

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