The influence of substituents and the environment on the NMR shielding constants of supramolecular complexes based on A-T and A-U base pairs

Abril C. Castro; Marcel Swart; Célia Fonseca Guerra

doi:10.1039/c7cp00397h

The influence of substituents and the environment on the NMR shielding constants of supramolecular complexes based on A-T and A-U base pairs

Abril C. Castro, Marcel Swart, Célia Fonseca Guerra^*

^*Corresponding author for this work

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Research output: Contribution to Journal › Article › Academic › peer-review

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Abstract

In the present study, we have theoretically analyzed supramolecular complexes based on the Watson-Crick A-T and A-U base pairs using dispersion-corrected density functional theory (DFT). Hydrogen atoms H8 and/or H6 in the natural adenine and thymine/uracil bases were replaced, respectively, by substituents X8, Y6 = NH^-, NH₂, NH₃ ⁺ (N series), O^-, OH, OH₂ ⁺ (O series), F, Cl or Br (halogen series). We examined the effect of the substituents on the hydrogen-bond lengths, strength and bonding mechanism, and the NMR shielding constants of the C2-adenine and C2-thymine/uracil atoms in the base pairs. The general belief in the literature that there is a direct connection between changes in the hydrogen-bond strength and the C2-adenine shielding constant is conclusively rejected by our computations.

Original language	English
Pages (from-to)	13496-13502
Number of pages	7
Journal	Physical Chemistry Chemical Physics
Volume	19
Issue number	21
Early online date	25 Apr 2017
DOIs	https://doi.org/10.1039/c7cp00397h
Publication status	Published - 7 Jun 2017

Funding

The following organizations are thanked for financial support: the Ministerio de Ciencia e Innovaci?n (MICINN, PhD-scholarship BES-2012-052792), the Ministerio de Econom?a y Competitividad (MINECO, CTQ2014-59212-P and CTQ2015-70851-ERC), GenCat (2014SGR1202 and XRQTC network) and European Fund for Regional Development (FEDER, UNGI10-4E-801).

Funders	Funder number
Ministerio de Economía y Competitividad	CTQ2014-59212-P, CTQ2015-70851-ERC, 2014SGR1202
Ministerio de Ciencia e Innovación	BES-2012-052792
European Regional Development Fund	UNGI10-4E-801

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The influence of substituents and the environment on the NMR shielding constants of supramolecular complexes based on A–T and A–U base pairsFinal published version, 2.94 MBLicence: Article 25fa Dutch Copyright Act

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AB - In the present study, we have theoretically analyzed supramolecular complexes based on the Watson-Crick A-T and A-U base pairs using dispersion-corrected density functional theory (DFT). Hydrogen atoms H8 and/or H6 in the natural adenine and thymine/uracil bases were replaced, respectively, by substituents X8, Y6 = NH-, NH2, NH3 + (N series), O-, OH, OH2 + (O series), F, Cl or Br (halogen series). We examined the effect of the substituents on the hydrogen-bond lengths, strength and bonding mechanism, and the NMR shielding constants of the C2-adenine and C2-thymine/uracil atoms in the base pairs. The general belief in the literature that there is a direct connection between changes in the hydrogen-bond strength and the C2-adenine shielding constant is conclusively rejected by our computations.

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The influence of substituents and the environment on the NMR shielding constants of supramolecular complexes based on A-T and A-U base pairs

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