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Influence of the Solvent on the Stability of Aminopurine Tautomers and Properties of the Amino Group

Amino derivatives of purine (2-, 6-, 8-, and N-NH(2)) have found many applications in biochemistry. This paper presents the results of a systematic computational study of the substituent and solvent effects in these systems. The issues considered are the electron-donating properties of NH(2), its ge...

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Autores principales: Jezuita, Anna, Wieczorkiewicz, Paweł A., Krygowski, Tadeusz M., Szatylowicz, Halina
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10095612/
https://www.ncbi.nlm.nih.gov/pubmed/37049758
http://dx.doi.org/10.3390/molecules28072993
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author Jezuita, Anna
Wieczorkiewicz, Paweł A.
Krygowski, Tadeusz M.
Szatylowicz, Halina
author_facet Jezuita, Anna
Wieczorkiewicz, Paweł A.
Krygowski, Tadeusz M.
Szatylowicz, Halina
author_sort Jezuita, Anna
collection PubMed
description Amino derivatives of purine (2-, 6-, 8-, and N-NH(2)) have found many applications in biochemistry. This paper presents the results of a systematic computational study of the substituent and solvent effects in these systems. The issues considered are the electron-donating properties of NH(2), its geometry, π-electron delocalization in purine rings and tautomeric stability. Calculations were performed in ten environments, with 1 < ε < 109, using the polarizable continuum model of solvation. Electron-donating properties were quantitatively described by cSAR (charge of the substituent active region) parameter and π-electron delocalization by using the HOMA (harmonic oscillator model of aromaticity) index. In aminopurines, NH(2) proximity interactions depend on its position and the tautomer. The results show that they are the main factor determining how solvation affects the electron-donating strength and geometry of NH(2). Proximity with the NH∙∙∙HN repulsive interaction between the NH(2) and endocyclic NH group results in stronger solvent effects than the proximity with two attractive NH∙∙∙N interactions. The effect of amino and nitro (previously studied) substitution on aromaticity was compared; these two groups have, in most cases, the opposite effect, with the largest being in N1H and N3H purine tautomers. The amino group has a smaller effect on the tautomeric preferences of purine than the nitro group. Only in 8-aminopurine do tautomeric preferences change: N7H is more stable than N9H in H(2)O.
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spelling pubmed-100956122023-04-13 Influence of the Solvent on the Stability of Aminopurine Tautomers and Properties of the Amino Group Jezuita, Anna Wieczorkiewicz, Paweł A. Krygowski, Tadeusz M. Szatylowicz, Halina Molecules Article Amino derivatives of purine (2-, 6-, 8-, and N-NH(2)) have found many applications in biochemistry. This paper presents the results of a systematic computational study of the substituent and solvent effects in these systems. The issues considered are the electron-donating properties of NH(2), its geometry, π-electron delocalization in purine rings and tautomeric stability. Calculations were performed in ten environments, with 1 < ε < 109, using the polarizable continuum model of solvation. Electron-donating properties were quantitatively described by cSAR (charge of the substituent active region) parameter and π-electron delocalization by using the HOMA (harmonic oscillator model of aromaticity) index. In aminopurines, NH(2) proximity interactions depend on its position and the tautomer. The results show that they are the main factor determining how solvation affects the electron-donating strength and geometry of NH(2). Proximity with the NH∙∙∙HN repulsive interaction between the NH(2) and endocyclic NH group results in stronger solvent effects than the proximity with two attractive NH∙∙∙N interactions. The effect of amino and nitro (previously studied) substitution on aromaticity was compared; these two groups have, in most cases, the opposite effect, with the largest being in N1H and N3H purine tautomers. The amino group has a smaller effect on the tautomeric preferences of purine than the nitro group. Only in 8-aminopurine do tautomeric preferences change: N7H is more stable than N9H in H(2)O. MDPI 2023-03-27 /pmc/articles/PMC10095612/ /pubmed/37049758 http://dx.doi.org/10.3390/molecules28072993 Text en © 2023 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Jezuita, Anna
Wieczorkiewicz, Paweł A.
Krygowski, Tadeusz M.
Szatylowicz, Halina
Influence of the Solvent on the Stability of Aminopurine Tautomers and Properties of the Amino Group
title Influence of the Solvent on the Stability of Aminopurine Tautomers and Properties of the Amino Group
title_full Influence of the Solvent on the Stability of Aminopurine Tautomers and Properties of the Amino Group
title_fullStr Influence of the Solvent on the Stability of Aminopurine Tautomers and Properties of the Amino Group
title_full_unstemmed Influence of the Solvent on the Stability of Aminopurine Tautomers and Properties of the Amino Group
title_short Influence of the Solvent on the Stability of Aminopurine Tautomers and Properties of the Amino Group
title_sort influence of the solvent on the stability of aminopurine tautomers and properties of the amino group
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10095612/
https://www.ncbi.nlm.nih.gov/pubmed/37049758
http://dx.doi.org/10.3390/molecules28072993
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