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Substituted adenine quartets: interplay between substituent effect, hydrogen bonding, and aromaticity
Adenine, one of the components of DNA/RNA helices, has the ability to form self-organizing structures with cyclic hydrogen bonds (A(4)), similar to guanine quartets. Here, we report a computational investigation of the effect of substituents (X = NO(2), Cl, F, H, Me, and NH(2)) on the electronic str...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9054646/ https://www.ncbi.nlm.nih.gov/pubmed/35520336 http://dx.doi.org/10.1039/d0ra04585c |
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author | Szatylowicz, Halina Marek, Paulina H. Stasyuk, Olga A. Krygowski, Tadeusz M. Solà, Miquel |
author_facet | Szatylowicz, Halina Marek, Paulina H. Stasyuk, Olga A. Krygowski, Tadeusz M. Solà, Miquel |
author_sort | Szatylowicz, Halina |
collection | PubMed |
description | Adenine, one of the components of DNA/RNA helices, has the ability to form self-organizing structures with cyclic hydrogen bonds (A(4)), similar to guanine quartets. Here, we report a computational investigation of the effect of substituents (X = NO(2), Cl, F, H, Me, and NH(2)) on the electronic structure of 9H-adenine and its quartets (A(4)-N1, A(4)-N3, and A(4)-N7). DFT calculations were used to show the relationships between the electronic nature of the substituents, strength of H-bonds in the quartets, and aromaticity of five- and six-membered rings of adenine. We demonstrated how the remote substituent X modifies the proton-donating properties of the NH(2) group involved in the H-bonds within quartets and how the position of the substituent and its electronic nature affect the stability of the quartets. We also showed the possible changes in electronic properties of the substituent and aromaticity of adenine rings caused by tetramer formation. The results indicate that the observed relationships depend on the A(4) type. Moreover, the same substituent can both strengthen and weaken intermolecular interactions, depending on the substitution position. |
format | Online Article Text |
id | pubmed-9054646 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-90546462022-05-04 Substituted adenine quartets: interplay between substituent effect, hydrogen bonding, and aromaticity Szatylowicz, Halina Marek, Paulina H. Stasyuk, Olga A. Krygowski, Tadeusz M. Solà, Miquel RSC Adv Chemistry Adenine, one of the components of DNA/RNA helices, has the ability to form self-organizing structures with cyclic hydrogen bonds (A(4)), similar to guanine quartets. Here, we report a computational investigation of the effect of substituents (X = NO(2), Cl, F, H, Me, and NH(2)) on the electronic structure of 9H-adenine and its quartets (A(4)-N1, A(4)-N3, and A(4)-N7). DFT calculations were used to show the relationships between the electronic nature of the substituents, strength of H-bonds in the quartets, and aromaticity of five- and six-membered rings of adenine. We demonstrated how the remote substituent X modifies the proton-donating properties of the NH(2) group involved in the H-bonds within quartets and how the position of the substituent and its electronic nature affect the stability of the quartets. We also showed the possible changes in electronic properties of the substituent and aromaticity of adenine rings caused by tetramer formation. The results indicate that the observed relationships depend on the A(4) type. Moreover, the same substituent can both strengthen and weaken intermolecular interactions, depending on the substitution position. The Royal Society of Chemistry 2020-06-18 /pmc/articles/PMC9054646/ /pubmed/35520336 http://dx.doi.org/10.1039/d0ra04585c Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/ |
spellingShingle | Chemistry Szatylowicz, Halina Marek, Paulina H. Stasyuk, Olga A. Krygowski, Tadeusz M. Solà, Miquel Substituted adenine quartets: interplay between substituent effect, hydrogen bonding, and aromaticity |
title | Substituted adenine quartets: interplay between substituent effect, hydrogen bonding, and aromaticity |
title_full | Substituted adenine quartets: interplay between substituent effect, hydrogen bonding, and aromaticity |
title_fullStr | Substituted adenine quartets: interplay between substituent effect, hydrogen bonding, and aromaticity |
title_full_unstemmed | Substituted adenine quartets: interplay between substituent effect, hydrogen bonding, and aromaticity |
title_short | Substituted adenine quartets: interplay between substituent effect, hydrogen bonding, and aromaticity |
title_sort | substituted adenine quartets: interplay between substituent effect, hydrogen bonding, and aromaticity |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9054646/ https://www.ncbi.nlm.nih.gov/pubmed/35520336 http://dx.doi.org/10.1039/d0ra04585c |
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