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Stereoselective Fluorescence Quenching in the Electron Transfer Photooxidation of Nucleobase-Related Azetidines by Cyanoaromatics

Electron transfer involving nucleic acids and their derivatives is an important field in bioorganic chemistry, specifically in connection with its role in the photo-driven DNA damage and repair. Four-membered ring heterocyclic oxetanes and azetidines have been claimed to be the intermediates involve...

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Autores principales: Fraga-Timiraos, Ana B., Rodríguez-Muñiz, Gemma M., Peiro-Penalba, Vicente, Miranda, Miguel A., Lhiaubet-Vallet, Virginie
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2016
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6273614/
https://www.ncbi.nlm.nih.gov/pubmed/27941606
http://dx.doi.org/10.3390/molecules21121683
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author Fraga-Timiraos, Ana B.
Rodríguez-Muñiz, Gemma M.
Peiro-Penalba, Vicente
Miranda, Miguel A.
Lhiaubet-Vallet, Virginie
author_facet Fraga-Timiraos, Ana B.
Rodríguez-Muñiz, Gemma M.
Peiro-Penalba, Vicente
Miranda, Miguel A.
Lhiaubet-Vallet, Virginie
author_sort Fraga-Timiraos, Ana B.
collection PubMed
description Electron transfer involving nucleic acids and their derivatives is an important field in bioorganic chemistry, specifically in connection with its role in the photo-driven DNA damage and repair. Four-membered ring heterocyclic oxetanes and azetidines have been claimed to be the intermediates involved in the repair of DNA (6-4) photoproduct by photolyase. In this context, we examine here the redox properties of the two azetidine isomers obtained from photocycloaddition between 6-aza-1,3-dimethyluracil and cyclohexene. Steady-state and time-resolved fluorescence experiments using a series of photoreductants and photooxidants have been run to evaluate the efficiency of the electron transfer process. Analysis of the obtained quenching kinetics shows that the azetidine compounds can act as electron donors. Additionally, it appears that the cis isomer is more easily oxidized than its trans counterpart. This result is in agreement with electrochemical studies performed on both azetidine derivatives.
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spelling pubmed-62736142018-12-28 Stereoselective Fluorescence Quenching in the Electron Transfer Photooxidation of Nucleobase-Related Azetidines by Cyanoaromatics Fraga-Timiraos, Ana B. Rodríguez-Muñiz, Gemma M. Peiro-Penalba, Vicente Miranda, Miguel A. Lhiaubet-Vallet, Virginie Molecules Article Electron transfer involving nucleic acids and their derivatives is an important field in bioorganic chemistry, specifically in connection with its role in the photo-driven DNA damage and repair. Four-membered ring heterocyclic oxetanes and azetidines have been claimed to be the intermediates involved in the repair of DNA (6-4) photoproduct by photolyase. In this context, we examine here the redox properties of the two azetidine isomers obtained from photocycloaddition between 6-aza-1,3-dimethyluracil and cyclohexene. Steady-state and time-resolved fluorescence experiments using a series of photoreductants and photooxidants have been run to evaluate the efficiency of the electron transfer process. Analysis of the obtained quenching kinetics shows that the azetidine compounds can act as electron donors. Additionally, it appears that the cis isomer is more easily oxidized than its trans counterpart. This result is in agreement with electrochemical studies performed on both azetidine derivatives. MDPI 2016-12-07 /pmc/articles/PMC6273614/ /pubmed/27941606 http://dx.doi.org/10.3390/molecules21121683 Text en © 2016 by the authors. 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 (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Fraga-Timiraos, Ana B.
Rodríguez-Muñiz, Gemma M.
Peiro-Penalba, Vicente
Miranda, Miguel A.
Lhiaubet-Vallet, Virginie
Stereoselective Fluorescence Quenching in the Electron Transfer Photooxidation of Nucleobase-Related Azetidines by Cyanoaromatics
title Stereoselective Fluorescence Quenching in the Electron Transfer Photooxidation of Nucleobase-Related Azetidines by Cyanoaromatics
title_full Stereoselective Fluorescence Quenching in the Electron Transfer Photooxidation of Nucleobase-Related Azetidines by Cyanoaromatics
title_fullStr Stereoselective Fluorescence Quenching in the Electron Transfer Photooxidation of Nucleobase-Related Azetidines by Cyanoaromatics
title_full_unstemmed Stereoselective Fluorescence Quenching in the Electron Transfer Photooxidation of Nucleobase-Related Azetidines by Cyanoaromatics
title_short Stereoselective Fluorescence Quenching in the Electron Transfer Photooxidation of Nucleobase-Related Azetidines by Cyanoaromatics
title_sort stereoselective fluorescence quenching in the electron transfer photooxidation of nucleobase-related azetidines by cyanoaromatics
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6273614/
https://www.ncbi.nlm.nih.gov/pubmed/27941606
http://dx.doi.org/10.3390/molecules21121683
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