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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| Format: | Article |
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MDPI AG
2016-12-01
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| Series: | Molecules |
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| Online Access: | http://www.mdpi.com/1420-3049/21/12/1683 |
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| author | Ana B. Fraga-Timiraos Gemma M. Rodríguez-Muñiz Vicente Peiro-Penalba Miguel A. Miranda Virginie Lhiaubet-Vallet |
| author_facet | Ana B. Fraga-Timiraos Gemma M. Rodríguez-Muñiz Vicente Peiro-Penalba Miguel A. Miranda Virginie Lhiaubet-Vallet |
| author_sort | Ana B. Fraga-Timiraos |
| collection | DOAJ |
| 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. |
| first_indexed | 2024-12-14T18:49:13Z |
| format | Article |
| id | doaj.art-942c97ff0d6e4e8db609aeb8a6464cf3 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-12-14T18:49:13Z |
| publishDate | 2016-12-01 |
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| record_format | Article |
| series | Molecules |
| spelling | doaj.art-942c97ff0d6e4e8db609aeb8a6464cf32022-12-21T22:51:19ZengMDPI AGMolecules1420-30492016-12-012112168310.3390/molecules21121683molecules21121683Stereoselective Fluorescence Quenching in the Electron Transfer Photooxidation of Nucleobase-Related Azetidines by CyanoaromaticsAna B. Fraga-Timiraos0Gemma M. Rodríguez-Muñiz1Vicente Peiro-Penalba2Miguel A. Miranda3Virginie Lhiaubet-Vallet4Instituto Mixto de Tecnología Química (UPV-CSIC), Universitat Politècnica de València—Consejo Superior de Investigaciones Científicas, Avda de los Naranjos s/n, 46022 Valencia, SpainInstituto Mixto de Tecnología Química (UPV-CSIC), Universitat Politècnica de València—Consejo Superior de Investigaciones Científicas, Avda de los Naranjos s/n, 46022 Valencia, SpainInstituto Mixto de Tecnología Química (UPV-CSIC), Universitat Politècnica de València—Consejo Superior de Investigaciones Científicas, Avda de los Naranjos s/n, 46022 Valencia, SpainInstituto Mixto de Tecnología Química (UPV-CSIC), Universitat Politècnica de València—Consejo Superior de Investigaciones Científicas, Avda de los Naranjos s/n, 46022 Valencia, SpainInstituto Mixto de Tecnología Química (UPV-CSIC), Universitat Politècnica de València—Consejo Superior de Investigaciones Científicas, Avda de los Naranjos s/n, 46022 Valencia, SpainElectron 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.http://www.mdpi.com/1420-3049/21/12/1683DNA repairenergy and charge transfernucleobase analoguesphotolyaseredox potential |
| spellingShingle | Ana B. Fraga-Timiraos Gemma M. Rodríguez-Muñiz Vicente Peiro-Penalba Miguel A. Miranda Virginie Lhiaubet-Vallet Stereoselective Fluorescence Quenching in the Electron Transfer Photooxidation of Nucleobase-Related Azetidines by Cyanoaromatics Molecules DNA repair energy and charge transfer nucleobase analogues photolyase redox potential |
| 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 | DNA repair energy and charge transfer nucleobase analogues photolyase redox potential |
| url | http://www.mdpi.com/1420-3049/21/12/1683 |
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