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Copper-assisted oxidation of catechols into quinone derivatives

Catechols are ubiquitous substances often acting as antioxidants, thus of importance in a variety of biological processes. The Fenton and Haber–Weiss processes are thought to transform these molecules into aggressive reactive oxygen species (ROS), a source of oxidative stress and possibly inducing d...

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Autores principales: Gómez-Herrero, Ana Cristina, Sánchez-Sánchez, Carlos, Chérioux, Frédéric, Martínez, Jose Ignacio, Abad, José, Floreano, Luca, Verdini, Alberto, Cossaro, Albano, Mazaleyrat, Estelle, Guisset, Valérie, David, Philippe, Lisi, Simone, Martín Gago, José Angel, Coraux, Johann
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8179264/
https://www.ncbi.nlm.nih.gov/pubmed/34163992
http://dx.doi.org/10.1039/d0sc04883f
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author Gómez-Herrero, Ana Cristina
Sánchez-Sánchez, Carlos
Chérioux, Frédéric
Martínez, Jose Ignacio
Abad, José
Floreano, Luca
Verdini, Alberto
Cossaro, Albano
Mazaleyrat, Estelle
Guisset, Valérie
David, Philippe
Lisi, Simone
Martín Gago, José Angel
Coraux, Johann
author_facet Gómez-Herrero, Ana Cristina
Sánchez-Sánchez, Carlos
Chérioux, Frédéric
Martínez, Jose Ignacio
Abad, José
Floreano, Luca
Verdini, Alberto
Cossaro, Albano
Mazaleyrat, Estelle
Guisset, Valérie
David, Philippe
Lisi, Simone
Martín Gago, José Angel
Coraux, Johann
author_sort Gómez-Herrero, Ana Cristina
collection PubMed
description Catechols are ubiquitous substances often acting as antioxidants, thus of importance in a variety of biological processes. The Fenton and Haber–Weiss processes are thought to transform these molecules into aggressive reactive oxygen species (ROS), a source of oxidative stress and possibly inducing degenerative diseases. Here, using model conditions (ultrahigh vacuum and single crystals), we unveil another process capable of converting catechols into ROSs, namely an intramolecular redox reaction catalysed by a Cu surface. We focus on a tri-catechol, the hexahydroxytriphenylene molecule, and show that this antioxidant is thereby transformed into a semiquinone, as an intermediate product, and then into an even stronger oxidant, a quinone, as final product. We argue that the transformations occur via two intramolecular redox reactions: since the Cu surface cannot oxidise the molecules, the starting catechol and the semiquinone forms each are, at the same time, self-oxidised and self-reduced. Thanks to these reactions, the quinone and semiquinone are able to interact with the substrate by readily accepting electrons donated by the substrate. Our combined experimental surface science and ab initio analysis highlights the key role played by metal nanoparticles in the development of degenerative diseases.
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spelling pubmed-81792642021-06-22 Copper-assisted oxidation of catechols into quinone derivatives Gómez-Herrero, Ana Cristina Sánchez-Sánchez, Carlos Chérioux, Frédéric Martínez, Jose Ignacio Abad, José Floreano, Luca Verdini, Alberto Cossaro, Albano Mazaleyrat, Estelle Guisset, Valérie David, Philippe Lisi, Simone Martín Gago, José Angel Coraux, Johann Chem Sci Chemistry Catechols are ubiquitous substances often acting as antioxidants, thus of importance in a variety of biological processes. The Fenton and Haber–Weiss processes are thought to transform these molecules into aggressive reactive oxygen species (ROS), a source of oxidative stress and possibly inducing degenerative diseases. Here, using model conditions (ultrahigh vacuum and single crystals), we unveil another process capable of converting catechols into ROSs, namely an intramolecular redox reaction catalysed by a Cu surface. We focus on a tri-catechol, the hexahydroxytriphenylene molecule, and show that this antioxidant is thereby transformed into a semiquinone, as an intermediate product, and then into an even stronger oxidant, a quinone, as final product. We argue that the transformations occur via two intramolecular redox reactions: since the Cu surface cannot oxidise the molecules, the starting catechol and the semiquinone forms each are, at the same time, self-oxidised and self-reduced. Thanks to these reactions, the quinone and semiquinone are able to interact with the substrate by readily accepting electrons donated by the substrate. Our combined experimental surface science and ab initio analysis highlights the key role played by metal nanoparticles in the development of degenerative diseases. The Royal Society of Chemistry 2020-12-21 /pmc/articles/PMC8179264/ /pubmed/34163992 http://dx.doi.org/10.1039/d0sc04883f Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/
spellingShingle Chemistry
Gómez-Herrero, Ana Cristina
Sánchez-Sánchez, Carlos
Chérioux, Frédéric
Martínez, Jose Ignacio
Abad, José
Floreano, Luca
Verdini, Alberto
Cossaro, Albano
Mazaleyrat, Estelle
Guisset, Valérie
David, Philippe
Lisi, Simone
Martín Gago, José Angel
Coraux, Johann
Copper-assisted oxidation of catechols into quinone derivatives
title Copper-assisted oxidation of catechols into quinone derivatives
title_full Copper-assisted oxidation of catechols into quinone derivatives
title_fullStr Copper-assisted oxidation of catechols into quinone derivatives
title_full_unstemmed Copper-assisted oxidation of catechols into quinone derivatives
title_short Copper-assisted oxidation of catechols into quinone derivatives
title_sort copper-assisted oxidation of catechols into quinone derivatives
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8179264/
https://www.ncbi.nlm.nih.gov/pubmed/34163992
http://dx.doi.org/10.1039/d0sc04883f
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