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.

Departamento de F ica Aplicada Universidad Politécnica de Cartagena Calle Doctor Fleming s n 30202 Cartagena Spain

Institute of Physics Academy of Sciences of the Czech Republic 162 00 Praha Czech Republic

Laboratorio TASC CNR IOM Basovizza SS 14 Km 163 5 34149 Trieste Italy

Materials Science Factory Instituto de Ciencia de Materiales de Madrid CSIC C Sor Juana Inés de la Cruz 3 Madrid 28049 Spain

Univ Bourgogne Franche Comté FEMTO ST CNRS UFC 15B avenue des Montboucons F 25030 Besançon Cedex France

Univ Grenoble Alpes CEA IRIG DEPHY PHELIQS 38000 Grenoble France

Univ Grenoble Alpes CNRS Grenoble INP Institut NEEL 38000 Grenoble France

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