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Cu bound to the peptide amyloid\u2010\u03b2 (A\u03b2) is found in AD brains, and Cu\u2010A\u03b2 could contribute to this oxidative stress, as it is able to produce in vitro H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> and HO<jats:sup>.<\/jats:sup> in the presence of oxygen and biological reducing agents such as ascorbate. The mechanism of Cu\u2010A\u03b2\u2010catalyzed H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> production is however not known, although it was proposed that H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> is directly formed from O<jats:sub>2<\/jats:sub> via a 2\u2010electron process. Here, we implement an electrochemical setup and use the specificity of superoxide dismutase\u20101 (SOD1) to show, for the first time, that H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> production by Cu\u2010A\u03b2 in the presence of ascorbate occurs mainly via a free O<jats:sub>2<\/jats:sub><jats:sup>.\u2212<\/jats:sup> intermediate. This finding radically changes the view on the catalytic mechanism of H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> production by Cu\u2010A\u03b2, and opens the possibility that Cu\u2010A\u03b2\u2010catalyzed O<jats:sub>2<\/jats:sub><jats:sup>.\u2212<\/jats:sup> contributes to oxidative stress in AD, and hence may be of interest.<\/jats:p>","DOI":"10.1002\/anie.201508597","type":"journal-article","created":{"date-parts":[[2015,12,2]],"date-time":"2015-12-02T13:47:27Z","timestamp":1449064047000},"page":"1085-1089","source":"Crossref","is-referenced-by-count":108,"title":["Free Superoxide is an Intermediate in the Production of H<sub>2<\/sub>O<sub>2<\/sub> by Copper(I)\u2010A\u03b2 Peptide and O<sub>2<\/sub>"],"prefix":"10.1002","volume":"55","author":[{"given":"Karine","family":"Reybier","sequence":"first","affiliation":[{"name":"University of Toulouse, UPS; UMR 152 PHARMA-DEV  118 route de Narbonne 31062 Toulouse cedex 9 France"},{"name":"IRD, UMR 152  31062 Toulouse cedex 9 France"}]},{"given":"Sara","family":"Ayala","sequence":"additional","affiliation":[{"name":"CNRS, LCC (Laboratoire de Chimie de Coordination)  205 route de Narbonne, BP 44099 31077 Toulouse Cedex 4 France"},{"name":"University of Toulouse, UPS, INPT  31077 Toulouse Cedex 4 France"}]},{"given":"Bruno","family":"Alies","sequence":"additional","affiliation":[{"name":"CNRS, LCC (Laboratoire de Chimie de Coordination)  205 route de Narbonne, BP 44099 31077 Toulouse Cedex 4 France"},{"name":"University of Toulouse, UPS, INPT  31077 Toulouse Cedex 4 France"}]},{"given":"Jo\u00e3o V.","family":"Rodrigues","sequence":"additional","affiliation":[{"name":"Instituto Tecnologia Qu\u00edmica e Biol\u00f3gica Universidade Nova de Lisboa  Oeiras Portugal"},{"name":"Harvard University Department of Chemistry and Chemical Biology  Cambridge MA USA"}]},{"given":"Susana","family":"Bustos\u2005Rodriguez","sequence":"additional","affiliation":[{"name":"CNRS, LCC (Laboratoire de Chimie de Coordination)  205 route de Narbonne, BP 44099 31077 Toulouse Cedex 4 France"},{"name":"University of Toulouse, UPS, INPT  31077 Toulouse Cedex 4 France"}]},{"given":"Giovanni","family":"La\u2005Penna","sequence":"additional","affiliation":[{"name":"CNR \u2013 National Research Council of Italy ICCOM \u2013 Institute for Chemistry of Organo-Metallic Compounds  via Madonna del Piano 10 50019 Sesto Fiorentino Firenze Italy"}]},{"given":"Fabrice","family":"Collin","sequence":"additional","affiliation":[{"name":"University of Toulouse, UPS; UMR 152 PHARMA-DEV  118 route de Narbonne 31062 Toulouse cedex 9 France"},{"name":"IRD, UMR 152  31062 Toulouse cedex 9 France"},{"name":"CNRS, LCC (Laboratoire de Chimie de Coordination)  205 route de Narbonne, BP 44099 31077 Toulouse Cedex 4 France"},{"name":"University of Toulouse, UPS, INPT  31077 Toulouse Cedex 4 France"}]},{"given":"Cl\u00e1udio M.","family":"Gomes","sequence":"additional","affiliation":[{"name":"Instituto Tecnologia Qu\u00edmica e Biol\u00f3gica Universidade Nova de Lisboa  Oeiras Portugal"},{"name":"Faculdade de Ci\u00eancias, Biosystems and Integrative Sciences Institute Department of Chemistry and Biochemistry Universidade de Lisboa, Campo Grande  Lisboa Portugal"}]},{"given":"Christelle","family":"Hureau","sequence":"additional","affiliation":[{"name":"CNRS, LCC (Laboratoire de Chimie de Coordination)  205 route de Narbonne, BP 44099 31077 Toulouse Cedex 4 France"},{"name":"University of Toulouse, UPS, INPT  31077 Toulouse Cedex 4 France"}]},{"given":"Peter","family":"Faller","sequence":"additional","affiliation":[{"name":"CNRS, LCC (Laboratoire de Chimie de Coordination)  205 route de Narbonne, BP 44099 31077 Toulouse Cedex 4 France"},{"name":"University of Toulouse, UPS, INPT  31077 Toulouse Cedex 4 France"},{"name":"Institute de Chimie (UMR 7177)  4 rue B. 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