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PublicationJournal of the American Chemical Society
Year2012
Volume134
Pages17212−17220
International

Gold Nanoparticles as Electronic Bridges for Laccase-Based Biocathodes

Authors:María Cristina Gutiérrez Sánchez, Marcos Pita Martínez, Cristina Vaz Dominguez, Sergey Shleev , Antonio López de Lacey
Groups of research:BioElectroCatalysis
Direct electron transfer (DET) reactions
between redox enzymes and electrodes can be maximized by
oriented immobilization of the enzyme molecules onto an
electroactive surface modified with functionalized gold nanoparticles
(AuNPs). Here, we present such strategy for
obtaining a DET-based laccase (Lc) cathode for O2 electroreduction
at low overpotentials. The stable nanostructured
enzymatic electrode is based on the step-by-step covalent
attachment of AuNPs and Lc molecules to porous graphite
electrodes using the diazonium salt reduction strategy. Oriented immobilization of the enzyme molecules on adequately
functionalized AuNPs allows establishing very fast DET with the electrode via their Cu T1 site. The measured electrocatalytic
waves of O2 reduction can be deconvoluted into two contributions. The one at lower overpotentials corresponds to immobilized
Lc molecules that are efficiently wired by the AuNPs with a heterogeneous electron transfer rate constant k0 ≫ 400 s−1.
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