title: How the Intricate Interactions between Carbon Nanotubes and Two Bilirubin Oxidases Control Direct and Mediated O2 Reduction.
abstract: Due to the lack of a valid approach in the design of electrochemical interfaces modified with enzymes for efficient catalysis, many oxidoreductases are still not addressed by electrochemistry. We report in this work an in-depth study of the interactions between two different bilirubin oxidases, (from the fungus Myrothecium verrucaria and from the bacterium Bacillus pumilus), catalysts of oxygen reduction, and carbon nanotubes bearing various surface charges (pristine, carboxylic-, and pyrene-methylamine-functionalized). The surface charges and dipole moment of the enzymes as well as the surface state of the nanomaterials are characterized as a function of pH. An original electrochemical approach allows determination of the best interface for direct or mediated electron transfer processes as a function of enzyme, nanomaterial type, and adsorption conditions. We correlate these experimental results to theoric voltammetric curves. Such an integrative study suggests strategies for designing efficient bioelectrochemical interfaces toward the elaboration of biodevices such as enzymatic fuel cells for sustainable electricity production.
authors.affiliation: Aix Marseille Univ, CNRS , BIP, Bioénergétique et Ingénierie des Protéines UMR7281, 31 chemin Joseph Aiguier 13402 Marseille Cedex 20, France.
authors.forename: Ievgen
authors.initials: I
authors.lastname: Mazurenko
authors.affiliation: Aix Marseille Univ, CNRS , BIP, Bioénergétique et Ingénierie des Protéines UMR7281, 31 chemin Joseph Aiguier 13402 Marseille Cedex 20, France.
authors.forename: Karen
authors.initials: K
authors.lastname: Monsalve
authors.affiliation: Centre de Recherche Paul Pascal, UPR 8641, CNRS, Bordeaux University , 33600 Pessac, France.
authors.forename: Jad
authors.initials: J
authors.lastname: Rouhana
authors.affiliation: Aix Marseille Université, CNRS , CINaM UMR 7325, 13288 Marseille, France.
authors.forename: Philippe
authors.initials: P
authors.lastname: Parent
authors.affiliation: Aix Marseille Université, CNRS , CINaM UMR 7325, 13288 Marseille, France.
authors.forename: Carine
authors.initials: C
authors.lastname: Laffon
authors.affiliation: Université Grenoble Alpes , DCM UMR 5250, 38000 Grenoble, France.
authors.forename: Alan Le
authors.initials: AL
authors.lastname: Goff
authors.affiliation: Institute of Electronics, Microelectronics and Nanotechnology (IEMN, UMR CNRS 8520) , , Université Lille 1, Cité Scientifique Avenue Poincaré-BP60069, 59652 Villeneuve d'Ascq, France.
authors.forename: Sabine
authors.initials: S
authors.lastname: Szunerits
authors.affiliation: Institute of Electronics, Microelectronics and Nanotechnology (IEMN, UMR CNRS 8520) , , Université Lille 1, Cité Scientifique Avenue Poincaré-BP60069, 59652 Villeneuve d'Ascq, France.
authors.forename: Rabah
authors.initials: R
authors.lastname: Boukherroub
authors.affiliation: Aix Marseille Univ, CNRS , BIP, Bioénergétique et Ingénierie des Protéines UMR7281, 31 chemin Joseph Aiguier 13402 Marseille Cedex 20, France.
authors.forename: Marie-Thérèse
authors.initials: MT
authors.lastname: Giudici-Orticoni
authors.affiliation: Centre de Recherche Paul Pascal, UPR 8641, CNRS, Bordeaux University , 33600 Pessac, France.
authors.forename: Nicolas
authors.initials: N
authors.lastname: Mano
authors.affiliation: Aix Marseille Univ, CNRS , BIP, Bioénergétique et Ingénierie des Protéines UMR7281, 31 chemin Joseph Aiguier 13402 Marseille Cedex 20, France.
authors.forename: Elisabeth
authors.initials: E
authors.lastname: Lojou
keywords: bilirubin oxidase; bioelectrocatalysis; carbon nanotubes; direct electron transfer; electrostatic interactions; mediated electron transfer