Diazonium Functionalisation of Carbon Nanotubes for Specific Orientation of Multicopper Oxidases: Controlling Electron Entry Points and Oxygen Diffusion to the Enzyme. Issue 30 (21st June 2016)

• Record Type: Journal Article
• Authors: Lalaoui, Noémie; Holzinger, Michael; Le Goff, Alan; Cosnier, Serge
• Is Part Of: Chemistry. Volume 22:Issue 30(2016)
• Page Start: 10494
• Page End: 10500
• Publication Date: 2016-06-21
• Subjects: bilirubin oxidases -- diazonium -- metalloenzymes -- nanotubes -- oxygen reduction; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201601377
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: We report the controlled orientation of bilirubin oxidases (BOD) from Myrothecium verrucaria on multiwalled carbon nanotubes (MWCNTs) functionalised by electrografting of 6‐carboxynaphthalenediazonium and 4‐(2‐aminoethyl)benzenediazonium salts. On negatively charged naphthoate‐modified MWCNTs, a high‐potential (0.44 V vs. SCE) oxygen reduction electrocatalysis is observed, occurring via the T1 copper centre. On positively charged ammonium‐modified MWCNTs, a low‐potential (0.15 V) oxygen reduction electrocatalysis is observed, occurring through a partially oxidised state of the T2/T3 trinuclear copper cluster. Finally, chemically modified naphthoate MWCNTs exhibit high bioelectrocatalytic current densities of 3.9 mA cm −2 under air at gas‐diffusion electrode. Abstract : Caught on the tube : The controlled orientation of bilirubin oxidases from Myrothecium verrucaria ( Mv BOD) on multiwalled carbon nanotubes (MWCNTs) functionalised by electrografting of 6‐carboxynaphthalenediazonium and 4‐(2‐aminoethyl)benzenediazonium salts is reported. Specific covalent functionalisation of carbon nanotubes (see figure) enables control over electron transfer and oxygen diffusion to the oxygen‐reducing copper enzyme.