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Diazonium Functionalisation of Carbon Nanotubes for Specific Orientation of Multicopper Oxidases: Controlling Electron Entry Points and Oxygen Diffusion to the Enzyme
Author(s) -
Lalaoui Noémie,
Holzinger Michael,
Le Goff Alan,
Cosnier Serge
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201601377
Subject(s) - electrocatalyst , chemistry , copper , carbon nanotube , oxygen , diffusion , carbon fibers , bilirubin oxidase , electrochemistry , inorganic chemistry , electrode , nanotechnology , organic chemistry , enzyme , materials science , physics , composite material , composite number , thermodynamics
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.