Fabrication of biomembrane-like films on carbon electrodes using alkanethiol and diazonium salt and their application for direct electrochemistry of myoglobin

• A new strategy for the modification of carbon electrodes with alkanethiols is developed.
• Carbon was modified with alkanethiol by reaction of alkanethiol with aldehyde groups.
• Aldehyde modified carbon is obtained by electrochemical reduction of p-nitrophenylaldehyde in the presence of nitrous acid.
• The fabrication of biomembrane-like films using diazonium salt is first reported.
• Myoglobin-modified biomembrane-like films show direct electrochemistry and good sensitivity.

Alkanethiols generally form self-assembled monolayers on gold electrodes and the electrochemical reduction of aromatic diazonium salts is a popular method for the covalent modification of carbon. Based on the reaction of alkanethiol with aldehyde groups covalently bound on carbon surface by the electrochemical reduction of aromatic diazonium salts, a new strategy for the modification of carbon electrodes with alkanethiols has been developed. The modification of carbon surface with aldehyde groups is achieved by the electrochemical reduction of aromatic diazonium salts in situ electrogenerated from a nitro precursor, p-nitrophenylaldehyde, in the presence of nitrous acid. By this way, in situ electrogenerated p-aminophenyl aldehyde from p-nitrophenylaldehyde immediately reacts with nitrous acid, effectively minimizing the side reaction of amine groups and aldehyde groups. The as-prepared alkanethiol-modified glassy carbon electrode was further used to make biomembrane-like films by casting didodecyldimethylammonium bromide on its surface. The biomembrane-like films enable the direct electrochemistry of immobilized myoglobin for the detection of hydrogen peroxide. The response is linear over the range of 1–600 μM with a detection limit of 0.3 μM.