Orientation Control of Trametes Laccases on a Carbon Electrode Surface to Understand the Orientation Effect on the Electrocatalytic Activity.

By using a carbon-coated anodic aluminum oxide (CAAO) film as a monolithic porous electrode for the immobilization of Trametes laccases (LACs), an attempt is made to control the orientation of LAC molecules toward the electrode surface simply by applying an electric potential to the CAAO film. Because the resulting film is characterized by a myriad of open, simple, and straight nanochannels with diameters as large as 40 nm, the O2 diffusion problem in pores is minimized, thereby making it possible to highlight the effect of such orientation on the electrocatalytic activity as a biocathode. It has been evidenced that LAC molecules are favorably oriented for a smooth electron transfer from the electrode when the LACs are immobilized with applying a positive voltage to the electrode, and such favorable orientation exhibits 3.7-times higher electrocatalytic activity than unfavorable orientation. Furthermore, the orientation mechanism has been rationally explained in terms of local surface chemistry on a LAC molecule.