Cooperative Control of Bioelectrocatalytic Activity for Thermo- and Photo-Switchable Cup-Stacked Carbon Nanofiber Electrodes Modified with Phase Transition Polymer and Heme Peptide.

ABSTRACT

Empowering biocatalyst-modified electrodes with the ability to both enforce and perceive will enable the development of intrinsically switchable bioelectrode systems, which exhibit autonomous and heteronomous actions specific to living organisms. However, the electrocatalytic activity of switchable bioelectrodes reported so far has been controlled by changes in the rate of substrate transport to biocatalysts. Here, we prepared a cup-stacked carbon nanofiber (CSCNF) electrode modified with a thermoresponsive N-isopropylacrylamide-based polymer containing peroxidase model compounds (HP). As CSCNFs worked as a converter from near-infrared (NIR) light to heat, bioelectrocatalytic activity of the electrode to H2O2 reduction was reversibly controlled by changes in the amount of electroactive HP, based on expanded and contracted states of the polymers induced by not only environmental temperature changes but also external NIR light irradiation. This intrinsically switchable bioelectrode technique would hold promise for adding new performances in electrochemical biosensors and biofuel cells, for example, autonomous and heteronomous tunable sensitivity and capacity.