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.