Switchable Bioelectrocatalysis Controlled by Dual Stimuli-Responsive Polymeric Interface.

The engineering of bionanointerfaces using stimuli-responsive polymers offers a new dimension in the design of novel bioelectronic interfaces. The integration of electrode surfaces with stimuli-responsive molecular cues provides a direct control and ability to switch and tune physical and chemical properties of bioelectronic interfaces in various biodevices. Here, we report a dual-responsive biointerface employing a positively responding dual-switchable polymer, poly(NIPAAm-co-DEAEMA)-b-HEAAm, to control and regulate enzyme-based bioelectrocatalysis. The design interface exhibits reversible activation-deactivation of bioelectrocatalytic reactions in response to change in temperature and in pH, which allows manipulation of biomolecular interactions to produce on/off switchable conditions. Using electrochemical measurements, we demonstrate that interfacial bioelectrochemical properties can be tuned over a modest range of temperature (i.e., 20-60 °C) and pH (i.e., pH 4-8) of the medium. The resulting dual-switchable interface may have important implications not only for the design of responsive biocatalysis and on-demand operation of biosensors, but also as an aid to elucidating electron-transport pathways and mechanisms in living organisms by mimicking the dynamic properties of complex biological environments and processes.