Stimuli‐Responsive Supramolecular Interfaces for Controllable Bioelectrocatalysis

AbstractInspired by natural biochemical promotion and inhibition of electron‐transport processes in response to real‐life physical/chemical stimuli, artificial signal‐triggered bioelectrocatalysis and modulation of the electron‐transfer processes of redox biomolecules are vitally important for understanding electron‐transport pathways in bioelectrochemical systems and for mimicking the dynamic properties of sensitive biochemical reactions in real bioprocesses. Recently, the reversible activation and deactivation of bioelectrocatalysis by external stimuli on functional electrodes integrated with redox enzymes has been established, especially at stimuli‐responsive supramolecular interfaces. Potential applications in various research fields include controllable biofuel cells, bioelectronic devices, stimuli‐responsive biosensors, energy transduction, information storage, and data processing. This Minireview aims to summarize the current state‐of‐the‐art knowledge on various controllable bioelectrocatalysts from diverse functional interfaces formed by supramolecular interactions and supramolecular assemblies. The role of the assembled interface is highlighted, and the electrochemical kinetics during “on” and “off” states of bioelectrocatalysis is discussed. Finally, possible strategies for the future design of stimuli‐responsive bioelectrocatalysts integrated with multifunctional supramolecular interfaces are presented.