Electron transport in biological and inorganic systems is mediated through distinct mechanisms and pathways. Their fundamental mismatch in structural and thermodynamic properties has imposed a significant challenge on the effective coupling at the biotic/abiotic interface, which is central to the design and development of bioelectronic devices and their translation toward various engineering applications. Using electrochemically active bacteria, such as G. sulfurreducens, as a model system, here we report a bottom-up, biosynthetic approach to synergize the electron transport and significantly enhance the coupling at the heterogeneous junction. In particular, graphene oxide was exploited as the respiratory electron acceptors, which can be directly reduced by G. sulfurreducens through extracellular electron transfer, closely coupled with outer membrane cytochromes in electroactive conformation, and actively "wire" the redox centers to external electrical contacts. Through this strategy, the contact resistance at the biofilm/electrode interface can be effectively reduced by 90%. Furthermore, the cyclic voltammetry reveals that the electron transfer of the DL-1 biofilm transformed from a low-current (∼0.36 μA), rate-limited profile to a high-current (∼5 μA), diffusion-limited profile. These results suggested that the integration of rGO can minimize the charge transfer barriers at the biofilm/electrode interface. The more transparent contact at the DL-1/electrode interface also enables unambiguous characterization of the inherent electron transport kinetics across the electroactive biofilm independent of cell/electrode interactions. The current work represents a strategically new approach toward the seamless integration of biological and artificial electronics, which is expected to provide critical insights into the fundamentals of biological electron transport and open up new opportunities for applications in biosensing, biocomputing, and bioenergy conversion.
Keywords: Extracellular electron transfer; biofilm; bioreduction; electron hopping; graphene oxide.