摘要：SummaryPhenazines are redox-active nitrogen-containing heterocyclic compounds that can be produced by either bacteria or synthetic approaches. As an electron shuttles (mediators), phenazines are involved in several biological processes facilitating extracellular electron transfer (EET). Therefore, it is of great importance to understand the structural and electronic properties of phenazines that promote EET in microbial electrochemical systems. Our previous study experimentally investigated a phenazine-based library as an exogenous mediator system to facilitate EET inEscherichia coli. Herein, we combine our experimental data with density functional theory (DFT) calculations and multivariate linear regression modeling to understand the structure-function relationships in phenazine-based mediated EET. These calculations demonstrate that the computed redox properties of phenazines in lipophilic environments (e.g., cell membrane) correlate to experimental mediated current densities. Additional DFT-derived molecular properties were considered to develop a predictive model, which could be used in metabolic engineering approaches to introduce phenazines as endogenous mediators into bacteria.Graphical abstractDisplay OmittedHighlights•Coupling experimental data on phenazine-mediated EET inE. coliwith DFT computations•Computational data suggest that electron transfer occurs in lipophilic cell membrane•Developed predictive mediated current density model for phenazine mediators•The model can be used in future design of mediated microbial electrochemical systemsChemistry; Electrochemistry; Bio-electrochemistry; Computational chemistry; Microbiology; Applied microbiology
