Bioelectrocatalysis is an interdisciplinary research field combining biocatalysis and electrocatalysis via the utilization of materials derived from biological systems as catalysts to catalyze the redox reactions occurring at an electrode. Bioelectrocatalysis synergistically couples the merits of both biocatalysis and electrocatalysis. The advantages of biocatalysis include high activity, high selectivity, wide substrate scope, and mild reaction conditions. The advantages of electrocatalysis include the possible utilization of renewable electricity as an electron source and high energy conversion efficiency. These properties are integrated to achieve selective biosensing, efficient energy conversion, and the production of diverse products. This review seeks to systematically and comprehensively detail the fundamentals, analyze the existing problems, summarize the development status and applications, and look toward the future development directions of bioelectrocatalysis. First, the structure, function, and modification of bioelectrocatalysts are discussed. Second, the essentials of bioelectrocatalytic systems, including electron transfer mechanisms, electrode materials, and reaction medium, are described. Third, the application of bioelectrocatalysis in the fields of biosensors, fuel cells, solar cells, catalytic mechanism studies, and bioelectrosyntheses of high-value chemicals are systematically summarized. Finally, future developments and a perspective on bioelectrocatalysis are suggested.

Fundamentals, Applications, and Future Directions of Bioelectrocatalysis.

Bioelectrocatalysis is a green, sustainable, efficient method to produce value-added chemicals, clean biofuels and degradable materials. As an alternative approach to modern biomanufacturing technology, bioelectrocatalysis fully combines the merits of both biocatalysis and electrocatalysis to realize the green, efficient production of target products from electricity. Here, we review the development status of bioelectrocatalysis, discussing the current challenges and looking toward future development directions. First, we detail the structure, function and modification methods of bioelectrocatalysis. Next, we describe the mechanism of electron transfer, including mediated electron transfer and directed electron transfer. Third, we discuss the impact of the electrode on bioelectrocatalysis. Then we analyse and summarize the application of bioelectrocatalysis methods in the production of chemicals, biofuels and materials. Finally, we detail future developments and perspectives on bioelectrocatalysis for electrosynthesis. Electrochemical reactions can provide necessary redox equivalents for biocatalysis. In this Review, Minteer and co-workers summarize the current status and challenges of enzymatic and microbial bioelectrocatalysis for the green and efficient production of target products using electricity.

The progress and outlook of bioelectrocatalysis for the production of chemicals, fuels and materials

Engineering cytochrome P450 enzyme systems for biomedical and biotechnological applications

Redox Partners: Function Modulators of Bacterial P450 Enzymes.

Cytochrome P450 enzymes in fungal natural product biosynthesis

Cytochrome P450 enzymes are highly diversified biocatalysts associated with steroid biosynthesis, xenobiotic metabolism, biosynthesis of natural products, and industrial oxidation reactions. A typical P450 catalytic cycle requires sequential transfer of two electrons from NAD(P)H to the heme-iron reactive center for O2 activation. For the most abundant bacterial Class I P450 systems, this important process is usually mediated by two redox partner proteins including an FAD-containing ferredoxin reductase (FdR) and a small iron–sulfur protein, ferredoxin (Fdx). However, it is often unclear which pair of Fdx and FdR among multiple redox partners is the optimal one for a specific Class I P450 enzyme. To address this important but underexplored question, herein, a reaction matrix network with 16 Fdxs, 8 FdRs, and 6 P450s (against 7 substrates) was constituted. By analyzing the reactivity profiles of 896 P450 reactions, together with phylogenetic analysis, redox potential measurements, structural simulations, a...

Lei Han

Papers

Mechanistic Insights into Interactions between Bacterial Class I P450 Enzymes and Redox Partners