Issue 9, 2021

Phenazines as model low-midpoint potential electron shuttles for photosynthetic bioelectrochemical systems

Abstract

Bioelectrochemical approaches for energy conversion rely on efficient wiring of natural electron transport chains to electrodes. However, state-of-the-art exogenous electron mediators give rise to significant energy losses and, in the case of living systems, long-term cytotoxicity. Here, we explored new selection criteria for exogenous electron mediation by examining phenazines as novel low-midpoint potential molecules for wiring the photosynthetic electron transport chain of the cyanobacterium Synechocystis sp. PCC 6803 to electrodes. We identified pyocyanin (PYO) as an effective cell-permeable phenazine that can harvest electrons from highly reducing points of photosynthesis. PYO-mediated photocurrents were observed to be 4-fold higher than mediator-free systems with an energetic gain of 200 mV compared to the common high-midpoint potential mediator 2,6-dichloro-1,4-benzoquinone (DCBQ). The low-midpoint potential of PYO led to O2 reduction side-reactions, which competed significantly against photocurrent generation; the tuning of mediator concentration was important for outcompeting the side-reactions whilst avoiding acute cytotoxicity. DCBQ-mediated photocurrents were generally much higher but also decayed rapidly and were non-recoverable with fresh mediator addition. This suggests that the cells can acquire DCBQ-resistance over time. In contrast, PYO gave rise to steadier current enhancement despite the co-generation of undesirable reactive oxygen species, and PYO-exposed cells did not develop acquired resistance. Moreover, we demonstrated that the cyanobacteria can be genetically engineered to produce PYO endogenously to improve long-term prospects. Overall, this study established that energetic gains can be achieved via the use of low-potential phenazines in photosynthetic bioelectrochemical systems, and quantifies the factors and trade-offs that determine efficacious mediation in living bioelectrochemical systems.

Graphical abstract: Phenazines as model low-midpoint potential electron shuttles for photosynthetic bioelectrochemical systems

Supplementary files

Article information

Article type
Edge Article
Submitted
13 okt 2020
Accepted
14 yan 2021
First published
15 yan 2021
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2021,12, 3328-3338

Phenazines as model low-midpoint potential electron shuttles for photosynthetic bioelectrochemical systems

E. R. Clifford, R. W. Bradley, L. T. Wey, J. M. Lawrence, X. Chen, C. J. Howe and J. Z. Zhang, Chem. Sci., 2021, 12, 3328 DOI: 10.1039/D0SC05655C

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