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

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.

Phenazines were explored as novel low-midpoint potential molecules for wiring cyanobacteria to electrodes.     

Floc strength characterization technique. An insight into silica aggregation

This paper tests an approach to the estimation of relative particle bond strength based on the nondimensional floc and aggregation factors. The strength of flocs formed by aggregating nanosized silica particles with the addition of potassium chloride (KCl) or cationic surfactants, alkyltrimethylammonium bromide (mixture of CTAB, DTAB, and MTAB) was analyzed. The bonding force of the flocs formed in surfactant compared to that formed in the KCl system was estimated using the new dimensional analysis approach. This force ratio was then compared to that obtained by atomic force microscopy.