Porous translucent electrodes enhance current generation from photosynthetic biofilms.

Some photosynthetically active bacteria transfer electrons across their membranes, generating electrical photocurrents in biofilms. Devices harvesting solar energy by this mechanism are currently limited by the charge transfer to the electrode. Here, we report the enhancement of bioelectrochemical photocurrent harvesting using electrodes with porosities on the nanometre and micrometre length scale. For the cyanobacteria Nostoc punctiforme and Synechocystis sp. PCC6803 on structured indium-tin-oxide electrodes, an increase in current generation by two orders of magnitude is observed compared to a non-porous electrode. In addition, the photo response is substantially faster compared to non-porous anodes. Electrodes with large enough mesopores for the cells to inhabit show only a small advantage over purely nanoporous electrode morphologies, suggesting the prevalence of a redox shuttle mechanism in the electron transfer from the bacteria to the electrode over a direct conduction mechanism. Our results highlight the importance of electrode nanoporosity in the design of electrochemical bio-interfaces

Photosynthetic, respiratory and extracellular electron transport pathways in cyanobacteria.

Cyanobacteria have evolved elaborate electron transport pathways to carry out photosynthesis and respiration, and to dissipate excess energy in order to limit cellular damage. Our understanding of the complexity of these systems and their role in allowing cyanobacteria to cope with varying environmental conditions is rapidly improving, but many questions remain. We summarize current knowledge of cyanobacterial electron transport pathways, including the possible roles of alternative pathways in photoprotection. We describe extracellular electron transport, which is as yet poorly understood. Biological photovoltaic devices, which measure electron output from cells, and which have been proposed as possible means of renewable energy generation, may be valuable tools in understanding cyanobacterial electron transfer pathways, and enhanced understanding of electron transfer may allow improvements in the efficiency of power output. This article is part of a Special Issue entitled Organization and dynamics of bioenergetic systems in bacteria, edited by Conrad Mullineaux.We are grateful to the Environmental Services Association Education Trust, EnAlgae (European Regional Development Fund: INTERREG IVB NEW programme), and the Department of Biotechnology, India, for financial support.This is the author accepted manuscript. The final version is available from Elsevier via http://dx.doi.org/10.1016/j.bbabio.2015.10.00

A High Power-Density, Mediator-Free, Microfluidic Biophotovoltaic Device for Cyanobacterial Cells.

Biophotovoltaics has emerged as a promising technology for generating renewable energy because it relies on living organisms as inexpensive, self-repairing, and readily available catalysts to produce electricity from an abundant resource: sunlight. The efficiency of biophotovoltaic cells, however, has remained significantly lower than that achievable through synthetic materials. Here, a platform is devised to harness the large power densities afforded by miniaturized geometries. To this effect, a soft-lithography approach is developed for the fabrication of microfluidic biophotovoltaic devices that do not require membranes or mediators. Synechocystis sp. PCC 6803 cells are injected and allowed to settle on the anode, permitting the physical proximity between cells and electrode required for mediator-free operation. Power densities of above 100 mW m-2 are demonstrated for a chlorophyll concentration of 100 μM under white light, which is a high value for biophotovoltaic devices without extrinsic supply of additional energy.RCUK, OtherThis is the final version of the article. It first appeared from Wiley via http://dx.doi.org/10.1002/aenm.20140129

A Storable Mediatorless Electrochemical Biosensor for Herbicide Detection.

A novel mediatorless photo-bioelectrochemical sensor operated with a biofilm of the cyanobacterium Synechocystis PCC6803 wt. for herbicide detection with long term stability (>20 days) was successfully developed and tested. Photoanodic current generation was obtained in the absence of artificial mediators. The inhibitory effect on photocurrent of three commonly used herbicides (i.e., atrazine, diuron, and paraquat) was used as a means of measuring their concentrations in aqueous solution. The injection of atrazine and diuron into the algal medium caused an immediate photocurrent drop due to the inhibition of photosynthetic electron transport. The detected concentrations were suitable for environmental analysis, as revealed by a comparison with the freshwater quality benchmarks set by the Environmental Protection Agency of the United States (US EPA). In contrast, paraquat caused an initial increase (~2 h) of the photocurrent effect of about 200%, as this compound can act as a redox mediator between the cells and the anode. A relatively long-term stability of the biosensor was demonstrated, by keeping anodes colonized with cyanobacterial biofilm in the dark at 4 °C. After 22 days of storage, the performance in terms of the photocurrent was comparable with the freshly prepared biosensor. This result was confirmed by the measurement of chlorophyll content, which demonstrated preservation of the cyanobacterial biofilm. The capacity of this biosensor to recover after a cold season or other prolonged environmental stresses could be a key advantage in field applications, such as in water bodies and agriculture. This study is a step forward in the biotechnological development and implementation of storable mediatorless electrochemical biosensors for herbicide detection

Photoelectrochemistry of Photosystem II in Vitro vs in Vivo.

Factors governing the photoelectrochemical output of photosynthetic microorganisms are poorly understood, and energy loss may occur due to inefficient electron transfer (ET) processes. Here, we systematically compare the photoelectrochemistry of photosystem II (PSII) protein-films to cyanobacteria biofilms to derive: (i) the losses in light-to-charge conversion efficiencies, (ii) gains in photocatalytic longevity, and (iii) insights into the ET mechanism at the biofilm interface. This study was enabled by the use of hierarchically structured electrodes, which could be tailored for high/stable loadings of PSII core complexes and Synechocystis sp. PCC 6803 cells. The mediated photocurrent densities generated by the biofilm were 2 orders of magnitude lower than those of the protein-film. This was partly attributed to a lower photocatalyst loading as the rate of mediated electron extraction from PSII in vitro is only double that of PSII in vivo. On the other hand, the biofilm exhibited much greater longevity (>5 days) than the protein-film (<6 h), with turnover numbers surpassing those of the protein-film after 2 days. The mechanism of biofilm electrogenesis is suggested to involve an intracellular redox mediator, which is released during light irradiation

Exploiting algal NADPH oxidase for biophotovoltaic energy.

Photosynthetic microbes exhibit light-dependent electron export across the cell membrane, which can generate electricity in biological photovoltaic (BPV) devices. How electrons are exported remains to be determined; the identification of mechanisms would help selection or generation of photosynthetic microbes capable of enhanced electrical output. We show that plasma membrane NADPH oxidase activity is a significant component of light-dependent generation of electricity by the unicellular green alga Chlamydomonas reinhardtii. NADPH oxidases export electrons across the plasma membrane to form superoxide anion from oxygen. The C. reinhardtii mutant lacking the NADPH oxidase encoded by RBO1 is impaired in both extracellular superoxide anion production and current generation in a BPV device. Complementation with the wild-type gene restores both capacities, demonstrating the role of the enzyme in electron export. Monitoring light-dependent extracellular superoxide production with a colorimetric assay is shown to be an effective way of screening for electrogenic potential of candidate algal strains. The results show that algal NADPH oxidases are important for superoxide anion production and open avenues for optimizing the biological component of these devices.We acknowledge the UK EPSRC, EnAlgae (European Regional Development Fund: INTERREG IVB NEW programme) and the US Department of Energy for funding. I.K.B. was supported by a training grant from the National Institutes of Health (T32ES015457). Work in the Merchant laboratory was supported by the U.S. Department of Energy (grant no. DE–FC02– 02ER63421).This is the final published version. It first appeared from Wiley via http://dx.doi.org/10.1111/pbi.1233

The Development of Biophotovoltaic Systems for Power Generation and Biological Analysis.

Biophotovoltaic systems (BPVs) resemble microbial fuel cells, but utilise oxygenic photosynthetic microorganisms associated with an anode to generate an extracellular electrical current, which is stimulated by illumination. Study and exploitation of BPVs have come a long way over the last few decades, having benefited from several generations of electrode development and improvements in wiring schemes. Power densities of up to 0.5 W m-2 and the powering of small electrical devices such as a digital clock have been reported. Improvements in standardisation have meant that this biophotoelectrochemical phenomenon can be further exploited to address biological questions relating to the organisms. Here, we aim to provide both biologists and electrochemists with a review of the progress of BPV development with a focus on biological materials, electrode design and interfacial wiring considerations, and propose steps for driving the field forward

Electrical output of bryophyte microbial fuel cell systems is sufficient to power a radio or an environmental sensor.

Plant microbial fuel cells are a recently developed technology that exploits photosynthesis in vascular plants by harnessing solar energy and generating electrical power. In this study, the model moss species Physcomitrella patens, and other environmental samples of mosses, have been used to develop a non-vascular bryophyte microbial fuel cell (bryoMFC). A novel three-dimensional anodic matrix was successfully created and characterized and was further tested in a bryoMFC to determine the capacity of mosses to generate electrical power. The importance of anodophilic microorganisms in the bryoMFC was also determined. It was found that the non-sterile bryoMFCs operated with P. patens delivered over an order of magnitude higher peak power output (2.6 ± 0.6 µW m-2) than bryoMFCs kept in near-sterile conditions (0.2 ± 0.1 µW m-2). These results confirm the importance of the microbial populations for delivering electrons to the anode in a bryoMFC. When the bryoMFCs were operated with environmental samples of moss (non-sterile) the peak power output reached 6.7 ± 0.6 mW m-2. The bryoMFCs operated with environmental samples of moss were able to power a commercial radio receiver or an environmental sensor (LCD desktop weather station).The authors are grateful for funding provided by the UK Engineering and Physical Sciences Research Council (EPSRC) (P.B., A.G.S. and C.J. Howe), EnAlgae (http://www.enalgae.eu/, INTERREG IVB NWE) (P.B. and C.J. Howe), the Royal Society URF (C.J. Harrison), the Gatsby Charitable Foundation (Fellowship GAT2962) (C.J. Harrison), the Leverhulme Trust (P.B. and C.J. Howe), the Shuttleworth Foundation (P.B.) and the Department of Science and Technology and the National Research Foundation of South Africa through the South African Research Chair Initiative Chair in Bioprocess Engineering (UID 64778) (S.T.L.H. and D.M.R.I.).This is the final version of the article. It first appeared from the Royal Society Publishing via https://doi.org/10.1098/rsos.16024