Bidirectional Extracellular Electron Transfer Research Articles

Dual detection of biochemical oxygen demand and nitrate in water based on bidirectional Shewanella loihica electron transfer

This study for the first time proposed a method for simultaneously measuring BOD and nitrate in water using electrochemically active bacteria. Firstly, the bidirectional extracellular electron transfer (EET) capability of a model electricigen Shewanella loihica PV-4 was revealed. Then, based on the respective outward and inward EET, S. loihica PV-4 was utilized to detection BOD and nitrate. The results demonstrated a positive correlation between the outward EET and BOD (from 0 mg/L to 435 mg/L) while a negative correlation between the inward EET and nitrate (from 0 mg/L to 7 mg/L); both the relationships were well fitted by the combination of traditional linear model and Michaelis-Menten model (R2>0.96). Finally, a dual detection method for BOD and nitrate measurements was established based on the ano-cathodophilic capability of S. loihica PV-4 biofilm, and exhibited the characteristics of high accuracy (>80%) and fast analysis (<1h), suggesting a promising prospect in water monitoring.

Promoting bidirectional extracellular electron transfer of Shewanella oneidensis MR-1 for hexavalent chromium reduction via elevating intracellular cAMP level.

The bioreduction capacity of Cr(VI) by Shewanella is mainly governed by its bidirectional extracellular electron transfer (EET). However, the low bidirectional EET efficiency restricts its wider applications in remediation of the environments contaminated by Cr(VI). Cyclic adenosine 3',5'-monophosphate (cAMP) commonly exists in Shewanella strains and cAMP-cyclic adenosine 3',5'-monophosphate receptor protein (CRP) system regulates multiple bidirectional EET-related pathways. This inspires us to strengthen the bidirectional EET through elevating the intracellular cAMP level in Shewanella strains. In this study, an exogenous gene encoding adenylate cyclase from the soil bacterium Beggiatoa sp. PS is functionally expressed in Shewanella oneidensis MR-1 (the strain MR-1/pbPAC) and a MR-1 mutant lacking all endogenous adenylate cyclase encoding genes (the strain Δca/pbPAC). The engineered strains exhibit the enhanced bidirectional EET capacities in microbial electrochemical systems compared with their counterparts. Meanwhile, a three times more rapid reduction rate of Cr(VI) is achieved by the strain MR-1/pbPAC than the control in batch experiments. Furthermore, a higher Cr(VI) reduction efficiency is also achieved by the strain MR-1/pbPAC in the Cr(VI)-reducing biocathode experiments. Such a bidirectional enhancement is attributed to the improved production of cAMP-CRP complex, which upregulates the expression levels of the genes encoding the c-type cytochromes and flavins synthetic pathways. Specially, this strategy could be used as a broad-spectrum approach for the other Shewanella strains. Our results demonstrate that elevating the intracellular cAMP levels could be an efficient strategy to enhance the bidirectional EET of Shewanella strains and improve their pollutant transformation capacity.

Promoting Shewanella Bidirectional Extracellular Electron Transfer for Bioelectrocatalysis by Electropolymerized Riboflavin Interface on Carbon Electrode.

The extracellular electron transfer (EET) that connects the intracellular metabolism of electroactive microorganisms to external electron donors/acceptors, is the foundation to develop diverse microbial electrochemical technologies. For a particular microbial electrochemical device, the surface chemical property of an employed electrode material plays a crucial role in the EET process owing to the direct and intimate biotic-abiotic interaction. The functional modification of an electrode surface with redox mediators has been proposed as an effectual approach to promote EET, but the underlying mechanism remains unclear. In this work, we investigated the enhancement of electrochemically polymerized riboflavin interface on the bidirectional EET of Shewanella putrefaciens CN32 for boosting bioelectrocatalytic ability. An optimal polyriboflavin functionalized carbon cloth electrode achieved about 4.3-fold output power density (∼707 mW/m2) in microbial fuel cells and 3.7-fold cathodic current density (∼0.78 A/m2) for fumarate reduction in three-electrode cells compared to the control, showing great increases in both outward and inward EET rates. Likewise, the improvement was observed for polyriboflavin-functionalized graphene electrodes. Through comparison between wild-type strain and outer-membrane cytochrome (MtrC/UndA) mutant, the significant improvements were suggested to be attributed to the fast interfacial electron exchange between the polyriboflavin interface with flexible electrochemical activity and good biocompatibility and the outer-membrane cytochromes of the Shewanella strain. This work not only provides an effective approach to boost microbial electrocatalysis for energy conversion, but also offers a new demonstration of broadening the applications of riboflavin-functionalized interface since the widespread contribution of riboflavin in various microbial EET pathways together with the facile electropolymerization approach.

Anodic and Cathodic Extracellular Electron Transfer by the Filamentous Bacterium Ardenticatena maritima 110S.

Ardenticatena maritima strain 110S is a filamentous bacterium isolated from an iron-rich coastal hydrothermal field, and it is a unique isolate capable of dissimilatory iron or nitrate reduction among the members of the bacterial phylum Chloroflexi. Here, we report the ability of A. maritima strain 110S to utilize electrodes as a sole electron acceptor and donor when coupled with the oxidation of organic compounds and nitrate reduction, respectively. In addition, multicellular filaments with hundreds of cells arranged end-to-end increased the extracellular electron transfer (EET) ability to electrodes by organizing filaments into bundled structures, with the aid of microbially reduced iron oxide minerals on the cell surface of strain 110S. Based on these findings, together with the attempt to detect surface-localized cytochromes in the genome sequence and the demonstration of redox-dependent staining and immunostaining of the cell surface, we propose a model of bidirectional electron transport by A. maritima strain 110S, in which surface-localized multiheme cytochromes and surface-associated iron minerals serve as a conduit of bidirectional EET in multicellular filaments.

Combined spectroelectrochemical and proteomic characterizations of bidirectional Alcaligenes faecalis-electrode electron transfer

Bioelectrochemical systems use microbes as catalysts for current production or consumption. Up to now only a few microbes have been demonstrated to be capable of both outward and inward extracellular electron transfer (EET) (i.e. bidirectional electron transfer). However, the mechanisms of electron exchange between microbes and extracellular solids remain uncertain. Here, we showed that Alcaligenes faecalis catalyzed an outward EET and generated electricity at a poised potential of +0.3V vs. SHE, whereas it conducted an inward EET for autotrophic denitrification at −0.5V vs. SHE. Both cyclic voltammetry and in situ electrochemical FTIR spectroscopy revealed that different redox components were utilized during the outward and inward EET. Electron transport inhibitor experiments indicated for the first time that complex I, II, III, and the quinone pool on the plasma membrane were involved in the bidirectional EET. Comparative proteomics showed that the protein expression profile of outward-EET biofilms differed greatly from those of inward-EET biofilms, implying that the pili and outer membrane proteins might be responsible for the interfacial outward and inward EET, respectively. These results suggest different electron transport conduits of A. faecalis biofilms could be used for bidirectional EET.

Analysis of electrode microbial communities in an up-flow bioelectrochemical system treating azo dye wastewater

Bioelectrochemical system (BES) is a rapidly developing technology covering contamination remediation, resource recovery and power generation. Electrode biofilms play a key role in BES operation. In this work, a single chamber up-flow bioelectrochemical system (UBES) was assembled with two preinoculated anodes and two raw cathodes for azo dye wastewater treatment. Microbial community structures of these electrodes after long-term operation (more than 200 days) were carried out by high-throughput Illumina 16S rRNA gene MiSeq sequencing platform. Microorganisms belonging to Enterobacter, Desulfovibrio and Enterococcus, which are capable of bidirectional extracellular electron transfer, were found to be the dominant members in all biofilms. Neither the polarity nor the position of the electrodes obviously altered the microbial community structures. This study provides a feasible strategy to build electrode active biofilms in a BES for azo dye wastewater treatment and gives great inspirations to bring this technology closer to application.

Nanotechnology to rescue bacterial bidirectional extracellular electron transfer in bioelectrochemical systems

Advanced nanostructured electrode materials largely improve the bacterial bidirectional extracellular electron transfer in bioelectrochemical systems.

Adjustable bidirectional extracellular electron transfer between Comamonas testosteroni biofilms and electrode via distinct electron mediators

Abstract Bidirectional extracellular electron transfer of strain Comamonas testosteroni I2 was for the first time investigated with electrochemical active biofilms developed under different conditions. The electrochemical active biofilm developed under microbial fuel cell conditions was capable of anodic electron transfer via attached redox species with standard potential of 0.04 V (vs. SCE). Meanwhile the above redox species lost its catalytic capability when the biofilm was developed under a constant potential (− 0.4 V vs. SCE). Instead, the microbe adjusted its electron transfer strategy to a soluble shuttle (standard potential − 0.20 V vs. SCE) and enabled a cathodic current. Air exposure experiment verified that the soluble shuttle at negative potential had a positive response to the oxygen; meanwhile the anodic electron transfer via the attached species was rarely influenced.

Enhancing Bidirectional Electron Transfer of Shewanella oneidensis by a Synthetic Flavin Pathway.

Flavins regulate the rate and direction of extracellular electron transfer (EET) in Shewanella oneidensis. However, low concentration of endogenously secreted flavins by the wild-type S. oneidensis MR-1 limits its EET efficiency in bioelectrochemical systems (BES). Herein, a synthetic flavin biosynthesis pathway from Bacillus subtilis was heterologously expressed in S. oneidensis MR-1, resulting in ∼25.7 times' increase in secreted flavin concentration. This synthetic flavin module enabled enhanced bidirectional EET rate of MR-1, in which its maximum power output in microbial fuel cells increased ∼13.2 times (from 16.4 to 233.0 mW/m(2)), and the inward current increased ∼15.5 times (from 15.5 to 255.3 μA/cm(2)).