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Typha angustifolia L. (TA) pollen has been utilized as a traditional Chinese medicine for treating various internal and external traumas. Moreover, bioactive compounds possess diverse pharmacological activities. This study aims to evaluate the antiviral properties of TA based on its ability to generate bioenergy, capable of inhibiting viruses. TA pollens were extracted using water and ethanol solvents. These extracts were utilized to identify the phytochemical contents and correlate with the antioxidant activity via 2,2-diphenyl-1-picrylhydrazyl (DPPH) and ferric reducing antioxidant power (FRAP) assays. HPLC analysis was conducted to identify its electron-shuttling compositions. The bioenergy-generating characteristics were determined via microbial fuel cells. The water extract (TA-W) showed higher antioxidant activity due to a higher phenolic and flavonoid content compared to the ethanol extract (TA-E). Quercetin-3- O -(2 G -α-L-rhamnosyl)-rutinoside, quercetin-3- O -neohesperidoside, and quercetin are the electron shuttles (ES) identified out of the 11 compounds. TA obtained a 1.39 ± 0.10 amplification factor of power generation that indicates potential bioenergy-generating and associated antiviral characteristic properties. The findings may provide a foundation for developing antiviral medications specifically designed to target virus-related diseases, while minimizing the risk of drug toxicity and reducing the costs of drug development.

The synchronous bioelectricity generation and dissimilatory nitrate reduction to ammonium (DNRA) pathway in Klebsiella variicola C1 was investigated. The presence of bioelectricity facilitated cell growth on the anodic biofilms, consequently enhancing the nitrate removal efficiency decreasing total nitrogen levels and causing a negligible accumulation of NO 2 in the supernatant. Genomic analysis revealed that K. variicola C1 possessed a complete DNRA pathway and largely annotated electron shuttles. The up-regulated expression of genes narG and nirB, encoding nitrite oxidoreductase and nitrite reductase respectively, was closely associated with increased extracellular electron transfer (EET). High-throughput sequencing analysis was employed to investigate the impact of bioelectricity on microbial community composition within cathodic biofilms. Results indicated that Halomonas, Marinobacter and Prolixibacteraceae were enriched at the cathode electrodes. In conclusion, the integration of a DNRA strain with MFC facilitated the efficient removal of wastewater containing high concentrations of NO - in the supernatant. Genomic analysis revealed that K. variicola C1 possessed a complete DNRA pathway and largely annotated electron shuttles. The up-regulated expression of genes narG and nirB, encoding nitrite oxidoreductase and nitrite reductase respectively, was closely associated with increased extracellular electron transfer (EET). High-throughput sequencing analysis was employed to investigate the impact of bioelectricity on microbial community composition within cathodic biofilms. Results indicated that Halomonas, Marinobacter and Prolixibacteraceae were enriched at the cathode electrodes. In conclusion, the integration of a DNRA strain with MFC facilitated the efficient removal of wastewater containing high concentrations of NO 3 - and enabled the environmentally friendly recovery of NH 4 + ., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Medium-chain fatty acids (MCFAs) production from sewage sludge is mainly restricted by the complex substrate structure, competitive metabolism and low electron transfer rate. This study proposes a novel permanganate (PM)-based strategy to promote sludge degradation and MCFAs production. Results show that PM pretreatment significantly increases MCFAs production, i.e., attaining 12,036 mg COD/L, and decreases the carbon fluxes of electron acceptor (EA)/electron donor (ED) to byproducts. Further analysis reveals that PM oxidation enhances the release and biochemical conversion of organic components via disrupting extracellular polymers (EPS) structure and reducing viable cells ratio, providing directly available EA for chain elongation (CE). The microbial activity positively correlated with MCFAs generation are apparently heightened, while the competitive metabolism of CE (i.e., methanogensis) can be completely inhibited. Accordingly, the functional bacteria related to critical bio-steps and dissimilatory manganese reduction are largely enriched. Further mechanism exploration indicates that the main contributors for sludge solubilization are 1 O 2 (61.6 %) and reactive manganese species (RMnS), i.e., Mn(V)/Mn(VI) (22.3 %) and Mn(III) (∼16.1 %). As the main reducing product of PM reaction, manganese dioxide (MnO 2 ) can enable the formation of microbial aggregates, and serve as electron shuttles to facilitate the carbon fluxes to MCFAs during CE process. Overall, this strategy can achieve simultaneous hydrogen recovery, weaken competitive metabolisms and provide electron transfer accelerator for CE reactions., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Three decades ago, dye-sensitized solar cells (DSSCs) emerged as a route for harnessing the sun's energy and converting it into electricity. Since then, an impressive amount of work has been devoted to improving the global photovoltaic efficiency of DSSCs, trying to optimize all components of the device. Up to now, the best efficiencies have usually been reached with ruthenium(II) photosensitizers, even if in the last few years many classes of organic compounds have shown record efficiencies. However, the future of DSSCs is stringently connected to the research and development of cheaper materials; in particular, the replacement of rare metals with abundant ones is an important topic in view of the long-term sustainability of DSSCs intended to replace the consolidated fossil-based technology. In this context, copper is a valid candidate, being both an alternative to ruthenium in the fabrication of photosensitizers and a material able to replace the common triiodide/iodide redox couple. Thus, recently, some research papers have confirmed the great potential of copper(I) coordination complexes as a cheap and convenient alternative to ruthenium dyes. Similarly, the use of copper compounds as electron transfer mediators for DSSCs can be an excellent way to solve the problems related to the more common I 3 - redox couple. The goal of this mini-review is to report on the latest research devoted to the use of versatile copper complexes as photosensitizers and electron shuttles in DSSCs. The coverage, from 2022 up to now, illustrates the most recent studies on dye-sensitized solar cells based on copper complexes as molecular materials.- redox couple. The goal of this mini-review is to report on the latest research devoted to the use of versatile copper complexes as photosensitizers and electron shuttles in DSSCs. The coverage, from 2022 up to now, illustrates the most recent studies on dye-sensitized solar cells based on copper complexes as molecular materials.

Electron shuttles (ESs) and Fe-bearing clay minerals are commonly found in subsurface environments and have shown potential in enhancing the bioreduction of Cr(VI). However, the synergistic effect of ESs at different redox potentials and Fe-bearing clay minerals on Cr(VI) bioreduction, as well as the fundamental principles governing this process, remain unclear. In our study, we investigated the role of ESs and Fe(III) in Cr(VI) bioreduction. We found that the acceleration of ESs and Fe(III) are crucial factors in this process. Interestingly, the promotion of ESs on Cr(VI) and Fe(III) showed opposite trends. Electrochemical methods confirmed the limited steps are the extent of reduced ESs and the redox potential difference between ESs and Fe(III), separately. Furthermore, we investigated the combined effect of ESs and NAu-2 on Cr(VI) bioreduction. Our results revealed two segments: in the first segment, the ES (5-HNQ) and NAu-2 did not synergistically enhance Cr(VI) reduction. However, in the second segment, ESs and NAu-2 demonstrated a synergistic effect, significantly increasing Cr(VI) reduction by MR-1. These bioreduction processes all follow linear free energy relationships (LFERs). Overall, our study highlights the fundamental principles governing multivariate systems and presents a promising approach for the remediation of Cr(VI)-contaminated sites., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

For low yield in dark fermentation (DF), in this study, the carbonized humic acid (CHA) was produced and added to DF for enhancing biohydrogen (bioH 2 ) yield at mesophilic condition. The highest bioH 2 yield was 151.08 mL/g glucose with the addition of CHA at 80 mg/L, which was 35.27% and 16.53% higher than those of 0 mg/L CHA and 80 mg/L mineral humic acid (MHA) groups, respectively. Electrons preferentially conducted via the butyrate pathway due to CHA amendments, which corresponded to the prediction of relevant functional genes. Furthermore, CHA possessed distinctive advantages over MHA, which acted as an electron shuttle to facilitate electron transfer, released metal ions as an essential signal mediator and favored the reduction of ferredoxin, obtaining more H 2 . The use of CHA in the field of H 2 -DF depicted the high-value utilization and industrial chain extension of MHA., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Extracellular electron transfer (EET) is the physiological process that enables the reduction or oxidation of molecules and minerals beyond the surface of a microbial cell. The first bacteria characterized with this capability were Shewanella and Geobacter , both reported to couple their growth to the reduction of iron or manganese oxide minerals located extracellularly. A key difference between EET and nearly every other respiratory activity on Earth is the need to transfer electrons beyond the cell membrane. The past decade has resolved how well-conserved strategies conduct electrons from the inner membrane to the outer surface. However, recent data suggest a much wider and less well understood collection of mechanisms enabling electron transfer to distant acceptors. This review reflects the current state of knowledge from Shewanella and Geobacter , specifically focusing on transfer across the outer membrane and beyond-an activity that enables reduction of highly variable minerals, electrodes, and even other organisms.

The interfacial electron transfer (ET) between electron shuttling compounds and iron (Fe) oxyhydroxides plays a crucial role in the reductive dissolution of Fe minerals and the fate of surface-bound arsenic (As). However, the impact of exposed facets of highly crystalline hematite on reductive dissolution and As immobilization is poorly understood. In this study, we systematically investigated the interfacial processes of the electron shuttling compound cysteine (Cys) on various facets of hematite and the reallocations of surface-bound As(III) or As(V) on the respective surfaces. Our results demonstrate that the ET process between Cys and hematite generates Fe(II) and leads to reductive dissolution, with more Fe(II) generated on {001} facets of exposed hematite nanoplates (HNPs). Reductive dissolution of hematite leads to significantly enhanced As(V) reallocations on hematite. Nevertheless, upon the addition of Cys, a raipd release of As(III) can be halted by its prompt re-adsorption, leaving the extent of As(III) immobilization on hematite unchanged throughout the course of reductive dissolution. This is due to that Fe(II) can form new precipitates with As(V), a process that is facet-dependent and influenced by water chemistry. Electrochemical analysis reveals that HNPs exhibit higher conductivity and ET ability, which is beneficial for reductive dissolution and As reallocations on hematite. These findings highlight the facet-dependent reallocations of As(III) and As(V) facilitated by electron shuttling compounds and have implications for the biogeochemical processes of As in soil and subsurface environments., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

Background: Jing Guan Fang (JGF) is an anti-COVID-19 Chinese Medicine decoction comprised of five medicinal herbs to possess anti-inflammatory and antiviral properties for treatment. This study aims to electrochemically decipher the anti-coronavirus activity of JGF and show that microbial fuel cells may serve as a platform for screening efficacious herbal medicines and providing scientific bases for the mechanism of action (MOA) of TCMs., Methods: Electrochemical techniques (e.g., cyclic voltammetry) and MFCs were adopted as the bioenergy-based platforms to assess the bioenergy-stimulating characteristics of JGF. Phytochemical analysis correlated polyphenolic and flavonoid content with antioxidant activity and bioenergy-stimulating properties. Network pharmacology on the active compounds was employed to identify anti-inflammatory and anti-COVID-19 protein targets, and molecular docking validated in silico results., Significant Findings: This first-attempt results show that JGF possesses significant reversible bioenergy-stimulation (amplification 2.02 ± 0.04) properties suggesting that its antiviral efficacy is both bioenergy-steered and electron mediated. Major flavonoids and flavone glycosides identified by HPLC (e.g., baicalein and baicalin, respectively) possess electron-shuttling (ES) characteristics that allow herbal medicines to treat COVID-19 via (1) reversible scavenging of ROS to lessen inflammation; (2) inhibition of viral proteins; and (3) targeting of immunomodulatory pathways to stimulate the immune response according to network pharmacology., Competing Interests: The authors declare no competing interests., (© 2023 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.)

Accelerating the rate-limiting Fe 3+ /Fe 2+ circulation in Fenton reactions through the addition of reducing agents (or co-catalysts) stands out as one of the most promising technologies for rapid water decontamination. However, conventional reducing agents such as hydroxylamine and metal sulfides are greatly restricted by three intractable challenges: (1) self-quenching effects, (2) heavy metal dissolution, and (3) irreversible capacity decline. To this end, we, for the first time, introduced redox-active polymers as electron shuttles to expedite the Fe 3+ /Fe 2+ cycle and promote H 2 O 2 activation. The reduction of Fe 3+ mainly took place at active N-H or O-H bonds through a proton-coupled electron transfer process. As electron carriers, H atoms at the solid phase could effectively inhibit radical quenching, avoid metal dissolution, and maintain long-term reducing capacity via facile regeneration. Experimental and density functional theory (DFT) calculation results indicated that the activity of different polymers shows a volcano curve trend as a function of the energy barrier, highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap, and vertical ionization potential. Thanks to the appropriate redox ability, polyaniline outperforms other redox-active polymers (e.g., poypyrrole, hydroquinone resin, poly(2,6-diaminopyridine), and hexaazatrinaphthalene framework) with a highest iron reduction capacity up to 5.5 mmol/g, which corresponds to the state transformation from leucoemeraldine to emeraldine. Moreover, the proposed system exhibited high pollutant removal efficiency in a flow-through reactor for 8000 bed volumes without an obvious decline in performance. Overall, this work established a green and sustainable oxidation system, which offers great potential for practical organic wastewater remediation.

The coexistence of multiple pollutants and lack of carbon sources are challenges for the biological treatment of wastewater. To achieve simultaneous removal of nitrate (NO 3 - -N) and cadmium (Cd 2+ ) at low carbon to nitrogen (C/N) ratios, 2-hydroxy-1,4-naphthoquinone (HNQ) was selected from three redox mediators as an accelerator for denitrification of heterotrophic strain Pseudomonas stutzeri sp. GF2 and autotrophic strain Zoogloea sp. FY6. Then, halloysite nanotubes immobilized with 2-hydroxy-1,4-naphthoquinone (HNTs-HNQ) were prepared and a bioreactor was constructed with immobilized redox mediator granules (IRMG) as the carrier, which was immobilized with HNTs-HNQ and inoculated with the two strains. The immobilized HNQ and the inoculated strains jointly improved the removal ability of NO 3 - -N and Cd 2+ and the removal efficiency of NO 3 - -N (25.0 mg L -1 ) and Cd 2+ (5.0 mg L -1 ) were 92.81% and 93.94% at C/N = 1.5 and hydraulic retention time (HRT) = 4 h. The Cd 2+ was removed by adsorption of iron oxides (FeO(OH) and Fe 3 O 4 ) and IRMG. The electron transport system activity (ETSA) of bacteria was improved and the composition of dissolved organic matter in the effluent was not affected by HNQ. The HNQ promoted the production of FeO(OH) and up-regulated the proportion of Zoogloea (54.75% in the microbial community), indicating that Zoogloea sp. FY6 was dominant in the microbial community. In addition, HNQ influenced the metabolic pathways and improved the relative abundance of some genes involved in nitrogen metabolism and the iron redox cycle., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Excess sludge (ES) largely produced in municipal wastewater treatment plants is known as a waste biomass and the traditional treatment processes such as landfill and incineration are considered as unsustainable due to the negative environmental impact. Fermentation process of ES for the biorefinery of zero-carbon hydrogen has attracted an increasing interesting and was extensively researched in the last decades. However, the technology is far from commercial application due to the insufficient effectivity. In the present study, anthraquinone-2-sulfonate (AQS) as electron shuttles was introduced into the fermentation process of ES for mediating the composition and activity of bacterial community to get an enhanced biohydrogen production. Inoculated with the same anaerobic activated sludge of 1.12 gVSS/L, a series of batch anaerobic fermentation systems with various dosage of AQS were conducted at the same ES load of 2.75 gVSS/L, initial pH 6.5 and 35 °C. The results showed that the fermentation process was remarkably enhanced by the introduction of 100 mg/L AQS, accompanying the lag phase was shortened to 1.35 h from 7.62. The obtained biohydrogen yield and the specific biohydrogen production rate were also remarkably enhanced to 24.9 mL/gVSS and 0.3 mL/(gVSS·h), respectively. Illumina Miseq sequencing showed that Longilinea and Guggenheimella as the dominant genera had been enriched from 9.2% to 0-12.0% and 4.7%, respectively, in the presence of 100 mg/L AQS. Function predicted analysis suggested that the presence of AQS had increased the abundance of genes involved in the transport and metabolism of carbohydrate, amino acid and energy production. Further redundancy analysis (RDA) revealed that the enhanced hydrogen production was highly positively correlated with the enrichment of genera such as Longilinea and Guggenheimella. The research work presents a novel potential biorefinery of ES for the effective production of zero-carbon hydrogen., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Bioreduction by electroactive bacteria (EAB) is considered as a potential and cost-effective approach for the removal of nitroaromatic compounds (NACs). However, little is known about how the widespread EAB sense and respond to slightly soluble NACs in aquatic environments. Here, the chemotactic behaviors of Shewanella oneidensis MR-1, a model EAB, toward several NACs were examined and their underlying molecular mechanism was elucidated. S. oneidensis MR-1 was found to exhibit a strong chemotactic response to nitrobenzene (NB), but not to other selected NACs under aerobic conditions. To sense NB, this bacterium requires both the histidine kinase (CheA-3)-involved chemotactic signal transduction pathway and an inner-membrane c-type cytochrome CymA. Such a chemotactic response is mediated by an energy taxis mechanism. Additionally, external riboflavin was shown to greatly enhance the Shewanella taxis toward NB, implying a feasible way to increase the bioavailability of NACs. The present study deepens our understanding of the role of microbial chemotaxis in the removal of NACs and provides more options for the bioremediation of NAC-contaminated sites., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Resistant bacteria are potential natural materials for the bioremediation of soil metalloid pollution. A strain isolated from farmland soil chronically exposed to Sb was identified as K. aerogenes X with high antimonite [Sb(III)] tolerance and oxidation ability. The resistance mechanism of K. aerogenes X and its extracellular polymeric substances (EPS), antioxidant enzymes, and oxidation characteristics in Sb(III) stress were investigated in this study by stress incubation experiments and FTIR. The biotoxicity of Sb was limited by the binding of the organic compounds in EPS, and the anionic functional groups (e.g., amino, carboxyl and hydroxyl groups, etc.) present in the cell envelope were the components primarily responsible for the metalloid-binding capability of K. aerogenes X. The K. aerogenes X can oxidize Sb(III), and its metabolites induce changes in reactive oxygen species (ROS), catalase (CAT), total superoxide dismutase (SOD) and glutathione s-transferase (GSH-S) activity, indicating that the resistance mechanisms of K. aerogenes X are mediated by oxidative stress, EPS restriction and cell damage. Oxidation of Sb(III) is driven by interactions in intracellular oxidation, cell electron transport, extracellular metabolism including proteins and low molecular weight components (LMWs). LMWs (molecular weight <3 kDa) are the main driving factor of Sb(III) oxidation. In addition, Sb resistance genes arsA, arsB, arsC, arsD and acr3 and potential oxidation gene arsH were identified in K. aerogenes X. Owing to its natural origin, high tolerance and oxidation ability, K. aerogenes X could serve as a potential bioremediation material for the mitigation of Sb(III) in contaminated areas., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

To this day, bioelectrochemical systems are still perceived as one of the rising technologies due to their versatile applications in electricity production, bioremediation, biosensors, and production of value-added products. While the majority of bioelectrochemical applications utilize Gram-negative bacteria, Gram-positive bacteria has not received sufficient attention. The lack of adequate knowledge about their electron transfer pathways along with the presence of a thick non-conductive cell wall are among the reasons behind their limited use. In this review, the electroactivity of Gram-positive bacteria will be covered describing the different pathways of electron transfer among different electroactive Gram-positive strains. Special emphasis will be given to the role of multiheme cytochromes, quorum sensing molecules, peptide-based signalling, and pili in the extracellular electron transfer. This review will also provide an overview of possible approaches for enhancement strategies of electron transfer such as enhancing biofilm formation, biocomposites and cell perforation. Understanding the fundamentals is critical for improving the use of Gram-positive bacteria in bioelectrochemical systems and may lead to the discovery of new applications., (© 2022. The Author(s), under exclusive licence to Springer Nature B.V.)

Pyrolytic carbon materials (PCMs) with various surface functionalities are widely used as environmentally friendly and cost-efficient adsorbents for the removal of organic and inorganic pollutants. Recent studies have illustrated that PCMs as electron shuttles (ESs) could also show excellent performances in promoting the anaerobic transformation of recalcitrant organic pollutants (ROPs). Numerous studies have demonstrated the excellent electron-shuttle capability (ESC) of PCMs to stimulate the anaerobic reductive transformation of ROPs. However, there is a lack of consistent understanding of the mechanism of ESC formation in PCMs and the stimulation mechanism for ROPs anaerobic transformation. To gain a more comprehensive understanding of the latest developments in the study of PCMs as ESs for ROPs anaerobic transformation, this review summarizes the formation mechanism, influencing factors, and stimulation mechanisms of ESC. ESC benefits from redox functional groups (quinone and phenol groups), persistent free radicals (PFRs), redox-active metal ions, conductive graphene phase, and porous nature of their surface. The factors influencing ESC include the highest treatment temperature (HTT), feedstocks, modification methods, and environmental conditions, of which, the HTT is the key factor. PCMs promote the reductive transformation of ROPs under anaerobic conditions via abiotic and biotic pathways. Eventually, the prospects for the ROPs anaerobic transformation enhanced by PCMs are proposed., Competing Interests: Declaration of competing interest We declare there are no known conflicting interests regarding the publication of this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Electroactive microorganisms (EAMs) are ubiquitous in nature and have attracted considerable attention as they can be used for energy recovery and environmental remediation via their extracellular electron transfer (EET) capabilities. Although the EET mechanisms of Shewanella and Geobacter have been rigorously investigated and are well characterized, much less is known about the EET mechanisms of other microorganisms. For EAMs, efficient EET is crucial for the sustainable economic development of bioelectrochemical systems (BESs). Currently, the low efficiency of EET remains a key factor in limiting the development of BESs. In this review, we focus on the EET mechanisms of different microorganisms, (i.e., bacteria, fungi, and archaea). In addition, we describe in detail three engineering strategies for improving the EET ability of EAMs: (1) enhancing transmembrane electron transport via cytochrome protein channels; (2) accelerating electron transport via electron shuttle synthesis and transmission; and (3) promoting the microbe-electrode interface reaction via regulating biofilm formation. At the end of this review, we look to the future, with an emphasis on the cross-disciplinary integration of systems biology and synthetic biology to build high-performance EAM systems., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Members of the genus Aeromonas prevail in aquatic habitats and have a great potential in biological wastewater treatment because of their unique extracellular electron transfer (EET) capabilities. However, the mediated EET mechanisms of Aeromonas have not been fully understood yet, hindering their applications in biological wastewater treatment processes. In this study, the electron shuttles in Aeromonas hydrophila, a model and widespread strain in aquatic environments and wastewater treatment plants, were explored. A. hydrophila was found to produce both flavins and 2-amino-3-carboxy-1,4-naphthoquinone (ACNQ) as electron shuttles and utilize them to accelerate its EET for the bioreduction of various pollutants. The Mtr-like respiratory pathway was essential for the reduction of flavins, but not involved in the ACNQ reduction. The electron shuttle activity of ACNQ for pollutant bioreduction involved the redox reactions that occurred inside the cell. These findings deepen our understanding about the underlying EET mechanisms in dissimilatory metal reducing bacteria and provide new insights into the roles of the genus Aeromonas in biological wastewater treatment., (© 2021 Wiley Periodicals LLC.)

Bioelectrochemical systems (BESs) are emerging as attractive routes for sustainable energy generation, environmental remediation, bio-based chemical production and beyond. Electron shuttles (ESs) can be reversibly oxidized and reduced among multiple redox reactions, thereby assisting extracellular electron transfer (EET) process in BESs. Here, we explored the effects of 14 ESs on EET in Shewanella oneidensis MR-1, and found that anthraquinone-2-sulfonate (AQS) led to the highest cathodic current density, total charge production and reduction product formation. Subsequently, we showed that the introduction of -OH or -NH 2 group into AQS at position one obviously affected redox potentials. The AQS-1-NH 2 exhibited a lower redox potential and a higher Coulombic efficiency compared to AQS, revealing that the ESs with a more negative potential are conducive to minimize energy losses and improve the reduction of electron acceptor. Additionally, the cytochromes MtrA and MtrB were required for optimal AQS-mediated EET of S. oneidensis MR-1. This study will provide new clues for rational design of efficient ESs in microbial electrosynthesis., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Xu, Wang, Li, Wang, Chen and Liu.)

For renewable and sustainable bioenergy utilization with cost-effectiveness, electron-shuttles (ESs) (or redox mediators (RMs)) act as electrochemical "catalysts" to enhance rates of redox reactions, catalytically accelerating electron transport efficiency for abiotic and biotic electrochemical reactions. ESs are popularly used in cellular respiratory systems, metabolisms in organisms, and widely applied to support global lives. Apparently, they are applicable to increase power-generating capabilities for energy utilization and/or fuel storage (i.e., dye-sensitized solar cell, batteries, and microbial fuel cells (MFCs)). This first-attempt review specifically deciphers the chemical structure association with characteristics of ESs, and discloses redox-mediating potentials of polyphenolics-abundant ESs via MFC modules. Moreover, to effectively convert electron-shuttling capabilities from non-sustainable antioxidant activities, environmental conditions to induce electrochemical mediation apparently play critical roles of great significance for bioenergy stimulation. For example, pH levels would significantly affect electrochemical potentials to be exhibited (e.g., alkaline pHs are electrochemically favorable for expression of such electron-shuttling characteristics). Regarding chemical structure effect, chemicals with ortho - and para -dihydroxyl substituents-bearing aromatics own convertible characteristics of non-renewable antioxidants and electrochemically catalytic ESs; however, ES capabilities of meta -dihydroxyl substituents can be evidently repressed due to lack of resonance effect in the structure for intermediate radical(s) during redox reaction. Moreover, this review provides conclusive remarks to elucidate the promising feasibility to identify whether such characteristics are non-renewable antioxidants or reversible ESs from natural polyphenols via cyclic voltammetry and MFC evaluation. Evidently, considering sustainable development, such electrochemically convertible polyphenolic species in plant extracts can be reversibly expressed for bioenergy-stimulating capabilities in MFCs under electrochemically favorable conditions., Competing Interests: Competing interestsThe authors declare that they have no competing interests., (© The Author(s) 2019.)

A novel Shewanella@graphene core-shell composite material was fabricated following one-step bioreduction of graphene oxide (GO) by Shewanella putrefaciens CN-32. The surface properties and microstructures were characterized by FTIR, TG-DTG, SEM and TEM, which indicate that GO was effectively reduced to rGO and subsequently loaded onto the outer surface of the microbe Shewanella. CLSM was performed to get insight into the growth of the bacteria after core-shell materials formation. The reduction properties of Shewanella@graphene materials were evaluated using nitrobenzene, a representative model pollutant, as an electron acceptor. The reduction efficiency of Shewanella was improved by strengthening the contact among electron donors, electron shuttles and electron acceptors and changed with the proportions of core-shell materials. The optimal proportion of the core-shell material was OD600 = 0.6:GO = 10 mg/L, which was enhanced by the wrapped rGO and improved adsorption capability. The reduction rate was elevated 30% in comparison with pure Shewanella. In addition, the core-shell material exhibited a favorable recycling performance, which can be reused for at least five times. Facile fabrication and enhanced reduction performance of Shewanella@graphene core-shell composite endows this material with considerable potential in environmental remediation., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Magnetite nanoparticles (nanoFe 3 O 4 ) have been reported to facilitate direct interspecies electron transfer (DIET) between syntrophic bacteria and methanogens thereby improving syntrophic methanogenesis. However, whether or how nanoFe 3 O 4 affects acetotrophic methanogenesis remain unknown. Herein, we demonstrate the unique role of nanoFe 3 O 4 in accelerating methane production from direct acetotrophic methanogenesis in Methanosarcina -enriched cultures, which was further confirmed by pure cultures of Methanosarcina barkeri. Compared with other nanomaterials of higher electrical conductivity such as carbon nanotubes and graphite, nanoFe 3 O 4 with mixed valence Fe(II) and Fe(III) had the most significant stimulatory effect on methane production, suggesting its redox activity rather than electrical conductivity led to enhanced methanogenesis by M. barkeri . Cell morphology and spectroscopy analysis revealed that nanoFe 3 O 4 penetrated into the cell membrane and cytoplasm of M. barkeri . These results provide the unprecedented possibility that nanoFe 3 O 4 in the cell membrane of methanogens serve as electron shuttles to facilitate intracellular electron transfer and thus enhance methane production. This work has important implications not only for understanding the mechanisms of mineral-methanogen interaction but also for optimizing engineered methanogenic processes.

Anaerobes respire extracellular electron acceptors by extracellular electron transfer (EET). It is widely recognized that flavins can act as electron shuttles to facilitate this process. Flavin synthesis genes are widely distributed in Geobacter species. However, the functions of flavins in the EET of Geobacter species are unclear. Here, we demonstrate that G. uraniireducens can secrete abundant riboflavin (up to 270 nM) to facilitate EET. When an electrode was used as the electron acceptor, the quick recovery of anodizing current after anolyte replacement and the electrochemical behavior of the G. uraniireducens biofilm characterized by differential pulse voltammetry suggest that the self-secreted riboflavin promoted EET by serving as bound redox cofactors for cytochromes. On the contrary, when Fe(III) oxide was the electron acceptor, free riboflavin acted as electron shuttle to mediate the reduction of Fe(III) oxide. The results demonstrate the flexibility of flavins in EET, suggesting that the properties of electron acceptors can affect the binding mode of extracellular flavins, and broaden the knowledge of the EET of Geobacter species.

Conductive materials facilitate direct interspecies electron transfer between acidogens and methanogens during methane (CH 4 ) production. Soluble microbial products (SMP) and extracellular polymeric substances (EPS) produced by microorganisms might act as the electron shuttle between microorganisms and conductive materials. In this study, effects of conductive ferroferric oxide (Fe 3 O 4 ) on anaerobic treatment process and the production of SMP and EPS were investigated. The maximum CH 4 production rate was enhanced by 23.3% with the dosage of Fe 3 O 4 . The concentrations of proteins, polysaccharides, and humic substances in tightly bound EPS (T-EPS) were promoted, suggesting that extracellular metabolisms were induced by conductive materials. Distribution of potential electron shuttles such as quinone-like substances, flavins, aromatic amino acids, and dipeptides in SMP and EPS phases were comprehensively investigated and these electron shuttles were significantly affected by Fe 3 O 4 . Dipeptides consisting of phenylalanine were widely detected in T-EPS of the Fe 3 O 4 reactor, indicating a potential different extracellular electron exchange pattern with the addition of conductive materials.

The ability of anthraquinone-2,6-disulfonate (AQDS) and riboflavin to enhance the sulfamethoxazole (SMX) degradation coupled with the Fe(III) reduction by Shewanella oneidensis MR-1 was investigated. The results indicated that the SMX degradation rate was 38.5% with an initial SMX concentration at 0.04 mM. For the overall performance of AQDS and riboflavin mediated SMX degradation and iron reduction, the SMX degradation rate was gradually increased with the enhancement of iron reduction. Riboflavin had a stronger enhancement on SMX degradation and iron reduction than AQDS, but the enhancement was not positively correlated with electron shuttles concentration. A quantitative characterization of the electron transfer capacity (ETC) of the electron shuttles showed that the ETC was higher for riboflavin than AQDS. The S. oneidensis MR-1 16S rRNA gene copies results indicated that electron shuttles had a positive effect on the microbial activity of S. oneidensis MR-1. The LCMS result indicated that the products of the SMX biodegradation were 3-amino-5-methylisoxazole and 4-aminobenzenesulfonic acid, which suggested that the SMX biodegradation was caused by SN bond cleavage. This study indicates that the biochemical mechanisms play a vital role in SMX transformation and Fe(II) generation in this system., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Electron shuttles extensively exist in various environments. Some kinds of organic substances can be applied by microorganisms to produce electrons, and then the electrons can be transferred to other substances or microorganisms through electron shuttles, resulting in coexistence and interaction of diverse species of microbes. In this review, the functional mechanisms of extracellular electron transfer mediated by different electron shuttles are described. And different subtypes as well as the application of electron shuttles in microbial degradation of pollutants, microbial electricity, and the promotion of energy generation are also discussed. Summary results show that extracellular electron transfer is based on the electrogenesis microorganism with the structure of cytochromes or pili. Materials were usually used in long-distance electron transfer because of their widespread presence and abundance. Therefore, the review is beneficial to perceive the pathways of extracellular electron transfer mediated by electron shuttles and explore the contribution of different electron shuttles in extracellular electron transfer.

Reduced graphene oxide (rGO) can enhance the bioreduction of nitrobenzene by Shewanella oneidensis MR-1. The effects of surface modification and coexisting soluble electron shuttles on rGO-enhanced bioreduction of nitrobenzene were investigated here. The results showed that rGO enhanced the secretion of extracellular polymeric substance and the bioreduction of nitrobenzene of several folds. No inhibition effect on nitrobenzene bioreduction was observed even when the concentration of rGO was as high as 200 mg/L. The surface modification of rGO might affect the electrical conductivity which was assumed as one of the main factors that contributed to the enhancement of nitrobenzene bioreduction by rGO materials. Moreover, the coexisting electron shuttles further enhanced the rGO-mediated nitrobenzene bioreduction. After the simultaneous addition of flavin mononucleotide (10 μM) and rGO (50 mg/L), the reduction rate increased 7.8 times to 424.98 ± 7.84 mg (nitrobenzene)/(g (dry cell)∙h), which was higher than those ever reported.

This first-attempt study quantitatively assessed electron-mediating characteristics of bicyclic aromatics - 1-amino-2-naphthol, 4-amino-1-naphthol (i.e., decolorized intermediates of azo dyes - orange I and II) for color removal and power generation in MFCs. According to cyclic-voltammetric profiles, the presence of reduction and oxidation peak potentials clearly suggested a crucial role of these intermediates as electron-shuttling mediators. Shake-flask cultures also showed that appropriate accumulation of 1A2N, 4A1N apparently enhanced color-removal efficiencies of bacterial decolorization. This study clearly suggested that suitable supplementation of electrochemically active electron shuttle(s) to dye-bearing MFCs is a promising strategy to stimulate reductive decolorization and bioelectricity generation., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Dissimilatory metal reducing organisms play key roles in the biogeochemical cycle of metals as well as in the durability of submerged and buried metallic structures. The molecular mechanisms that support electron transfer across the microbe-metal interface in these organisms remain poorly explored. It is known that outer membrane proteins, in particular multiheme cytochromes, are essential for this type of metabolism, being responsible for direct and indirect, via electron shuttles, interaction with the insoluble electron acceptors. Soluble electron shuttles such as flavins, phenazines, and humic acids are known to enhance extracellular electron transfer. In this work, this phenomenon was explored. All known outer membrane decaheme cytochromes from Shewanella oneidensis MR-1 with known metal terminal reductase activity and a undecaheme cytochrome from Shewanella sp. HRCR-6 were expressed and purified. Their interactions with soluble electron shuttles were studied using stopped-flow kinetics, NMR spectroscopy, and molecular simulations. The results show that despite the structural similarities, expected from the available structural data and sequence homology, the detailed characteristics of their interactions with soluble electron shuttles are different. MtrC and OmcA appear to interact with a variety of different electron shuttles in the close vicinity of some of their hemes, and with affinities that are biologically relevant for the concentrations typical found in the medium for this type of compounds. All data support a view of a distant interaction between the hemes of MtrF and the electron shuttles. For UndA a clear structural characterization was achieved for the interaction with AQDS a humic acid analog. These results provide guidance for future work of the manipulation of these proteins toward modulation of their role in metal attachment and reduction.

Microbial fuel cells (MFCs) are promising for generating bioenergy and treating organic waste simultaneously. However, low extracellular electron transfer (EET) efficiency between electrogens and anodes remains one of the major bottlenecks in practical applications of MFCs. In this paper, pyocyanin (PYO) synthesis pathway was manipulated to improve the EET efficiency in Pseudomonas aeruginosa-inoculated MFCs. By overexpression of phzM (methyltransferase encoding gene), the maximum power density of P. aeruginosa-phzM-inoculated MFC was enhanced to 166.68 μW/cm(2), which was four folds of the original strain. In addition, the phzM overexpression strain exhibited an increase of 1.6 folds in PYO production and about a onefold decrease in the total internal resistance than the original strain, which should underlie the enhancement of the EET efficiency and the electricity power output (EPT). On the basis of these results, the manipulation of electron shuttles synthesis pathways could be an efficient approach to improve the EPT of MFCs., (Copyright © 2013 Elsevier Ltd. All rights reserved.)