Electron Transfer Function Research Articles

2D-3D electron transfer functions and stability of sustainable graphitic biocarbon for bipolar plate application

Biocarbon being a highly demanding renewable source of carbon is important for many applications such as soil enrichment, electronic applications, etc. In this research, sustainable waste biomass-to-energy materials conversion, kinetic, thermodynamic and electronic properties of carbonized forest biomaterials were investigated to evaluate their high-potential in bipolar plate for fuel cell application. In thermogravimetric analysis, the lignin biocarbon showed the least activation energy of 95 KJ/mol compared to 127 and 145 KJ/mol for hardwood and softwood biocarbons respectively. The crystallographic nature of carbonized ligneous and cellulosic biomaterials was also investigated, showing its intrinsic properties and exotic functionality through semi-metallic properties determined from density function theory, transmission electron microscopy and UV–Vis absorption. Finally, the electrochemical properties of bio-carbon composites were examined to prove stability and corrosion resistance comparable to metallic plates. Biocarbon composites showed high polarization resistance up to 5.96 kΩ-cm2 with non-reactive properties, favorable to use in bipolar plates as an alternative to metallic plate which is expensive and prone to corrosion. Overall, sustainable biocarbon shows its ability as a high-performance functional material alternative to expensive nanofillers as well as to enhance the attributes of the bipolar plate composite by increasing connectivity between primary filler and insulating resin.

Multilevel assault dominated by electron-transfer nonradical pathway via electronic metal–support interactions of Bi-C bonds for disinfection

Multilevel assaults on aqueous pathogenic microorganisms were realized by persulfate (PS) activation system with Bi–C based electronic metal-supported interactions (EMSI) of bismuth-embedded carbon chainmail catalyst (Bi@CC) dominated by electron-transfer nonradical pathway. The Bi@CC/PS disinfection system achieved approximately 100 % bacterial inactivation (6.5 log10 cfu/mL) within 35 min. The electron transfer from Bi to the carbon layer via Bi-C bond leading to higher work functions, thus realizing primary assault to the extracellular membrane via bacterial extracellular electron transfer (EET) function. Electron rearrangement of Bi-C is conducive to forming the intermediate complexes (Bi@CC-PS*), leading to higher work functions and enhancing electron transfer pathway (ETP) process to aggravate cell destruction, while radicals (∙OH andSO4∙-) directly attacks the interior cell. The Bi@CC/PS disinfection system possesses excellent environmental adaptability, cycling performance, and safety. This study enriches the heterogeneous mechanism of PS activation and proposes a promising strategy for sewage effluent treatment.

Algae promotes the biogenic oxidation of Mn(II) by accelerated extracellular superoxide production

Microbial manganese (Mn) oxidation, predominantly occurs within the anaerobic-aerobic interfaces, plays an important role in environmental pollution remediation. The anaerobic-aerobic transition zones, notably riparian and lakeside zones, are hotspots for algae-bacteria interactions. Here, we adopted a Mn(II)-oxidizing bacterium Pseudomonas sp. QJX-1 to investigate the impact of algae on microbial Mn(II) oxidation and verify the underlying mechanisms. Interestingly, we achieved a remarkable enhancement in bacterial Mn(II)-oxidizing activity within the algae-bacteria co-culture, despite the inability to oxidize Mn(II) for the algae used in this study. In addition, the bacterial density almost remains constant in the presence of algal cells. Therefore, the increased Mn(II) oxidation by QJX-1 in the presence of algae cannot be due to the increased biomass. Within this co-culture system, the Mn(II) oxidation rate surged to an impressive 0.23 mg/L/h, in stark contrast to 0.02 mg/L/h recorded within pure QJX-1 system. The presence of algae could inhibit the Fe-S cluster activity of QJX-1 by the produced active substance in co-culture, and result in the acceleration of extracellular superoxide production due to the impairment of electron transfer functions located in QJX-1 cell membranes. Moreover, elevated peroxidase gene expression and heightened extracellular catalase activity not only expedited Mn(II) ions oxidation but also facilitated conversion of intermediate Mn(III) ions into microbial Mn oxides, achieved through the degradation of hydrogen peroxide. Therefore, the acceleration of extracellular superoxide production and the decomposition of hydrogen peroxide are identified as the principal mechanisms behind the observed enhancement in Mn(II) oxidation within algae-bacteria co-cultures. Our findings highlight the need to consider the effect of algae on microbial Mn(II) oxidation, which plays an important role in the environmental pollution remediation.

Inoculum source determines the stress resistance of electroactive functional taxa in biofilms: A metagenomic perspective

The inoculum has a crucial impact on bioreactor initialization and performance. However, there is currently a lack of guidance on selecting appropriate inocula for applications in environmental biotechnology. In this study, we applied microbial electrolysis cells (MECs) as models to investigate the differences in the functional potential of electroactive microorganisms (EAMs) within anodic biofilms developed from four different inocula (natural or artificial), using shotgun metagenomic techniques. We specifically focused on extracellular electron transfer (EET) function and stress resistance, which affect the performance and stability of MECs. Community profiling revealed that the family Geobacteraceae was the key EAM taxon in all biofilms, with Geobacter as the dominant genus. The c-type cytochrome gene imcH showed universal importance for Geobacteraceae EET and was utilized as a marker gene to evaluate the EET potential of EAMs. Additionally, stress response functional genes were used to assess the stress resistance potential of Geobacter species. Comparative analysis of imcH gene abundance revealed that EAMs with comparable overall EET potential could be enriched from artificial and natural inocula (P > 0.05). However, quantification of stress response gene copy numbers in the genomes demonstrated that EAMs originating from natural inocula possessed superior stress resistance potential (196 vs. 163). Overall, this study provides novel perspectives on the inoculum effect in bioreactors and offers theoretical guidance for selecting inoculum in environmental engineering applications.

Electrical Wiring of Malarial Parasite Intermediate Hematin on a Tailored N-Doped Carbon Nanomaterial Surface and Its Bioelectrocatalytic Hydrogen Peroxide Reduction and Sensing.

Hematin, an iron-containing porphyrin compound, plays a crucial role in various biological processes, including oxygen transport, storage, and functionality of the malarial parasite. Specifically, hematin-Fe interacts with the nitrogen atom of antimalarial drugs, forming an intermediate step crucial for their function. The electron transfer functionality of hematin in biological systems has been scarcely investigated. In this study, we developed a biomimicking electrical wiring of hematin-Fe with a model N-drug system, represented as {hematin-Fe---N-drug}. We achieved this by immobilizing hematin on a multiwalled carbon nanotube (MWCNT)/N-graphene quantum dot (N-GQD) modified electrode (MWCNT/N-GQD@Hemat). N-GQD serves as a model molecular drug system containing nitrogen atoms to mimic the {hematin-Fe---N-drug} interaction. The prepared bioelectrode exhibited a distinct redox peak at a measured potential (E1/2) of -0.410 V vs Ag/AgCl, accompanied by a surface excess value of 3.54 × 10-9 mol cm-2. This observation contrasts significantly with the weak or electroinactive electrochemical responses documented in literature-based hematin systems. We performed a comprehensive set of physicochemical and electrochemical characterizations on the MWCNT/N-GQD@Hemat system, employing techniques including FESEM, TEM, Raman spectroscopy, IR spectroscopy, and AFM. To evaluate the biomimetic electrode's electroactivity, we investigated the selective-mediated reduction of H2O2 as a model system. As an important aspect of our research, we demonstrated the use of scanning electrochemical microscopy to visualize the in situ electron transfer reaction of the biomimicking electrode. In an independent study, we showed enzyme-less electrocatalytic reduction and selective electrocatalytic sensing of H2O2 with a detection limit of 319 nM. We achieved this using a batch injection analysis-coupled disposable screen-printed electrode system in physiological solution.

Expression of filaments of the Geobacter extracellular cytochrome OmcS in Shewanella oneidensis.

The physiological role of Geobacter sulfurreducens extracellular cytochrome filaments is a matter of debate and the development of proposed electronic device applications of cytochrome filaments awaits methods for large-scale cytochrome nanowire production. Functional studies in G. sulfurreducens are stymied by the broad diversity of redox-active proteins on the outer cell surface and the redundancy and plasticity of extracellular electron transport routes. G. sulfurreducens is a poor chassis for producing cytochrome nanowires for electronics because of its slow, low-yield, anaerobic growth. Here we report that filaments of the G. sulfurreducens cytochrome OmcS can be heterologously expressed in Shewanella oneidensis. Multiple lines of evidence demonstrated that a strain of S. oneidensis, expressing the G. sulfurreducens OmcS gene on a plasmid, localized OmcS on the outer cell surface. Atomic force microscopy revealed filaments with the unique morphology of OmcS filaments emanating from cells. Electron transfer to OmcS appeared to require a functional outer-membrane porin-cytochrome conduit. The results suggest that S. oneidensis, which grows rapidly to high culture densities under aerobic conditions, may be suitable for the development of a chassis for producing cytochrome nanowires for electronics applications and may also be a good model microbe for elucidating cytochrome filament function in anaerobic extracellular electron transfer.

Effect of proline content and histidine ligation on the dynamics of Ω-loop D and the peroxidase activity of iso-1-cytochrome c

To study how proline residues affect the dynamics of Ω-loop D (residues 70 to 85) of cytochrome c, we prepared G83P and G83A variants of yeast iso-1-cytochrome c (iso-1-Cytc) in the presence and absence of a K73H mutation. Ω-loop D is important in controlling both the electron transfer function of Cytc and the peroxidase activity of Cytc used in apoptosis because it provides the Met80 heme ligand. The G83P and G83A mutations have no effect on the global stability of iso-1-Cytc in presence or absence of the K73H mutation. However, both mutations destabilize the His73-mediated alkaline conformer relative to the native state. pH jump stopped-flow experiments show that the dynamics of the His73-mediated alkaline transition are significantly enhanced by the G83P mutation. Gated electron transfer studies show that the enhanced dynamics result from an increased rate of return to the native state, whereas the rate of loss of Met80 ligation is unchanged by the G83P mutation. Thus, the G83P substitution does not stiffen the conformation of the native state. Because bis-His heme ligation occurs when Cytc binds to cardiolipin-containing membranes, we studied the effect of His73 ligation on the peroxidase activity of Cytc, which acts as an early signal in apoptosis by causing oxygenation of cardiolipin. We find that the His73 alkaline conformer suppresses the peroxidase activity of Cytc. Thus, the bis-His ligated state of Cytc formed upon binding to cardiolipin is a negative effector for the peroxidase activity of Cytc early in apoptosis.

The phylogeny of Acetobacteraceae : photosynthetic traits and deranged respiratory enzymes

ABSTRACT We present here a comprehensive phylogenomic analysis of Acetobacteraceae , a vast group of alphaproteobacteria that has been widely studied for their economic importance. Our results indicate that the ancestor of Acetobacteraceae most likely was photosynthetic and evolved via a progressive transition from versatile photoferrotrophy to the incomplete oxidation of organic substrates defining acetous physiology. Vestigial signs of photosynthetic carotenoid metabolism are present in non-photosynthetic acetous taxa that have lost cytochrome oxidase, while their sister taxa retain such traits. The dominant terminal oxidase of acetous bacteria, the bo 3 ubiquinol oxidase, is derived from duplication and diversification of operons present in Acidocella taxa that have lost photosynthesis. We analyzed the bioenergetic traits that can compensate for the electron transfer function of photosynthetic reaction centers or constitute alternative pathways for the oxidoreduction of c -type cytochromes, such as iron oxidation. The latter pathway bypasses the deranged cytochrome bc 1 complex that is characteristically present in acidophilic taxa due to the loss of conserved ligands in both the Rieske iron-sulfur protein and cytochrome b subunit. The deranged or non-functional bc 1 complex may be retained for its structural role in stabilizing Complex I. The combination of our phylogenetic analysis with in-depth functional evaluations indicates that the order Acetobacterales needs to be emended to include three families: Acetobacteraceae sensu stricto , Roseomonadaceae fam. nov., and Acidocellaceae fam. nov. IMPORTANCE Acetobacteraceae are one of the best known and most extensively studied groups of bacteria, which nowadays encompasses a variety of taxa that are very different from the vinegar-producing species defining the family. Our paper presents the most detailed phylogeny of all current taxa classified as Acetobacteraceae , for which we propose a taxonomic revision. Several of such taxa inhabit some of the most extreme environments on the planet, from the deserts of Antarctica to the Sinai desert, as well as acidic niches in volcanic sites like the one we have been studying in Patagonia. Our work documents the progressive variation of the respiratory chain in early branching Acetobacteraceae into the different respiratory chains of acidophilic taxa such as Acidocella and acetous taxa such as Acetobacter . Remarkably, several genomes retain remnants of ancestral photosynthetic traits and functional bc 1 complexes. Thus, we propose that the common ancestor of Acetobacteraceae was photosynthetic.

Clinical and genetic analysis of essential hypertension with CYB gene m.15024G>A mutation.

To explore the role of mitochondrial CYB 15024G>A mutation in the development of essential hypertension. Mitochondrial genome sequences of hypertensive patients were obtained from previous studies. Clinical and genetic data of a hypertensive patient with mitochondrial CYB 15024G>A mutation and its pedigree were analyzed. Lymphocytes derived from patient and family members were transformed into immortalized lymphoblastoid cell lines, and the levels of adenosine triphosphate (ATP), mitochondrial membrane potential and intracellular reactive oxygen species (ROS) were detected. The penetrance of this essential hypertension family was 42.9%, and the age of onset was 46-68 years old. Mitochondrial genome sequencing results showed that all maternal members carried a highly conserved mitochondrial CYB 15024G>A mutation. This mutation could affect the free energy of mitochondrial CYB for secondary and tertiary structure and protein folding, thereby changing its structural stability and the structure of the electron transfer function area around the mutation site. Compared with the control, the cell line carrying the mitochondrial CYB 15024G>A mutation showed significantly decreased levels of mitochondrial CYB, ATP and mitochondrial membrane potential, and increased levels of ROS (P<0.01). Mitochondrial CYB 15024G>A mutation may affect the structure of respiratory chain subunits and mitochondrial function, leading to cell dysfunction, which suggests that the mutation may play a synergistic role in essential hypertension.

Mechanistic insights into the response of electroactive biofilms to Cd2+ shock: bacterial viability and electron transfer behavior at the cellular and community levels

Electroactive biofilms (EABs) play a crucial role in environmental bioremediation due to their excellent extracellular electron transfer (EET) capabilities. However, Cd2+ can have toxic effects on the electrochemical performance of EABs, and the comprehensive inhibition mechanism of EABs in response to Cd2+ shock remains elusive. This study indicated that Cd2+ shock significantly reduced biomass and increased oxidative stress in EABs at the cellular level. The bacterial viability of EABs in phase III under 0.5 mM Cd2+ shock (EABCd2+-III0.5) decreased by 16.31% compared to EABCK-III. Moreover, intracellular NADH, c-Cyts, and the abundance of electroactive species were essential indicators to evaluate EET behavior of EABs. In EABCd2+-III0.5, these indicators decreased by 26.32%, 33.40%, and 20.65%, respectively. Structural equation modeling analysis established quantitative correlations between core components and electrochemical activity at cellular and community levels. The correlation analysis revealed that the growth and electron transfer functions of EABs were predictive indicators for their electrochemical performance, with standardized path coefficients of 0.407 and 0.358, respectively. These findings enhance our understanding of EABs’ response to Cd2+ shock and provide insights for improving their performance in heavy metal wastewater.

A π-π Bonding-Assisted Molecular-Wiring of Folded-Cytochrome c and Naphthoquinone and Its Electron-Relay-Based Bioelectrocatalytic H2O2 Reduction Reaction Visualized by Redox-Competitive Scanning Electrochemical Microscopy.

The electron-transfer (ET) reaction of cytochrome c (Cytc) protein with biomolecules is a cutting-edge research area of interest in understanding the functionalities of natural systems. Several electrochemical biomimicking studies based on Cytc-protein-modified electrodes prepared via electrostatic interaction and covalent bonding approaches have been reported. Indeed, natural enzymes involve multiple types of bonding, such as hydrogen, ionic, covalent, and π-π, etc. In this work, we explore a Cytc-protein chemically modified glassy carbon electrode (GCE/CB@NQ/Cytc) prepared via π-π bonding using graphitic carbon as an underlying surface and an aromatic organic molecule, naphthoquinone (NQ), as a cofactor for an effective ET reaction. A simple drop-casting technique-based preparation of GCE/CB@NQ showed a distinct surface-confined redox peak at a standard electrode potential (E°) = -0.2 V vs Ag/AgCl (surface excess = 21.3 nmol cm-2) in pH 7 phosphate buffer solution. A control experiment of modification of NQ on an unmodified GCE failed to show any such unique feature. For the preparation of GCE/CB@NQ/Cytc, a dilute solution of Cytc-pH 7 phosphate buffer was drop-cast on the GCE/CB@NQ surface, wherein the protein folding and denaturalization-based complication and its associated ET functionalities were avoided. Molecular dynamics simulation studies show the complexation of NQ with Cytc at the protein binding sites. The protein-bound surface shows an efficient and selective bioelectrocatalytic reduction performance of H2O2, as demonstrated using cyclic voltammetry and amperometric i-t techniques. Finally, the redox-competition scanning electrochemical microscopy (RC-SECM) technique was adopted for in situ visualization of the electroactive adsorbed surface. The RC-SECM images clearly show the regions of highly bioelectrocatalytic active sites of Cytc-proteins bound to NQ molecules on a graphitic carbon surface. The binding of Cytc with NQ has significant implications for studying the biological electron transport mechanism, and the proposed method provides the requisite framework for such a study.

Corrosion inhibition efficiency and quantum chemical studies of some organic compounds: theoretical evaluation

Abstract When most or all of the atoms on a single metal surface are oxidized, corrosion takes place, causing damage to the whole surface. The effects of adsorption and corrosion inhibition on different types of functional groups were studied. A review of these inhibitors based on concentration effect was performed to establish the theoretical results. It has been investigated the effects of 5-(5-(3,5-diaminophenyl)-1,3,4-oxadiazol-2-yl)-N1,N3-di-p-tolylbenzene-1,3-diamine (BATP) on mild steel in 1 M H2SO4 at 30 °C, Levamisole (LMS) and 4-phenylimidazole (PIZ) on copper in 0.5 M H2SO4, 2-phenyl-1, 4-dihydroquinoxaline (PHQ) on carbon steel in 1.0 M HCl. Based on DFT calculations in the 6–311++G(d,p) basis set in gas and aqueous phases, several quantum chemical parameters were determined to evaluate the array of selected molecules such as HOMO, LUMO, ionization energy, bandgap energy, electronegativity, chemical potential, electrophilicity, nucleophilicity, electron transfer, back-donation energy and Fukui function analysis. The most stable low-energy adsorption configurations of the materials employed in this investigation on the Fe (110) surface were induced using Monte Carlo simulations.

Wide distribution of extracellular electron transfer functionality in natural proteinaceous organic materials for microbial reductive dehalogenation.

Extracellular electron transfer materials (EETMs) in the environment, such as humic substances and biochar, are formed from the humification/heating of natural organic materials. However, the distribution of extracellular electron transfer (EET) functionality in fresh natural organic materials has not yet been explored. In the present study, we reveal the wide distribution of EET functionality in proteinaceous materials for the first time using an anaerobic pentachlorophenol dechlorinating consortium, whose activity depends on EETM. Out of 11 natural organic materials and 13 reference compounds, seven proteinaceous organic materials (albumin, beef, milk, pork, soybean, yolk, and bovine serum albumin) functioned as EETMs. Carbohydrates and lipids did not function as EETMs. Comparative spectroscopic analyses suggested that a β-sheet secondary structure was essential for proteins to function as EETMs, regardless of water solubility. A high content of reduced sulfur was potentially involved in EET functionality. Although proteinaceous materials have thus far been considered simply as nutrients, the wide distribution of EET functionality in these materials provides new insights into their impact on biogeochemical cycles. In addition, structural information on EET functionality can provide a scientific basis for the development of eco-friendly EETMs.

Optimizing the parameters of microbial fuel cells using response surface methodology to increase Cr(VI) removal efficiency and power production

Cr(VI) is present naturally as Cr2O72- and its negative charge repels electrons (e-), preventing direct reduction to Cr(III). The Cr(VI) reduction process consumes H+ , suggesting that conventional Cr(VI) reduction techniques a strictly require a low pH, increasing their cost. Therefore, the development of a process that enables Cr(VI) reduction at neutral pH conditions is of interest. In this work, Cu(II) was used as an electron shuttle medium in a microbial fuel cell (MFC). The effects of MFC operating conditions, such as Cu(II)/Cr(VI) ratio, substrate (sodium acetate) concentration and external resistance on the power density (PD) and Cr(VI) removal efficiency were investigated using the response surface methodology (RSM). The maximum Cr(VI) removal efficiency (73%) and power production capacity (30.57 mW/m2) were achieved under pH-neutral conditions with a Cu(II)/Cr(VI) ratio of 1.65, a substrate concentration of 1.36 g/L, and an external resistance of 1360 Ω. The Cr(VI) removal efficiency of the MFC system without added Cu(II) was only 43%, and the power production capacity (15.85 mW/m2) was only half of that under optimal conditions. The removal efficiency of Cu(II) was 100% after seven days. Chromium and copper deposits were observed on the cathode surface, indicating that Cu(II) was deposited on the cathode surface following Cr(VI) removal, eliminating the secondary contamination that is caused by the addition of excess Cu(II). An RSM-optimized MFC system exhibits improved chemical oxygen demand removal, Coulombic efficiency and normalized energy recovery (NER). Its NER is at least 1.5 times higher than that of an unoptimized MFC system, indicating that the MFC most efficiently converts substrates into electrons when the operating conditions are optimized. This work demonstrates that Cu(II) plays a critical role as an electron-shuttle mediator in the removal of Cr(VI). The electron transfer function of Cu(II) increases the efficiency of the reduction that involves Cr(VI), electrons and H+, and eliminates the cost of adding acidic agents, as required in the conventional method in wastewater treatment. The obtained Cu(II)/Cr(VI) ratio is used to determine the maximum amount of Cr(VI) that can be removed by a scaled-up MFC system.

Metal-Coated Polymer Fiber Mesh as an Ultralightweight Gas-Diffusible Current Collector for High-Energy-Density Rechargeable Lithium–Oxygen Batteries

Lithium–oxygen batteries (LOBs) have received great attention as next-generation energy storage devices owing to their superior theoretical energy densities. Although there has been considerable technological progress in the field of LOBs, the development of gas diffusion layer materials at the positive oxygen electrode is limited despite their importance in providing an oxygen supply needed to achieve practical power densities. In the present study, we demonstrate the concept of a gas-diffusible current collector, which combines the functions of oxygen mass transport and electron transfer with minimal mass loading. To verify this concept, we fabricated a Ni-coated polymer fiber mesh and investigated its applicability in LOBs. LOB cells equipped with an ultralightweight gas-diffusible current collector exhibit a performance equivalent to that of cells equipped with conventional heavy components at 0.4 mA/cm2 current density and 4.0 mAh/cm2 areal capacity. We believe that the concept of an ultralightweight gas-diffusible current collector demonstrated in this study opens future directions in the search for metal–air batteries with high energy and power densities.

Mitochondrial ferredoxin-like is essential for forming complex I-containing supercomplexes in Arabidopsis.

In eukaryotes, mitochondrial ATP is mainly produced by the oxidative phosphorylation (OXPHOS) system, which is composed of 5 multiprotein complexes (complexes I-V). Analyses of the OXPHOS system by native gel electrophoresis have revealed an organization of OXPHOS complexes into supercomplexes, but their roles and assembly pathways remain unclear. In this study, we characterized an atypical mitochondrial ferredoxin (mitochondrial ferredoxin-like, mFDX-like). This protein was previously found to be part of the bridge domain linking the matrix and membrane arms of the complex I. Phylogenetic analysis suggested that the Arabidopsis (Arabidopsis thaliana) mFDX-like evolved from classical mitochondrial ferredoxins (mFDXs) but lost one of the cysteines required for the coordination of the iron-sulfur (Fe-S) cluster, supposedly essential for the electron transfer function of FDXs. Accordingly, our biochemical study showed that AtmFDX-like does not bind an Fe-S cluster and is therefore unlikely to be involved in electron transfer reactions. To study the function of mFDX-like, we created deletion lines in Arabidopsis using a CRISPR/Cas9-based strategy. These lines did not show any abnormal phenotype under standard growth conditions. However, the characterization of the OXPHOS system demonstrated that mFDX-like is important for the assembly of complex I and essential for the formation of complex I-containing supercomplexes. We propose that mFDX-like and the bridge domain are required for the correct conformation of the membrane arm of complex I that is essential for the association of complex I with complex III2 to form supercomplexes.

Endogenous mechanism of microbial functional gene and exogenous nitrogen removal factors driven by sustainable iron-nitrogen cycling

Feammox and nitrate-dependent Fe(II) oxidation (NDFO) play an important role in the iron-nitrogen cycle, respectively. To further understand the intrinsic molecular biological mechanism of Feammox with NDFO and improve the total nitrogen (TN) removal efficiency of the culture system, functional gene endogenous development and exogenous factors affecting nitrogen removal driven by the iron-nitrogen cycle were analyzed. Principal component analysis (PCA) showed that the three different ecological groups all formed a similar stable iron-nitrogen bacteria community structure. For 16S rRNA and qPCR, the dominant bacterial genera of Feammox coupled with NDFO were closely related, the amount of nxrB, nirS, and nosZ gene are 1-2 orders of magnitude larger than the amoA, narG, and AMX gene, which are the most important endogenous factors affecting nitrogen removal in the system. And an interesting result is that amoA, nxrB, narG, nirS and nosZ genes were all significantly positively correlated with each other (p < 0.05), indicating that the nitrogen cycle function genes changed synchronously, which was consistent with the changes in the microbial genera. The experimental process was optimized by changing environmental factors such as pH, organic carbon and extracellular electron shuttle to improve nitrogen removal. The results indicated that TN removal efficiency (67.05–76.12%) was greatly increased compared with the previous experiments (18.62–19.38%), which was the highest in pH = 8 groups (COD/TN = 3) because pH of the enrichment system stabilized to approximately 8. Moreover, the added 9,10-anthraquinone-2,6-disulfonate (AQDS) has improved TN removal efficiency to 67.27–87.75% through its extracellular electron transfer function, which was higher than that of control groups (without AQDS). This study provides a new scientific perspective and sustainable practical support for nitrogen pollution removal in the natural ecosystems or wastewater treatment systems.

Detoxification mechanisms of electroactive microorganisms under toxicity stress: A review.

Remediation of environmental toxic pollutants has attracted extensive attention in recent years. Microbial bioremediation has been an important technology for removing toxic pollutants. However, microbial activity is also susceptible to toxicity stress in the process of intracellular detoxification, which significantly reduces microbial activity. Electroactive microorganisms (EAMs) can detoxify toxic pollutants extracellularly to a certain extent, which is related to their unique extracellular electron transfer (EET) function. In this review, the extracellular and intracellular aspects of the EAMs' detoxification mechanisms are explored separately. Additionally, various strategies for enhancing the effect of extracellular detoxification are discussed. Finally, future research directions are proposed based on the bottlenecks encountered in the current studies. This review can contribute to the development of toxic pollutants remediation technologies based on EAMs, and provide theoretical and technical support for future practical engineering applications.

Anaerobic mineralization of toluene by enriched soil-free consortia with solid-phase humin as a terminal electron acceptor

The anaerobic biodegradation of toluene proceeds very slowly owing to limited electron acceptors in contaminated aquifer. The liquid reagents traditionally used to enhance this process readily migrate away from the contaminated site, and continuous addition would cause secondary pollution. In our previous study, the reduced solid-phase humic substances (humin), which are redox active, were found to act as electron donors to promote the microbial reactions. Here, we provide new evidence that humin can promote the anaerobic biodegradation of toluene as a terminal electron acceptor. When inoculating nitrate-reducing (NR) and iron-reducing (IR) consortia with toluene degradation activities, the average toluene degradation rates reached 21.20 ± 1.18 μmol/(L·d) and 15.43 ± 0.41 μmol/(L·d) in the presence of a sediment humin (HMcj), and 94.69% ± 4.26% and 93.20% ± 3.73% of the electrons released from toluene oxidation to CO2 could be recovered by the reduction of HMcj, respectively. Spectroscopy analyses revealed that quinone moieties and nitrogen-containing moieties may be the electron-accepting groups of HMcj. Based on 16S rRNA sequencing, Cellulomonas spp. were the possible functional bacteria in the culture with NR consortium as the inoculum, while Azospira spp., Cellulomonas spp. and Bacillus spp. were the possible functional bacteria in the culture with IR consortium as the inoculum. Further Phylogenetic Investigation of Communities by Reconstruction of Unobserved States (PICRUSt) analyses indicated that toluene oxidation and extracellular electron transfer functions were more abundant in HMcj amended cultures, suggesting a possible enhancement mechanism by HMcj. Additionally, experiments using natural groundwater illustrated that toluene degradation was highly dependent on its concentration, HMcj dosage, pH, and salinity. The study of a column filled with HMcj-coated quartz sand demonstrated a desirable level of toluene degradation in a continuous-flow mode without the presence of other electron acceptors. This study provided an effective and green approach for the remediation of the toluene-contaminated groundwater.

Reconstructing electron transfer components from an Fe(II) oxidizing bacterium.

Neutrophilic Fe(II) oxidizing bacteria play an important role in biogeochemical processes and have also received attention for multiple technological applications. These micro-organisms are thought to couple their metabolism with extracellular electron transfer (EET) while oxidizing Fe(II) as electron donor outside the cell. Sideroxydans lithotrophicus ES-1 is a freshwater chemolithoautotrophic Fe(II) oxidizing bacterium that is challenging to culture and not yet genetically tractable. Analysis of the S. lithotrophicus ES-1 genome predicts multiple EET pathways, which are proposed to be involved in Fe(II) oxidation, but not yet validated. Here we expressed components of two of the proposed EET pathways, including the Mto and Slit_0867-0870 PCC3 pathways, from S. lithotrophicus ES-1 into Aeromonas hydrophila, an established model EET organism. We demonstrate that combinations of putative inner membrane and periplasmic components from the Mto and Slit_0867-0870 PCC3 pathways partially complemented EET activity in Aeromonas mutants lacking native components. Our results provide evidence for electron transfer functionality and interactions of inner membrane and periplasmic components from the Mto and Slit_0867-0870 PCC3 pathways. Based on these findings, we suggest that EET in S. lithotrophicus ES-1 could be more complicated than previously considered and raises questions regarding directionality of these electron transfer pathways.