RESUMEN
Microbial oxidation and the mechanism of Sb(III) are key governing elements in biogeochemical cycling. A novel Sb oxidizing bacterium, Klebsiella aerogenes HC10, was attracted early and revealed that extracellular metabolites were the main fractions driving Sb oxidation. However, linkages between the extracellular metabolite driven Sb oxidation process and mechanism remain elusive. Here, model phenolic and quinone compounds, i.e., anthraquinone-2,6-disulfonate (AQDS) and hydroquinone (HYD), representing extracellular oxidants secreted by K. aerogenes HC10, were chosen to further study the Sb(III) oxidation mechanism. N2 purging and free radical quenching showed that oxygen-induced oxidation accounted for 36.78% of Sb(III) in the metabolite reaction system, while hydroxyl free radicals (·OH) accounted for 15.52%. ·OH and H2O2 are the main driving factors for Sb oxidation. Radical quenching, methanol purification and electron paramagnetic resonance (EPR) analysis revealed that ·OH, superoxide radical (O2â¢-) and semiquinone (SQ-â¢) were reactive intermediates of the phenolic induced oxidation process. Phenolic-induced ROS are one of the main oxidants in metabolites. Cyclic voltammetry (CV) showed that electron transfer of quinone also mediated Sb(III) oxidation. Part of Sb(V) was scavenged by the formation of the secondary Sb(V)-bearing mineral mopungite [NaSb(OH)6] in the incubation system. Our study demonstrates the microbial role of oxidation detoxification and mineralization of Sb and provides scientific references for the biochemical remediation of Sb-contaminated soil.
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Antimonio , Oxidación-Reducción , Especies Reactivas de Oxígeno , Transporte de Electrón , Antimonio/metabolismo , Especies Reactivas de Oxígeno/metabolismoRESUMEN
-Action potential (AP) of excitable plant cells is an important signaling event that can differentially alter physicochemical and physiological processes in various parts of the same cell. In giant cells of characean algae, the AP propagation has minor effect on photosynthetic electron transport in areas with high activity of plasmalemmal H+-pump but inhibits linear electron flow in regions featuring high passive H+/OH- conductance of the plasma membrane (PM). Uneven spatial distributions of local periplasmic and cytoplasmic pH facilitate the operation of distinct (CO2-dependent and O2-mediated) pathways of photoinduced electron flow, which presumably accounts for differential influence of AP on photosynthesis. The excitation of Chara australis cell in the presence of methyl viologen (MV), a redox mediator with the prooxidant action, provides a convenient model system to clarify the influence of voltage-dependent ion fluxes across PM on photosynthetic activity of chloroplasts. This study shows that permeation of MV to their target sites in chloroplasts is restricted by PM in resting cells, but MV easily passes through ionic channels opened during the PM depolarization. This gated permeation of MV gives rise to strong non-photochemical quenching, decrease in the effective quantum yield of linear electron flow, apparent O2 uptake, and, finally, the enhanced ROS production, as detected by the fluorescent probe dichlorofluorescein. Taken together, the results indicate that the AP generation in the presence of MV acts as trigger for instant redirection of photosynthetic linear electron flow from CO2-dependent route to the path of O2 reduction with the eventual formation of H2O2 as a dominant and most stable ROS form.
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Membrana Celular , Chara , Oxígeno , Paraquat , Fotosíntesis , Fotosíntesis/efectos de los fármacos , Transporte de Electrón/efectos de los fármacos , Paraquat/farmacología , Membrana Celular/metabolismo , Oxígeno/metabolismo , Chara/metabolismo , Chara/efectos de los fármacos , Oxidación-Reducción , Cloroplastos/metabolismoRESUMEN
Teicoplanin has been banned in the veterinary field due to the drug resistance of antibiotics. However, teicoplanin residue from the antibiotic abuse of humans and animals poses a threat to people's health. Therefore, it is necessary to develop an efficient way for the highly accurate and reliable detection of teicoplanin from humans, food, and water. In this study, novel imprinted quantum dots of teicoplanin were prepared based on boronate affinity-based precisely controlled surface imprinting. The imprinting factor (IF) for teicoplanin was evaluated and reached a high value of 6.51. The results showed excellent sensitivity and selectivity towards teicoplanin. The relative fluorescence intensity was inversely proportional to the concentration of teicoplanin, in the range of 1.0-17 µM. And its limit of detection (LOD) was obtained as 0.714 µM. The fluorescence quenching process was mainly controlled by a static quenching mechanism via the non-radiative electron-transfer process between QDs and the five-membered cyclic boronate esters. The recoveries for the spiked urine, milk, and water samples ranged from 95.33 to 104.17%, 91.83 to 97.33, and 94.22 to 106.67%, respectively.
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Antibacterianos , Ácidos Borónicos , Puntos Cuánticos , Teicoplanina , Puntos Cuánticos/química , Humanos , Teicoplanina/química , Teicoplanina/análisis , Ácidos Borónicos/química , Antibacterianos/análisis , Antibacterianos/química , Espectrometría de Fluorescencia/métodos , Límite de Detección , Agua/química , Impresión Molecular/métodos , Ésteres/química , Ésteres/análisis , Transporte de Electrón , Contaminación de Alimentos/análisis , Análisis de los Alimentos/métodos , Animales , Técnicas Biosensibles/métodos , Leche/química , FluorescenciaRESUMEN
This study investigated the molecular mechanism behind the highly efficient performance of nitrogen-doped carbon dots (NCDs)-assisted microbial electrosynthesis systems (MESs). The impact of NCDs (C:N precursor = 1:0.5-1:3) on acetogens was examined in the biocathode. The highest electrocatalytic performance was observed with NCDs1:1. The maximum acetate production rate of 1.9 ± 0.1 mM d-1 was achieved in NCDs1:1-modified MESs, which was 26.7-216.7 % higher than other MESs (0.6-1.5 mM d-1). With NCDs1:1 modified, the biocathode exhibited a 129.3-186.8 % increase in the abundance of Sporomusa, and 38.5-104.6 % increase in cytochrome expression (cydAB, cybH). Transcriptome confirmed that cytochromes played a crucial role in the extracellular electron uptake (EEU) of NCDs1:1-modified Sporomusa. NCDs1:1 enhanced EEU efficiency, thereby increasing the two H+-pumping steps and accelerating microbial CO2 fixation. These results provide valuable insights into increasing CO2 fixation by maximizing EEU efficiency in acetogens.
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Carbono , Nitrógeno , Carbono/farmacología , Acetatos/metabolismo , Electrones , Electrodos , Dióxido de Carbono/metabolismo , Fuentes de Energía Bioeléctrica , Puntos Cuánticos/química , Transporte de ElectrónRESUMEN
Many bacteria perform extracellular electron transfer (EET), whereby electrons are transferred from the cell to an extracellular terminal electron acceptor. This electron acceptor can be an electrode and electrons can be delivered indirectly via a redox-active mediator molecule. Here, we present a protocol to study mediated EET in Lactiplantibacillus plantarum, a probiotic lactic acid bacterium widely used in the food industry, using a bioelectrochemical system. We detail how to assemble a three-electrode, two-chambered bioelectrochemical system and provide guidance on characterizing EET in the presence of a soluble mediator using chronoamperometry and cyclic voltammetry techniques. We use representative data from 1,4-dihydroxy-2-naphthoic acid (DHNA)-mediated EET experiments with L. plantarum to demonstrate data analysis and interpretation. The techniques described in this protocol can open new opportunities for electro-fermentation and bioelectrocatalysis. Recent applications of this electrochemical technique with L. plantarum demonstrated an acceleration of metabolic flux towards producing fermentation end-products, which are critical flavor components in food fermentation. As such, this system has the potential to be further developed to alter flavors in food production or produce valuable chemicals.
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Técnicas Electroquímicas , Electrodos , Transporte de Electrón , Técnicas Electroquímicas/métodos , Técnicas Electroquímicas/instrumentación , Lactobacillus plantarum/metabolismoRESUMEN
Femtosecond transient absorption spectroscopy was used to study the dynamics of the excited primary electron donor in the reaction centers of the purple bacterium Rhodobacter sphaeroides. Using global analysis and the interval method, we found a correlation between the vibrational coherence damping of the excited primary electron donor and the lifetime of the charge-separated state P+BA-, indicating the reversibility of electron transfer to the primary electron acceptor, the BA molecule. In the reaction centers, the signs of superposition of two electronic states of P were found for a delay time of less than 200 fs. It is suggested that the admixture value of the charge transfer state PA+PB- with the excited primary electron donor P* is about 24%. The results obtained are discussed in terms of the two-step electron transfer mechanism.
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Proteínas del Complejo del Centro de Reacción Fotosintética , Rhodobacter sphaeroides , Rhodobacter sphaeroides/metabolismo , Proteínas del Complejo del Centro de Reacción Fotosintética/metabolismo , Proteínas del Complejo del Centro de Reacción Fotosintética/química , Transporte de Electrón , Electrones , Proteínas Bacterianas/química , Proteínas Bacterianas/metabolismoRESUMEN
Filamentous multicellular cable bacteria perform centimeter-scale electron transport in a process that couples oxidation of an electron donor (sulfide) in deeper sediment to the reduction of an electron acceptor (oxygen or nitrate) near the surface. While this electric metabolism is prevalent in both marine and freshwater sediments, detailed electronic measurements of the conductivity previously focused on the marine cable bacteria (Candidatus Electrothrix), rather than freshwater cable bacteria, which form a separate genus (Candidatus Electronema) and contribute essential geochemical roles in freshwater sediments. Here, we characterize the electron transport characteristics of Ca. Electronema cable bacteria from Southern California freshwater sediments. Current-voltage measurements of intact cable filaments bridging interdigitated electrodes confirmed their persistent conductivity under a controlled atmosphere and the variable sensitivity of this conduction to air exposure. Electrostatic and conductive atomic force microscopies mapped out the characteristics of the cell envelope's nanofiber network, implicating it as the conductive pathway in a manner consistent with previous findings in marine cable bacteria. Four-probe measurements of microelectrodes addressing intact cables demonstrated nanoampere currents up to 200 µm lengths at modest driving voltages, allowing us to quantify the nanofiber conductivity at 0.1 S/cm for freshwater cable bacteria filaments under our measurement conditions. Such a high conductivity can support the remarkable sulfide-to-oxygen electrical currents mediated by cable bacteria in sediments. These measurements expand the knowledgebase of long-distance electron transport to the freshwater niche while shedding light on the underlying conductive network of cable bacteria.
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Agua Dulce , Transporte de Electrón , Agua Dulce/microbiología , Sedimentos Geológicos/microbiología , Sulfuros/metabolismo , California , Conductividad Eléctrica , Oxidación-ReducciónRESUMEN
Ethanol pre-fermentation of food waste effectively alleviates acidification; however, its effects on interspecies electron transfer remain unknown. This study configured the feed according to COD ratios of ethanol: sodium acetate: sodium propionate: sodium butyrate of 5:2:1.5:1.5 (ethanol-type anaerobic digestion) and 0:5:2.5:2.5 (control), and conducted semi-continuous anaerobic digestion (AD) experiments. The results showed that ethanol-type AD increased maximum tolerable organic loading rate (OLR) to 6.0 gCOD/L/d, and increased the methane production by 1.2-14.8 times compared to the control at OLRs of 1.0-5.0 gCOD/L/d. The abundance of the pilA gene, which was associated with direct interspecies electron transfer (DIET), increased by 5.6 times during ethanol-type AD. Hydrogenase genes related to interspecies hydrogen transfer (IHT), including hydA-B, hoxH-Y, hnd, ech, and ehb, were upregulated during ethanol-type AD. Ethanol-type AD improved methanogenic performance and enhanced microbial metabolism by stimulating DIET and IHT.
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Etanol , Hidrógeno , Metano , Metano/metabolismo , Hidrógeno/metabolismo , Anaerobiosis , Etanol/metabolismo , Transporte de Electrón , Reactores Biológicos , Fermentación , Hidrogenasas/metabolismoRESUMEN
The sulfur powder as electron donor in driving dual-chamber microbial fuel cell denitrification (S) process has the advantages in economy and pollution-free to treat nitrate-contained groundwater. However, the low efficiency of electron utilization in sulfur oxidation (ACE) is the bottleneck to this method. In this study, the addition of calcined pyrite to the S system (SCP) accelerated electron generation and intra/extracellular transfer efficiency, thereby improving ACE and denitrification performance. The highest nitrate removal rate reached to 3.55 ± 0.01 mg N/L/h in SCP system, and the ACE was 103 % higher than that in S system. More importantly, calcined pyrite enhanced the enrichment of functional bacteria (Burkholderiales, Thiomonas and Sulfurovum) and functional genes which related to sulfur metabolism and electron transfer. This study was more effective in removing nitrate from groundwater without compromising the water quality.
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Fuentes de Energía Bioeléctrica , Desnitrificación , Hierro , Nitratos , Sulfuros , Azufre , Azufre/metabolismo , Nitratos/metabolismo , Sulfuros/metabolismo , Sulfuros/química , Transporte de Electrón , Hierro/metabolismo , Hierro/química , Agua Subterránea/química , Electrones , Bacterias/metabolismo , Oxidación-ReducciónRESUMEN
Singlet oxygen generation has long been considered the key feature that allows genetically encoded fluorescent tags to produce polymeric contrast agents for electron microscopy. Optimization of the singlet oxygen sensitization quantum yield has not included the effects of electron-rich monomers on the sensitizer's photocycle. We report that at monomer concentrations employed for staining, quenching by electron transfer is the primary deactivation pathway for photoexcitations. A simple photochemical model including contributions from both processes reproduces the observed reaction rates and indicates that most of the product is driven by pathways that involve electron transfer with monomersânot by the sensitization of singlet oxygen. Realizing the importance of these competing reaction pathways offers a new paradigm to guide the development of genetically encodable tags and suggests opportunities to expand the materials scope and growth conditions for polymeric contrast agents (e.g., biocompatible monomers, O2 poor environments).
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Medios de Contraste , Polimerizacion , Transporte de Electrón , Medios de Contraste/química , Oxígeno Singlete/química , Flavoproteínas/química , Flavoproteínas/metabolismo , Fármacos Fotosensibilizantes/química , Procesos FotoquímicosRESUMEN
This article proposes an evolutionary trajectory for the development of biological energy producing systems. Six main stages of energy producing system evolution are described, from early evolutionary pyrite-pulled mechanism through the Last Universal Common Ancestor (LUCA) to contemporary systems. We define the Last Pure Chemical Entity (LPCE) as the last completely non-enzymatic entity. LPCE could have had some life-like properties, but lacked genetic information carriers, thus showed greater instability and environmental dependence than LUCA. A double bubble model is proposed for compartmentalization and cellularization as a prerequisite to both highly efficient protein synthesis and transmembrane ion-gradient. The article finds that although LUCA predominantly functioned anaerobically, it was a non-exclusive anaerobe, and sulfur dominated metabolism preceded phosphate dominated one.
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Evolución Biológica , Metabolismo Energético , Metabolismo Energético/genética , Transporte de Electrón , Origen de la Vida , Modelos Biológicos , HumanosRESUMEN
Photosystem I (PSI) serves as a model system for studying fundamental processes such as electron transfer (ET) and energy conversion, which are not only central to photosynthesis but also have broader implications for bioenergy production and biomimetic device design. In this study, we employed electron paramagnetic resonance (EPR) spectroscopy to investigate key light-induced charge separation steps in PSI isolated from several green algal and cyanobacterial species. Following photoexcitation, rapid sequential ET occurs through either of two quasi-symmetric branches of donor/acceptor cofactors embedded within the protein core, termed the A and B branches. Using high-frequency (130 GHz) time-resolved EPR (TR-EPR) and deuteration techniques to enhance spectral resolution, we observed that at low temperatures prokaryotic PSI exhibits reversible ET in the A branch and irreversible ET in the B branch, while PSI from eukaryotic counterparts displays either reversible ET in both branches or exclusively in the B branch. Furthermore, we observed a notable correlation between low-temperature charge separation to the terminal [4Fe-4S] clusters of PSI, termed FA and FB, as reflected in the measured FA/FB ratio. These findings enhance our understanding of the mechanistic diversity of PSI's ET across different species and underscore the importance of experimental design in resolving these differences. Though further research is necessary to elucidate the underlying mechanisms and the evolutionary significance of these variations in PSI charge separation, this study sets the stage for future investigations into the complex interplay between protein structure, ET pathways, and the environmental adaptations of photosynthetic organisms.
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Luz , Complejo de Proteína del Fotosistema I , Complejo de Proteína del Fotosistema I/metabolismo , Complejo de Proteína del Fotosistema I/química , Espectroscopía de Resonancia por Spin del Electrón/métodos , Transporte de Electrón , Cianobacterias/metabolismo , Fotosíntesis , Chlorophyta/metabolismoRESUMEN
In recent years, inorganic nanoparticles, including calcium hydroxide nanoparticles [Ca Ca(OH)2 NPs], have attracted significant interest for their ability to impact plant photosynthesis and boost agricultural productivity. In this study, the effects of 15 and 30 mg L-1 oleylamine-coated calcium hydroxide nanoparticles [Ca(OH)2@OAm NPs] on photosystem II (PSII) photochemistry were investigated on tomato plants at their growth irradiance (GI) (580 µmol photons m-2 s-1) and at high irradiance (HI) (1000 µmol photons m-2 s-1). Ca(OH)2@OAm NPs synthesized via a microwave-assisted method revealed a crystallite size of 25 nm with 34% w/w of oleylamine coater, a hydrodynamic size of 145 nm, and a ζ-potential of 4 mV. Compared with the control plants (sprayed with distilled water), PSII efficiency in tomato plants sprayed with Ca(OH)2@OAm NPs declined as soon as 90 min after the spray, accompanied by a higher excess excitation energy at PSII. Nevertheless, after 72 h, the effective quantum yield of PSII electron transport (ΦPSII) in tomato plants sprayed with Ca(OH)2@OAm NPs enhanced due to both an increase in the fraction of open PSII reaction centers (qp) and to the enhancement in the excitation capture efficiency (Fv'/Fm') of these centers. However, the decrease at the same time in non-photochemical quenching (NPQ) resulted in an increased generation of reactive oxygen species (ROS). It can be concluded that Ca(OH)2@OAm NPs, by effectively regulating the non-photochemical quenching (NPQ) mechanism, enhanced the electron transport rate (ETR) and decreased the excess excitation energy in tomato leaves. The delay in the enhancement of PSII photochemistry by the calcium hydroxide NPs was less at the GI than at the HI. The enhancement of PSII function by calcium hydroxide NPs is suggested to be triggered by the NPQ mechanism that intensifies ROS generation, which is considered to be beneficial. Calcium hydroxide nanoparticles, in less than 72 h, activated a ROS regulatory network of light energy partitioning signaling that enhanced PSII function. Therefore, synthesized Ca(OH)2@OAm NPs could potentially be used as photosynthetic biostimulants to enhance crop yields, pending further testing on other plant species.
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Hidróxido de Calcio , Nanopartículas , Complejo de Proteína del Fotosistema II , Solanum lycopersicum , Complejo de Proteína del Fotosistema II/metabolismo , Hidróxido de Calcio/química , Nanopartículas/química , Solanum lycopersicum/efectos de los fármacos , Solanum lycopersicum/metabolismo , Fotosíntesis/efectos de los fármacos , Hormesis , Transporte de Electrón/efectos de los fármacos , Especies Reactivas de Oxígeno/metabolismoRESUMEN
Photoinduced enhanced Raman spectroscopy (PIERS) has emerged as an efficient technique for enhancing the vibrational modes of analyte molecules adsorbed on a plasmonic nanoparticle-semiconductor hybrid material through chemical enhancement governed by electron transfer from the semiconductor to the plasmonic nanoparticles under an additional ultraviolet (UV) preirradiation step. The increase in chemical enhancement is imperative in analyzing and detecting pharmaceutically important moieties, such as amino acids and proteins, with a low Raman scattering cross section, even in complex biological environments. Herein, we demonstrate that UV preirradiation induced the creation of additional oxygen vacancies by introducing a low concentration (≈1%) of Ni as a dopant in the 2D platelike morphology of the BiOCl semiconductor; i.e., defect states in the semiconductor can induce charge transfer from the semiconductor to the plasmonic nanoparticles. This phenomenon facilitates electron transfer to the adsorbed analyte on the plasmonic surface. Additionally, we have shown the usefulness of this method in protein immobilization on the substrate surface, followed by the identification of a specific protein in the mixture of proteins. Proteins containing cysteine residues capture these electrons to form a surface-bound thiol group via a transient disulfide electron adduct radical. This allows differential binding of the protein molecules to the semiconductor plasmonic hybrid depending on the concentration of surface cysteine residues in proteins. Through PIERS and principal component analysis, we demonstrate the possibility of probing and distinguishing biomolecules based on their surface composition and secondary structure components even in their mixtures, thus paving the way for efficient analysis of complex biological systems.
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Semiconductores , Espectrometría Raman , Transporte de Electrón , Rayos Ultravioleta , Propiedades de Superficie , Proteínas/química , Nanopartículas del Metal/química , Nanopartículas del Metal/efectos de la radiación , AdsorciónRESUMEN
Cellular redox homeostasis is essential for maintaining cellular activities, such as DNA synthesis and gene expression. Inspired by this, new therapeutic interventions have been rapidly developed to modulate the intracellular redox state using artificial transmembrane electron transport. However, current approaches that rely on external electric field polarization can disrupt cellular functions, limiting their in vivo application. Therefore, it is crucial to develop novel electric-field-free modulation methods. In this work, we for the first time found that graphene could spontaneously insert into living cell membranes and serve as an electron tunnel to regulate intracellular reactive oxygen species and NADH based on the spontaneous bipolar electrochemical reaction mechanism. This work provides a wireless and electric-field-free approach to regulating cellular redox states directly and offers possibilities for biological applications such as cell process intervention and treatment for neurodegenerative diseases.
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Membrana Celular , Grafito , Oxidación-Reducción , Especies Reactivas de Oxígeno , Grafito/química , Humanos , Especies Reactivas de Oxígeno/metabolismo , Especies Reactivas de Oxígeno/química , Transporte de Electrón , Membrana Celular/metabolismo , Membrana Celular/química , NAD/química , NAD/metabolismo , ElectronesRESUMEN
Microcystis and bacteria always live together in the mucilage of Microcystis colonies. Extracellular electrons between Microcystis and bacteria can be translated from bioenergy to electric energy. Here, photosynthetic microbial fuel cells (PMFCs) were constructed to make clear the electron transfer mechanism between Microcystis and bacteria. A remarkable enhancement of current density with 2.5-fold change was detected in the coculture of Microcystis and bacteria than pure culture of Microcystis. Transcriptome analyses showed that photosynthesis efficiency of Microcystis was upregulated and may release more electron to improve extracellular electron transfer rate. Significant increase on oxidative phosphorylation of bacterial community was observed according to meta-transcriptome. Bacterial electrons were transferred out of cell membranes by enhancing VgrG and IcmF copies though the type II bacterial secretion system. Not only Microcystis and bacteria attached with each other tightly by filamentous, but also more gene copies relating to pilin and riboflavin production were detected from Microcystis culture. A confirmatory experiment found that riboflavin can upregulate the electron transfer and current density by adding riboflavin into cocultures. Thus, the direct contact and indirect interspecies electron transfer processes between Microcystis and bacteria were observed. Results enlarge knowledge for activities of Microcystis colonies in cyanobacterial blooms, and provide a better understanding for energy transformation.
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Microcystis , Transcriptoma , Microcystis/genética , Microcystis/fisiología , Transporte de Electrón , Fotosíntesis , Bacterias/genética , Bacterias/metabolismo , MicrobiotaRESUMEN
Fusobacterium nucleatum, a Gram-negative obligate anaerobe, is common to the oral microbiota, but the species is known to infect other sites of the body where it is associated with a range of pathologies. At present, little is known about the mechanisms by which F. nucleatum mitigates against oxidative and nitrosative stress. Inspection of the F. nucleatum subsp. polymorphum ATCC 10953 genome reveals that it encodes a flavodiiron protein (FDP; FNP2073) that is known in other organisms to reduce NO to N2O and/or O2 to H2O. FNP2073 is dicistronic with a gene encoding a multicomponent enzyme termed BCR for butyryl-CoA reductase. BCR is composed of a butyryl-CoA dehydrogenase domain (BCD), the C-terminal domain of the α-subunit of the electron-transfer flavoprotein (Etfα), and a rubredoxin domain. We show that BCR and the FDP form an α4ß4 heterotetramic complex and use butyryl-CoA to selectively reduce O2 to H2O. The FAD associated with the Etfα domain (α-FAD) forms red anionic semiquinone (FADâ¢-), whereas the FAD present in the BCD domain (δ-FAD) forms the blue-neutral semiquinone (FADHâ¢), indicating that both cofactors participate in one-electron transfers. This was confirmed in stopped-flow studies where the reduction of oxidized BCR with an excess of butyryl-CoA resulted in rapid (<1.6 ms) interflavin electron transfer evidenced by the formation of the FADâ¢-. Analysis of bacterial genomes revealed that the dicistron is present in obligate anaerobic gut bacteria considered to be beneficial by virtue of their ability to produce butyrate. Thus, BCR-FDP may help to maintain anaerobiosis in the colon.
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Proteínas Bacterianas , Fusobacterium nucleatum , Oxidación-Reducción , Oxígeno , Fusobacterium nucleatum/metabolismo , Fusobacterium nucleatum/genética , Fusobacterium nucleatum/enzimología , Oxígeno/metabolismo , Oxígeno/química , Proteínas Bacterianas/metabolismo , Proteínas Bacterianas/química , Proteínas Bacterianas/genética , Flavoproteínas Transportadoras de Electrones/metabolismo , Flavoproteínas Transportadoras de Electrones/genética , Flavoproteínas Transportadoras de Electrones/química , Transporte de Electrón , Acilcoenzima A/metabolismo , Butiril-CoA Deshidrogenasa/metabolismo , Butiril-CoA Deshidrogenasa/genética , Butiril-CoA Deshidrogenasa/químicaRESUMEN
Reverse electron transfer (RET), an abnormal backward flow of electrons from complexes III/IV to II/I of mitochondria, causes the overproduction of a reduced-type CoQ to boost downstream production of mitochondrial superoxide anions that leads to ischemia-reperfusion injury (IRI) to organs. Herein, we studied low-coordinated gold nanoclusters (AuNCs) with abundant oxygen-binding sites to form an electron-demanding trapper that allowed rapid capture of electrons to compensate for the CoQ/CoQH2 imbalance during RET. The AuNCs were composed of only eight gold atoms that formed a Cs-symmetrical configuration with all gold atoms exposed on the edge site. The geometry and atomic configuration enhance oxygen intercalation to attain a d-band electron deficiency in frontier orbitals, forming an unusually high oxidation state for rapid mitochondrial reverse electron capture under a transient imbalance of CoQ/CoQH2 redox cycles. Using hepatic IRI cells/animals, we corroborated that the CoQ-like AuNCs prevent inflammation and liver damage from IRI via recovery of the mitochondrial function.
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Electrones , Oro , Nanopartículas del Metal , Oxígeno , Oro/química , Nanopartículas del Metal/química , Oxígeno/química , Oxígeno/metabolismo , Transporte de Electrón , Sitios de Unión , Animales , Ubiquinona/química , Ubiquinona/análogos & derivados , Mitocondrias/metabolismo , Daño por Reperfusión/metabolismo , Oxidación-Reducción , Humanos , RatonesRESUMEN
In type-II reaction centers, such as photosystem II (PSII) and reaction centers from purple bacteria (PbRC), light-induced charge separation involves electron transfer from pheophytin (PheoD1) to quinone (QA), occurring near a conserved tryptophan residue (D2-Trp253 in PSII and Trp-M252 in PbRC). This study investigates the route of the PheoD1-to-QA electron transfer, focusing on the superexchange coupling (|HPheoD1···QA|) in the PSII protein environment. |HPheoD1···QA| is significantly larger for the PheoD1-to-QA electron transfer via the unoccupied molecular orbitals of D2-Trp253 ([Trp]â¢--like intermediate state, 0.73 meV) compared to direct electron transfer (0.13 meV), suggesting that superexchange is the dominant mechanism in the PSII protein environment. While the overall impact of the protein environment is limited, local interactions, particularly H-bonds, enhance superexchange electron transfer by directly affecting the delocalization of molecular orbitals. The D2-W253F mutation significantly decreases the electron transfer rate. The conservation of D2-Trp253/D1-Phe255 (Trp-M252/Phe-L216 in PbRC) in the two branches appears to differentiate superexchange coupling, contributing to the branches being either active or inactive in electron transfer.
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Complejo de Proteína del Fotosistema II , Transporte de Electrón , Complejo de Proteína del Fotosistema II/química , Complejo de Proteína del Fotosistema II/metabolismo , Feofitinas/química , Feofitinas/metabolismo , Proteínas del Complejo del Centro de Reacción Fotosintética/química , Proteínas del Complejo del Centro de Reacción Fotosintética/metabolismo , Enlace de HidrógenoRESUMEN
The functionality of electroactive biofilms (EABs) is profoundly influenced by the proteomic dynamics within microbial communities, particularly through the participation of proteins in electron transfer. This study explored the impact of electrode surface orientation, measured by varying oblique angles, on the performance of EABs in bioelectrochemical systems (BES). Utilizing quantitative proteomics, results indicated that a slightly oblique angle (45°) optimized the spatial arrangement of microbial cells, enhancing electron transport efficiency compared to other angles tested. Specifically, the 45° orientation resulted in a 2.36-fold increase in the abundance of c-type cytochromes compared to the 90°. Additionally, Geobacter, showed a relative abundance of 83.25 % at 45°, correlating with a peak current density of 1.87 ± 0.04 A/m2. These microbial and proteomic adaptations highlighted the intricate balance between microbial behavior and the physical environment, which could be tuned to optimize operations. The findings provided new insights into the design and enhancement of BES.