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1.
Bioresour Technol ; 413: 131433, 2024 Sep 03.
Artículo en Inglés | MEDLINE | ID: mdl-39236908

RESUMEN

Two parallel pilot-scale reactors were operated to investigate pollutant removal performance and metabolic pathways in elemental sulfur-driven autotrophic denitrification (SDAD) process under low temperature and after addition of external electron donors. The results showed that low temperature slightly inhibited SDAD (average total nitrogen removal of ∼4.7 mg L-1) while supplement of sodium thiosulfate (stage 2) and sodium acetate (stage 3) enhanced denitrification and secretion of extracellular polymeric substances (EPS), leading to the average removal rate of 0.75 and 1.01 kg N m-3 d-1, respectively with over twice higher total EPS. Correspondingly, nitrogen and sulfur related microbial metabolisms especially nitrite reductase and nitric oxide reductase encoding were promoted by genera including Thermomonas and Thiobacillus. The variations revealed that extra sodium acetate improved denitrification and enriched more SDAD-related microorganisms compared with sodium thiosulfate, which potentially catalyzed the refinement of practical strategies for optimizing denitrification in low carbon to nitrogen ratio wastewater treatment.

2.
Waste Manag ; 189: 185-195, 2024 Dec 01.
Artículo en Inglés | MEDLINE | ID: mdl-39208755

RESUMEN

In the leachate-saturation zone of landfills, sulfate reduction is influenced by temperature and electron donors. This study assessed sulfate reduction behaviors under varied electron donor conditions by establishing multiple temperature variation scenarios based on stable temperature fields within the leachate-saturation zone. The results showed that temperature variations altered the microbial community structure and significantly influenced the sulfate reduction process. A more pronounced effect was observed with a temperature difference of 30 °C compared to one of 10 °C. In addition, sulfate reduction was influenced by the presence of electron donors and acceptors. In the middle and low-temperature regions (35 °C and 25 °C), sulfate reduction reaction of acidic organic matter was more significant, while alcohol and saccharide organic substances were more effective in promoting sulfate reduction at high-temperature regions (55 °C). Notably, a 30 °C temperature difference within the leachate-saturation zone significantly altered the microbial community structure, which influenced the sulfate reduction behavior. In particular, Firmicutes and Synergistota played essential roles in mediating the variance in sulfate reduction efficiency with a 30 °C decrease and 30 °C increase, respectively. The results also revealed that temperature changes within landfills were influenced by leachate migration, therefore, controlling leachate recharge can help prevent secondary risks associated with sulfate reduction processes.


Asunto(s)
Temperatura , Contaminantes Químicos del Agua , Contaminantes Químicos del Agua/análisis , Sulfatos/química , Instalaciones de Eliminación de Residuos , Compuestos de Azufre , Oxidación-Reducción , Eliminación de Residuos/métodos
3.
Environ Pollut ; 358: 124491, 2024 Oct 01.
Artículo en Inglés | MEDLINE | ID: mdl-38964646

RESUMEN

The deep geological repository (DGR) concept consists of storing radioactive waste in metal canisters, surrounded by compacted bentonite, and placed deeply into a geological formation. Here, bentonite slurry microcosms with copper canisters, inoculated with bacterial consortium and amended with acetate, lactate and sulfate were set up to investigate their geochemical evolution over a year under anoxic conditions. The impact of microbial communities on the corrosion of the copper canisters in an early-stage (45 days) was also assessed. The amended bacterial consortium and electron donors/acceptor accelerated the microbial activity, while the heat-shocked process had a retarding effect. The microbial communities partially oxidize lactate to acetate, which is subsequently consumed when the lactate is depleted. Early-stage microbial communities showed that the bacterial consortium reduced microbial diversity with Pseudomonas and Stenotrophomonas dominating the community. However, sulfate-reducing bacteria such as Desulfocurvibacter, Anaerosolibacter, and Desulfosporosinus were enriched coupling oxidation of lactate/acetate with reduction of sulfates. The generated biogenic sulfides, which could mediate the conversion of copper oxides (possibly formed by trapped oxygen molecules on the bentonite or driven by the reduction of H2O) to copper sulfide (Cu2S), were identified by X-ray photoelectron spectroscopy (XPS). Overall, these findings shed light on the ideal geochemical conditions that would affect the stability of DGR barriers, emphasizing the impact of the SRB on the corrosion of the metal canisters, the gas generation, and the interaction with components of the bentonite.


Asunto(s)
Bentonita , Cobre , Residuos Radiactivos , Bentonita/química , Corrosión , Bacterias/metabolismo , España , Consorcios Microbianos
4.
Carbohydr Polym ; 342: 122387, 2024 Oct 15.
Artículo en Inglés | MEDLINE | ID: mdl-39048228

RESUMEN

Lytic polysaccharide monooxygenases (LPMOs) are copper-dependent enzymes which are categorized in the CAZy database under auxiliary activities families AA9-11, 13, 14-17. Secreted by various microorganisms, they play a crucial role in carbon recycling, particularly in fungal saprotrophs. LPMOs oxidize polysaccharides through monooxygenase/peroxygenase activities and exhibit peroxidase and oxidase activities, with variations among different families. AA16, a newly identified LPMO family, is noteworthy due to limited studies on its members, thus rendering the characterization of AA16 enzymes vital for addressing controversies around their functions. This study focused on heterologous expression and biochemical study of an AA16 LPMO from Thermothelomyces thermophilus (formerly known as Myceliophthora thermophila), namely MtLPMO16A. Substrate specificity evaluation of MtLPMO16A showed oxidative cleavage of hemicellulosic substrates and no activity on cellulose, accompanied by a strong oxidase activity. A comparative analysis with an LPMO from AA9 family explored correlations between these families, while MtLPMO16A was shown to boost the activity of some AA9 family LPMOs. The results offer new insights into the AA16 family's action mode and microbial hemicellulose decomposition mechanisms in nature.


Asunto(s)
Oxigenasas de Función Mixta , Polisacáridos , Oxigenasas de Función Mixta/metabolismo , Oxigenasas de Función Mixta/química , Oxigenasas de Función Mixta/genética , Polisacáridos/química , Polisacáridos/metabolismo , Especificidad por Sustrato , Proteínas Fúngicas/metabolismo , Proteínas Fúngicas/química , Proteínas Fúngicas/genética , Sordariales/enzimología
5.
J Photochem Photobiol B ; 257: 112969, 2024 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-38959527

RESUMEN

Light-induced electron flow between reaction center and cytochrome bc1 complexes is mediated by quinones and electron donors in purple photosynthetic bacteria. Upon high-intensity excitation, the contribution of the cytochrome bc1 complex is limited kinetically and the electron supply should be provided by the pool of reduced electron donors. The kinetic limitation of electron shuttle between reaction center and cytochrome bc1 complex and its consequences on the photocycle were studied by tracking the redox changes of the primary electron donor (BChl dimer) via absorption change and the opening of the closed reaction center via relaxation of the bacteriochlorophyll fluorescence in intact cells of wild type and pufC mutant strains of Rubrivivax gelatinosus. The results were simulated by a minimum model of reversible binding of different ligands (internal and external electron donors and inhibitors) to donor and acceptor sides of the reaction center. The calculated binding and kinetic parameters revealed that control of the rate of the photocycle is primarily due to 1) the light intensity, 2) the size and redox state of the donor pool, and 3) the unbinding rates of the oxidized donor and inhibitor from the reaction center. The similar kinetics of strains WT and pufC lacking the tetraheme cytochrome subunit attached to the reaction center raise the issue of the physiological importance of this subunit discussed from different points of view. SIGNIFICANCE: A crucial factor for the efficacy of electron donors in photosynthetic photocycle is not just the substantial size of the pool and large binding affinity (small dissociation constant KD = koff/kon) to the RC, but also the mean residence time (koff)-1 in the binding pocket. This is an important parameter that regulates the time of re-activation of the RC during multiple turnovers. The determination of koff has proven challenging and was performed by simulation of widespread experimental data on the kinetics of P+ and relaxation of fluorescence. This work is a step towards better understanding the complex pathways of electron transfer in proteins and simulation-based design of more effective electron transfer components in natural and artificial systems.


Asunto(s)
Oxidación-Reducción , Cinética , Ligandos , Transporte de Electrón , Fotosíntesis , Luz , Complejo III de Transporte de Electrones/metabolismo , Complejo III de Transporte de Electrones/química , Proteínas del Complejo del Centro de Reacción Fotosintética/metabolismo , Proteínas del Complejo del Centro de Reacción Fotosintética/química , Bacterioclorofilas/metabolismo , Bacterioclorofilas/química
6.
Biotechnol Biofuels Bioprod ; 17(1): 79, 2024 Jun 12.
Artículo en Inglés | MEDLINE | ID: mdl-38867271

RESUMEN

BACKGROUND: The need for addition of external electron donors such as ethanol or lactate impairs the economic viability of chain elongation (CE) processes for the production of medium-chain carboxylates (MCC). However, using feedstocks with inherent electron donors such as silages of waste biomass can improve the economics. Moreover, the use of an appropriate inoculum is critical to the overall efficiency of the CE process, as the production of a desired MCC can significantly be influenced by the presence or absence of specific microorganisms and their metabolic interactions. Beyond, it is necessary to generate data that can be used for reactor design, simulation and optimization of a given CE process. Such data can be obtained using appropriate mathematical models to predict the dynamics of the CE process. RESULTS: In batch experiments using silages of sugar beet leaves, cassava leaves, and Elodea/wheat straw as substrates, caproate was the only MCC produced with maximum yields of 1.97, 3.48, and 0.88 g/kgVS, respectively. The MCC concentrations were accurately predicted with the modified Gompertz model. In a semi-continuous fermentation with ensiled sugar beet leaves as substrate and digestate from a biogas reactor as the sole inoculum, a prolonged lag phase of 7 days was observed for the production of MCC (C6-C8). The lag phase was significantly shortened by at least 4 days when an enriched inoculum was added to the system. With the enriched inoculum, an MCC yield of 93.67 g/kgVS and a productivity of 2.05 gMCC/L/d were achieved. Without the enriched inoculum, MCC yield and productivity were 43.30 g/kgVS and 0.95 gMCC/L/d, respectively. The higher MCC production was accompanied by higher relative abundances of Lachnospiraceae and Eubacteriaceae. CONCLUSIONS: Ensiled waste biomass is a suitable substrate for MCC production using CE. For an enhanced production of MCC from ensiled sugar beet leaves, the use of an enriched inoculum is recommended for a fast process start and high production performance.

7.
J Environ Manage ; 360: 121066, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38744202

RESUMEN

The biotic nitrate reduction rate in freshwater ecosystems is typically constrained by the scarcity of carbon sources. In this study, 'two-chambers' - 'two-electrodes' photoautotrophic biofilm-soil microbial fuel cells (P-SMFC) was developed to accelerate nitrate reduction by activating in situ electron donors that originated from the soil organic carbon (SOC). The nitrate reduction rate of P-SMFC (0.1341 d-1) improved by âˆ¼ 1.6 times on the 28th day compared to the control photoautotrophic biofilm. The relative abundance of electroactive bacterium increased in the P-SMFC and this bacterium contributed to obtain electrons from SOC. Biochar amendment decreased the resistivity of P-SMFC, increased the electron transferring efficiency, and mitigated anodic acidification, which continuously facilitated the thriving of putative electroactive bacterium and promoted current generation. The results from physiological and ecological tests revealed that the cathodic photoautotrophic biofilm produced more extracellular protein, increased the relative abundance of Lachnospiraceae, Magnetospirillaceae, Pseudomonadaceae, and Sphingomonadaceae, and improved the activity of nitrate reductase and ATPase. Correspondingly, P-SMFC in the presence of biochar achieved the highest reaction rate constant for nitrate reduction (kobs) (0.2092 d-1) which was 2.4 times higher than the control photoautotrophic biofilm. This study provided a new strategy to vitalize in situ carbon sources in paddy soil for nitrate reduction by the construction of P-SMFC.


Asunto(s)
Fuentes de Energía Bioeléctrica , Biopelículas , Nitratos , Suelo , Nitratos/metabolismo , Suelo/química , Microbiología del Suelo , Electrodos , Carbono/metabolismo , Oxidación-Reducción
8.
Sci Total Environ ; 930: 172510, 2024 Jun 20.
Artículo en Inglés | MEDLINE | ID: mdl-38641119

RESUMEN

Although complexation between dissolved organic matter (DOM) and ubiquitous Fe is known to have a major influence on electron transferring ability in redoximorphic soil, it was unclear whether and how this complexation affected nitrate reduction and N2O productivity. The nitrate reduction of paddy soil in the presence of crop residues returning under flooding conditions was explored in this study. The rate of nitrate reduction in control soil was 0.0677 d-1, while it improved 1.99 times in treatment soil with Chinese milk vetch (CMV) straw returning. During a 28-day incubation period, N2O productivity decreased 0.08-0.91 ppb in CMV soil and 0.43-0.50 ppb in rice straw soil compared with control. The presence of crop residue increased DOC content and Fe (III) reduction rate, which aided in the formation of Fe (II)-DOC complexation. Meanwhile, the addition of CMV increased the content of DOC by 5.14-78.77 mg/kg and HCl extractable Fe (II) by 35.12-1221.03 mg/kg. Crop residues returning to soil increased the relative abundance of iron reductive and electroactive genera, as well as denitrifying genera with more copies of denitrification genes (Archangiaceae, Gemmatimonadaceae, and Burkholderiaceae). The synergistic effect of Fe-DOC complexation, electroactive genera, and denitrifying genera contributed to up-regulated expression of napA and narG (5.84 × 106 and 3.39 × 107 copies increased in the CMV soil compared to the control) numbers and equally accelerated reduction of nitrate to nitrite, while further nitrite reduction was primarily attributed to the abiotic reaction by Fe (II). From a bio-electrochemical point of view, this work provided new insight into the nitrate reduction of paddy soil impacted by Fe-DOC complexation.


Asunto(s)
Nitratos , Suelo , Suelo/química , Oryza , Hierro/química , Agricultura/métodos , Oxidación-Reducción , Productos Agrícolas , Microbiología del Suelo , Desnitrificación , Contaminantes del Suelo
9.
Biotechnol Biofuels Bioprod ; 17(1): 19, 2024 Feb 01.
Artículo en Inglés | MEDLINE | ID: mdl-38303072

RESUMEN

BACKGROUND: The field of enzymology has been profoundly transformed by the discovery of lytic polysaccharide monooxygenases (LPMOs). LPMOs hold a unique role in the natural breakdown of recalcitrant polymers like cellulose and chitin. They are characterized by a "histidine brace" in their active site, known to operate via an O2/H2O2 mechanism and require an electron source for catalytic activity. Although significant research has been conducted in the field, the relationship between these enzymes, their electron donors, and H2O2 production remains complex and multifaceted. RESULTS: This study examines TthLPMO9G activity, focusing on its interactions with various electron donors, H2O2, and cellulose substrate interactions. Moreover, the introduction of catalase effectively eliminates H2O2 interference, enabling an accurate evaluation of each donor's efficacy based on electron delivery to the LPMO active site. The introduction of catalase enhances TthLPMO9G's catalytic efficiency, leading to increased cellulose oxidation. The current study provides deeper insights into specific point mutations, illuminating the crucial role of the second coordination sphere histidine at position 140. Significantly, the H140A mutation not only impacted the enzyme's ability to oxidize cellulose, but also altered its interaction with H2O2. This change was manifested in the observed decrease in both oxidase and peroxidase activities. Furthermore, the S28A substitution, selected for potential engagement within the His1-electron donor-cellulose interaction triad, displayed electron donor-dependent alterations in cellulose product patterns. CONCLUSION: The interaction of an LPMO with H2O2, electron donors, and cellulose substrate, alongside the impact of catalase, offers deep insights into the intricate interactions occurring at the molecular level within the enzyme. Through rational alterations and substitutions that affect both the first and second coordination spheres of the active site, this study illuminates the enzyme's function. These insights enhance our understanding of the enzyme's mechanisms, providing valuable guidance for future research and potential applications in enzymology and biochemistry.

10.
Environ Res ; 246: 118159, 2024 Apr 01.
Artículo en Inglés | MEDLINE | ID: mdl-38218519

RESUMEN

Zoogloea sp. MFQ7 achieved excellent denitrification of 91.71% at ferrous to manganous ratio (Fe/Mn) of 3:7, pH of 6.5, nitrate concentration of 25 mg L-1 and carbon to nitrogen ratio of 1.5. As the Fe/Mn ratio increasd, the efficiency of nitrate removal gradually decreased, indicating that strain MFQ7 had a higher affinity for Mn2+ than Fe2+. In situ generated biogenic Fe-Mn oxides (BFMO) contained many iron-manganese oxides (MnO2, Mn3O4, FeO(OH), Fe2O3, and Fe3O4) as well as reactive functional groups, which play an significant part in tetracycline (TC) and cadmium (Cd2+) adsorption. The adsorption of TC and Cd2+ by BFMO can better fit the pseudo-second-order and Langmuir models. In addition, multiple characterization results of before and after adsorption indicated that the removal mechanism of BFMO on TC and Cd2+ was probably surface complexation adsorption and redox reactions.


Asunto(s)
Cadmio , Compuestos Férricos , Óxidos , Óxidos/química , Nitratos , Compuestos de Manganeso/química , Desnitrificación , Tetraciclina , Antibacterianos , Compuestos Orgánicos , Adsorción
11.
J Biotechnol ; 381: 1-10, 2024 Feb 10.
Artículo en Inglés | MEDLINE | ID: mdl-38176540

RESUMEN

The effects of hydraulic retention time (HRT) on the performance of two-phase anaerobic fermentation for caproic acid production from Chinese cabbage waste (CCW) were investigated. In the electron donor phase, yeast was inoculated to achieve efficient autopoietic ethanol, providing electron donors for the chain elongation process. Shorter HRT led to drastic fluctuations in microorganisms, thus resulting in lower acid yields at HRT of 6 days. At HRT of 10 days, the balanced collaboration of various key bacteria avoided the accumulation of intermediate by-products, and the caproic acid production reached 4660 mg COD/L, which was 119.5% and 154.8% higher than that at HRTs of 6 and 14 days, respectively. At HRT of 14 days, the low ethanol loading rate resulted in ethanol excessive-oxidation to acetic acid. Acetic acid accounted for 41.5% of the total product, while the selectivity of caproic acid was only 15.3%. The main contributor to the production process of caproic acid was Caproiciproducens, while the Ruminalococcaceae also played a role in the process. This study provided a theoretical basis for the efficient production of caproic acid through continuous fermentation with autopoietic electron donors.


Asunto(s)
Reactores Biológicos , Caproatos , Electrones , Fermentación , Reactores Biológicos/microbiología , Anaerobiosis , Ácido Acético , Etanol
12.
J Hazard Mater ; 465: 133153, 2024 Mar 05.
Artículo en Inglés | MEDLINE | ID: mdl-38056268

RESUMEN

Glomalin-related soil protein (GRSP) is a stable iron-organic carbon mixture that can enhance heavy metal sequestration in soils. However, the roles of GRSP in the transformation and fate of Cr(VI) have been rarely reported. Herein, we investigated the electrochemical and photocatalytic properties of GRSP and its mechanisms in Cr(VI) adsorption and reduction. Results showed that GRSP had a stronger ability for Cr(VI) adsorption and reduction than other biomaterials, with the highest adsorption amount of up to 0.126 mmol/g. The removal efficiency of Cr(VI) by GRSP was enhanced (4-7%) by ultraviolet irradiation due to the hydrated electrons produced by GRSP. Fe(II) ions, persistent free radicals, and oxygen-containing functional groups on the GRSP surface as electron donors participated in the reduction of Cr(VI) under dark condition. Moreover, Cr(III) was mainly adsorbed on the -COOH groups of GRSP via electrostatic interactions. Based on 2D correlation spectroscopy, the preferential adsorption occurred on the GRSP surface for Cr(VI) in the sequential order of CO → COO- → O-H → C-O. This work provides new insights into the Cr(VI) adsorption and reduction mechanism by GRSP. Overall, GRSP can serve as a natural iron-organic carbon for the photo-reduction of Cr(VI) pollution in environments.


Asunto(s)
Cromo , Suelo , Suelo/química , Cromo/análisis , Hierro , Proteínas Fúngicas/química , Glicoproteínas/química , Carbono , Adsorción
13.
Environ Sci Pollut Res Int ; 31(5): 7227-7245, 2024 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-38157180

RESUMEN

Characterizing uranium (U) mine water is necessary to understand and design an effective bioremediation strategy. In this study, water samples from two former U-mines in East Germany were analysed. The U and sulphate (SO42-) concentrations of Schlema-Alberoda mine water (U: 1 mg/L; SO42-: 335 mg/L) were 2 and 3 order of magnitude higher than those of the Pöhla sample (U: 0.01 mg/L; SO42-: 0.5 mg/L). U and SO42- seemed to influence the microbial diversity of the two water samples. Microbial diversity analysis identified U(VI)-reducing bacteria (e.g. Desulfurivibrio) and wood-degrading fungi (e.g. Cadophora) providing as electron donors for the growth of U-reducers. U-bioreduction experiments were performed to screen electron donors (glycerol, vanillic acid, and gluconic acid) for Schlema-Alberoda U-mine water bioremediation purpose. Thermodynamic speciation calculations show that under experimental conditions, U(VI) is not coordinated to the amended electron donors. Glycerol was the best-studied electron donor as it effectively removed 99% of soluble U, 95% of Fe, and 58% of SO42- from the mine water, probably by biostimulation of indigenous microbes. Vanillic acid removed 90% of U, and no U removal occurred using gluconic acid.


Asunto(s)
Gluconatos , Uranio , Uranio/análisis , Agua/análisis , Biodegradación Ambiental , Glicerol , Ácido Vanílico , Oxidación-Reducción
14.
N Biotechnol ; 78: 29-41, 2023 Dec 25.
Artículo en Inglés | MEDLINE | ID: mdl-37793602

RESUMEN

The present study used Cr(VI)-polluted microcosms amended with lactate or yeast extract, and nonamended microcosms as control, to investigate how a native bacterial community varied in response to the treatment and during the pollutant removal. Results suggested that providing electron donors resulted in a proliferation of a few bacterial species, with the consequent decrease in observed species richness and evenness, and was a driving force for the bacterial compositional shift. Lactate promoted, in the first instance, the enrichment of fermentative bacteria belonging to Chromobacteriaceae, including Paludibacterium, and Micrococcaceae as observed after 4 days. When the rate of Cr(VI) removal was maximum in microcosms amended with lactate, the most represented taxa were Pseudarcicella and Azospirillum. Using yeast extract as a carbon source and electron donor led instead to the significant enrichment of Shewanella, followed by Vogesella and Acinetobacter on the 4th day, corresponding to 90% of Cr(VI) removed from the system. After the complete Cr(VI) removal, achieved in 7 days in the presence of yeast extract, α-diversity was notably increased. The amendment-specific turnover of the enriched bacterial taxa resulted in a different kinetic of pollutant removal. In particular, yeast extract promoted the quickest Cr(VI) reduction, while lactate supported a slower, but also considerable, pollutant removal from water. Since it is reasonable to assume that a macroscopic effect, such as the observed Cr(VI) removal, involved the overrepresented taxa, deepening the knowledge of the native bacterial community and its changes were used to hypothesize the possible microbial pathways involved.


Asunto(s)
Contaminantes Ambientales , Microbiota , Contaminantes Químicos del Agua , Oxidación-Reducción , Cromo , Bacterias/metabolismo , Ácido Láctico , Contaminantes Químicos del Agua/metabolismo
15.
J Hazard Mater ; 459: 132256, 2023 10 05.
Artículo en Inglés | MEDLINE | ID: mdl-37567138

RESUMEN

Sulfate-reducing bacteria (SRB) were effective in stabilizing Sb. However, the influence of electron donors and acceptors during SRB remediation, as well as the ecological principles involved, remained unclear. In this study, Desulfovibrio desulfuricans ATCC 7757 was utilized to stabilize soil Sb within microcosm. Humic acid (HA) or sodium sulfate (Na2SO4) were employed to enhance SRB capacity. The SRB+HA treatment exhibited the highest Sb stabilization rate, achieving 58.40%. Bacterial community analysis revealed that SRB altered soil bacterial diversity, community composition, and assembly processes, with homogeneous selection as the predominant assembly processes. When HA and Na2SO4 significantly modified the stimulated microbial community succession trajectories, shaped the taxonomic composition and interactions of the bacterial community, they showed converse effect in shaping bacterial community which were both helpful for promoting dissimilatory sulfate reduction. Na2SO4 facilitated SRB-mediated anaerobic reduction and promoted interactions between SRB and bacteria involved in nitrogen and sulfur cycling. The HA stimulated electron generation and storage, and enhanced the interactions between SRB and bacteria possessing heavy metal tolerance or carbohydrate degradation capabilities.


Asunto(s)
Antimonio , Desulfovibrio , Antimonio/metabolismo , Oxidación-Reducción , Suelo , Disponibilidad Biológica , Desulfovibrio/metabolismo , Bacterias/metabolismo , Sulfatos/metabolismo
16.
Chemosphere ; 338: 139515, 2023 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-37474034

RESUMEN

Energy conversion of waste activated sludge alkaline fermentation liquor (WASAFL) to medium-chain fatty acids (MCFAs) is promising for sludge treatment and carbon recovery. However, the single electron donor (ED) fermentation for MCFAs production has irreparable defects. To resolve the respective shortcomings of single electron donor (ED) and improve the MCFAs production efficiency from WASAFL, a novel biotechnical process utilizing ethanol and lactate as co-EDs within different combination ratios were investigated. The results verified that MCFAs production was highest with ethanol to lactate ratio of 1:3 (6988.54 ± 208.18 mg COD/L), being 1.46 and 1.87 times of that with ethanol and lactate as single ED. The kinetic analysis results confirmed that ethanol to lactate ratio of 1:3 resulted in the highest MCFAs yield and formation rate. The microbial taxa results uncovered that the relative abundance of Sphaerochaeta and Haloimpatiens showed positive correlation with MCFAs production. The metabolic pathway analysis indicated that the ethanol oxidization, lactate oxidization, acrylate pathway, reverse ß oxidization and fatty acid biosynthesis pathway might take place in the WASAFL fermentation system, contributing to the WASAFL-to-MCFAs conversion.


Asunto(s)
Electrones , Aguas del Alcantarillado , Cinética , Ácidos Grasos/metabolismo , Fermentación , Etanol , Ácido Láctico , Redes y Vías Metabólicas , Ácidos Grasos Volátiles
17.
Angew Chem Int Ed Engl ; 62(33): e202305571, 2023 Aug 14.
Artículo en Inglés | MEDLINE | ID: mdl-37312245

RESUMEN

Maximizing hole-transfer kinetics-usually a rate-determining step in semiconductor-based artificial photosynthesis-is pivotal for simultaneously enabling high-efficiency solar hydrogen production and hole utilization. However, this remains elusive yet as efforts are largely focused on optimizing the electron-involved half-reactions only by empirically employing sacrificial electron donors (SEDs) to consume the wasted holes. Using high-quality ZnSe quantum wires as models, we show that how hole-transfer processes in different SEDs affect their photocatalytic performances. We found that larger driving forces of SEDs monotonically enhance hole-transfer rates and photocatalytic performances by almost three orders of magnitude, a result conforming well with the Auger-assisted hole-transfer model in quantum-confined systems. Intriguingly, further loading Pt cocatalyts can yield either an Auger-assisted model or a Marcus inverted region for electron transfer, depending on the competing hole-transfer kinetics in SEDs.

18.
Angew Chem Int Ed Engl ; 62(33): e202306667, 2023 Aug 14.
Artículo en Inglés | MEDLINE | ID: mdl-37378963

RESUMEN

Catalysts with metal-Nx sites have long been considered as effective electrocatalysts for oxygen reduction reaction (ORR), yet the accurate structure-property correlations of these active sites remain debatable. Report here is a proof-of-concept method to construct 1,4,8,11-tetraaza[14]annulene (TAA)-based polymer nanocomposites with well-managed electronic microenvironment via electron-donors/acceptors interaction of altering electron-withdrawing ß-site substituents. DFT calculation proves the optimal -Cl substituted catalyst (CoTAA-Cl@GR) tailored the key OH* intermediate interaction with Co-N4 sites under the d-orbital regulation, hence reaching the top of ORR performance with excellent turnover frequency (0.49 e s-1 site-1 ). The combination of in situ scanning electrochemical microscopy and variable-frequency square wave voltammetry techniques contribute the great ORR kinetics of CoTAA-Cl@GR to the relatively high accessible site density (7.71×1019  site g-1 ) and fast electron outbound propagation mechanism. This work provides theoretical guidance for rational design of high-performance catalysts for ORR and beyond.

19.
ACS Synth Biol ; 12(4): 947-962, 2023 04 21.
Artículo en Inglés | MEDLINE | ID: mdl-37052416

RESUMEN

The construction from scratch of synthetic cells by assembling molecular building blocks is unquestionably an ambitious goal from a scientific and technological point of view. To realize functional life-like systems, minimal enzymatic modules are required to sustain the processes underlying the out-of-equilibrium thermodynamic status hallmarking life, including the essential supply of energy in the form of electrons. The nicotinamide cofactors NAD(H) and NADP(H) are the main electron carriers fueling reductive redox reactions of the metabolic network of living cells. One way to ensure the continuous availability of reduced nicotinamide cofactors in a synthetic cell is to build a minimal enzymatic module that can oxidize an external electron donor and reduce NAD(P)+. In the diverse world of metabolism there is a plethora of potential electron donors and enzymes known from living organisms to provide reducing power to NAD(P)+ coenzymes. This perspective proposes guidelines to enable the reduction of nicotinamide cofactors enclosed in phospholipid vesicles, while avoiding high burdens of or cross-talk with other encapsulated metabolic modules. By determining key requirements, such as the feasibility of the reaction and transport of the electron donor into the cell-like compartment, we select a shortlist of potentially suitable electron donors. We review the most convenient proteins for the use of these reducing agents, highlighting their main biochemical and structural features. Noting that specificity toward either NAD(H) or NADP(H) imposes a limitation common to most of the analyzed enzymes, we discuss the need for specific enzymes─transhydrogenases─to overcome this potential bottleneck.


Asunto(s)
Células Artificiales , NAD , NAD/metabolismo , NADP/metabolismo , Coenzimas/metabolismo , Oxidación-Reducción , Niacinamida
20.
Small ; 19(31): e2206222, 2023 08.
Artículo en Inglés | MEDLINE | ID: mdl-36907994

RESUMEN

Optimizing photosynthesis is imperative for providing energy and organics for all life on the earth. Here, carbon dots doped with pyridinic nitrogen (named lev-CDs) are synthesized by the one-pot hydrothermal method, and the structure-function relationship between functional groups on lev-CDs and photosynthesis of Chlorella pyrenoidosa (C. pyrenoidosa) is proposed. Pyridinic nitrogen plays a key role in the positive effect on photosynthesis caused by lev-CDs. In detail, lev-CDs act as electron donors to supply photo-induced electrons to P680+ and QA+ , causing electron transfer from lev-CDs to the photosynthetic electron transport chain in the photosystems. In return, the recombination efficiency of electron-hole pairs on lev-CDs decreases. As a result, the electron transfer rate in the electron transport chain, the activity of photosystem II, and the Calvin cycle are enhanced. Moreover, the electron transfer rate between C. pyrenoidosa and external circumstances enhanced by lev-CDs is about 50%, and electrons exported from C. pyrenoidosa can be used to reduce iron(III). This study is of great significance for engineering nanomaterials to improve photosynthesis.


Asunto(s)
Chlorella , Puntos Cuánticos , Transporte de Electrón , Electrones , Carbono/farmacología , Nitrógeno , Compuestos Férricos/farmacología , Fotosíntesis
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