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1.
Nano Lett ; 24(29): 9011-9016, 2024 Jul 24.
Artículo en Inglés | MEDLINE | ID: mdl-38985522

RESUMEN

Electroreduction of nitrate/nitrite to high-value-added products, including NH2OH, is an important way to achieve sustainable production of green energy. However, this electrosynthesis of NH2OH still suffers from poor selectivity due to the various competing reactions. Here, we screen out Ni-N4 and Cu-N4 catalysts for highly efficient nitrite electroreduction to NH2OH by adopting density functional theory (DFT) calculations. DFT calculations reveal that the high selectivity of Ni-N4 and Cu-N4 is ascribed to their weak adsorption of *NH2OH and *NH intermediates, thereby preventing the further reduction of NH2OH. Moreover, using *NO as a model intermediate, we studied the relationship between the 3d orbital occupancy and adsorption strength of the intermediate. It is found that Ni-N4 and Cu-N4 with fully occupied dxz, dyz, and dz2 orbitals have poor adsorption of *NO intermediate. This work provides a new route for NH2OH synthesis and offers perspectives on the crucial factors in determining the catalytic selectivity.

2.
Small ; : e2310409, 2024 Mar 13.
Artículo en Inglés | MEDLINE | ID: mdl-38477694

RESUMEN

Electrochemical nitrite reduction reaction ( NO 2 - RR ${\mathrm{NO}}_{\mathrm{2}}^{\mathrm{ - }}{\mathrm{RR}}$ ), as a green and sustainable ammonia synthesis technology, has broad application prospects and environmental friendliness. Herein, an unconventional p-d orbital hybridization strategy is reported to realize the fabrication of defect-rich CuSb porous nanonetwork (CuSb PNs) electrocatalyst for NO 2 - RR ${\mathrm{NO}}_{\mathrm{2}}^ - {\mathrm{RR}}$ . The crystalline/amorphous heterophase structure is cleverly introduced into the porous nanonetworks, and this defect-rich structure exposes more atoms and activated boundaries. CuSb PNs exhibit a large NH3 yield ( r N H 3 ${{r}_{{\mathrm{N}}{{{\mathrm{H}}}_{\mathrm{3}}}}}$ ) of 946.1 µg h-1 m cat - 1 ${\mathrm{m}}_{{\mathrm{cat}}}^{ - {\mathrm{1}}}$ and a high faradaic efficiency (FE) of 90.7%. Experimental and theoretical studies indicate that the excellent performance of CuSb PNs results from the defect-rich porous nanonetworks structure and the p-d hybridization of Cu and Sb elements. This work describes a powerful pathway for the fabrication of p-d orbital hybrid defect-rich porous nanonetworks catalysts, and provides hope for solving the problem of nitrogen oxide pollution in the field of environment and energy.

3.
Small ; 20(29): e2400538, 2024 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-38600896

RESUMEN

This research adopts a new method combining calcination and pulsed laser irradiation in liquids to induce a controlled phase transformation of Fe, Co, Ni, Cu, and Mn transition-metal-based high-entropy Prussian blue analogs into single-phase spinel high-entropy oxide and face-centered cubic high-entropy alloy (HEA). The synthesized HEA, characterized by its highly conductive nature and reactive surface, demonstrates exceptional performance in capturing low-level nitrite (NO2 -) in an electrolyte, which leads to its efficient conversion into ammonium (NH4 +) with a Faradaic efficiency of 79.77% and N selectivity of 61.49% at -0.8 V versus Ag/AgCl. In addition, the HEA exhibits remarkable durability in the continuous nitrite reduction reaction (NO2 -RR), converting 79.35% of the initial NO2 - into NH4 + with an impressive yield of 1101.48 µm h-1 cm-2. By employing advanced X-ray absorption and in situ electrochemical Raman techniques, this study provides insights into the indirect NO2 -RR, highlighting the versatility and efficacy of HEA in sustainable electrochemical applications.

4.
Arch Microbiol ; 206(4): 179, 2024 Mar 18.
Artículo en Inglés | MEDLINE | ID: mdl-38498215

RESUMEN

Sediments underlying marine hypoxic zones are huge sinks of unreacted complex organic matter, where despite acute O2 limitation, obligately aerobic bacteria thrive, and steady depletion of organic carbon takes place within a few meters below the seafloor. However, little knowledge exists about the sustenance and complex carbon degradation potentials of aerobic chemoorganotrophs in these sulfidic ecosystems. We isolated and characterized a number of aerobic bacterial chemoorganoheterotrophs from across a ~ 3 m sediment horizon underlying the perennial hypoxic zone of the eastern Arabian Sea. High levels of sequence correspondence between the isolates' genomes and the habitat's metagenomes and metatranscriptomes illustrated that the strains were widespread and active across the sediment cores explored. The isolates catabolized several complex organic compounds of marine and terrestrial origins in the presence of high or low, but not zero, O2. Some of them could also grow anaerobically on yeast extract or acetate by reducing nitrate and/or nitrite. Fermentation did not support growth, but enabled all the strains to maintain a fraction of their cell populations over prolonged anoxia. Under extreme oligotrophy, limited growth followed by protracted stationary phase was observed for all the isolates at low cell density, amid high or low, but not zero, O2 concentration. While population control and maintenance could be particularly useful for the strains' survival in the critically carbon-depleted layers below the explored sediment depths (core-bottom organic carbon: 0.5-1.0% w/w), metagenomic data suggested that in situ anoxia could be surmounted via potential supplies of cryptic O2 from previously reported sources such as Nitrosopumilus species.


Asunto(s)
Ecosistema , Oxígeno , Humanos , Oxígeno/metabolismo , Sedimentos Geológicos/microbiología , Carbono/metabolismo , Bacterias , Hipoxia
5.
J Environ Manage ; 357: 120843, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38588621

RESUMEN

Nitrite-dependent anaerobic methane oxidation (n-DAMO) is a novel denitrification process that simultaneously further removes and utilizes methane from anaerobic effluent from wastewater treatment plants. However, the metabolic activity of n-DAMO bacteria is relative low for practical application. In this study, conductive magnetite was added into lab-scale sequencing batch reactor inoculated with n-DAMO bacteria to study the influence on n-DAMO process. With magnetite amendment, the nitrogen removal rate could reach 34.9 mg N·L-1d-1, nearly 2.5 times more than that of control group. Magnetite significantly facilitated the interspecies electron transfer and built electrically connected community with high capacitance. Enzymatic activities of electron transport chain were significantly elevated. Functional gene expression and enzyme activities associated with nitrogen and methane metabolism had been highly up-regulated. These results not only propose a useful strategy in n-DAMO application but also provide insights into the stimulating mechanism of magnetite in n-DAMO process.


Asunto(s)
Óxido Ferrosoférrico , Nitritos , Nitritos/metabolismo , Transporte de Electrón , Anaerobiosis , Metano , Electrones , Desnitrificación , Oxidación-Reducción , Bacterias/metabolismo , Bacterias Anaerobias/metabolismo , Nitrógeno/metabolismo , Reactores Biológicos/microbiología
6.
Angew Chem Int Ed Engl ; 63(2): e202313434, 2024 Jan 08.
Artículo en Inglés | MEDLINE | ID: mdl-37996973

RESUMEN

The development of environmentally sustainable and highly efficient technologies for ammonia production is crucial for the future advancement of carbon-neutral energy systems. The nitrite reduction reaction (NO2 RR) for generating NH3 is a promising alternative to the low-efficiency nitrogen reduction reaction (NRR), owing to the low N=O bond energy and high solubility of nitrite. In this study, we designed a highly efficient dual-atom catalyst with Fe-Cu atomic pair sites (termed FeCu DAC), and the as-developed FeCu DAC was able to afford a remarkable NH3 yield of 24,526 µg h-1 mgcat. -1 at -0.6 V, with a Faradaic Efficiency (FE) for NH3 production of 99.88 %. The FeCu DAC also exhibited exceptional catalytic activity and selectivity in a Zn-NO2 battery, achieving a record-breaking power density of 23.6 mW cm-2 and maximum NH3 FE of 92.23 % at 20 mA cm-2 . Theoretical simulation demonstrated that the incorporation of the Cu atom changed the energy of the Fe 3d orbital and lowered the energy barrier, thereby accelerating the NO2 RR. This study not only demonstrates the potential of galvanic nitrite-based cells for expanding the field of Zn-based batteries, but also provides fundamental interpretation for the synergistic effect in highly dispersed dual-atom catalysts.

7.
Angew Chem Int Ed Engl ; 63(29): e202405459, 2024 Jul 15.
Artículo en Inglés | MEDLINE | ID: mdl-38711309

RESUMEN

The hydrogen evolution and nitrite reduction reactions are key to producing green hydrogen and ammonia. Antenna-reactor nanoparticles hold promise to improve the performances of these transformations under visible-light excitation, by combining plasmonic and catalytic materials. However, current materials involve compromising either on the catalytic activity or the plasmonic enhancement and also lack control of reaction selectivity. Here, we demonstrate that ultralow loadings and non-uniform surface segregation of the catalytic component optimize catalytic activity and selectivity under visible-light irradiation. Taking Pt-Au as an example we find that fine-tuning the Pt content produces a 6-fold increase in the hydrogen evolution compared to commercial Pt/C as well as a 6.5-fold increase in the nitrite reduction and a 2.5-fold increase in the selectivity for producing ammonia under visible light excitation relative to dark conditions. Density functional theory suggests that the catalytic reactions are accelerated by the intimate contact between nanoscale Pt-rich and Au-rich regions at the surface, which facilitates the formation of electron-rich hot-carrier puddles associated with the Pt-based active sites. The results provide exciting opportunities to design new materials with improved photocatalytic performance for sustainable energy applications.

8.
Small ; 19(30): e2300620, 2023 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-37058080

RESUMEN

Electroreduction of nitrite (NO2 - ) to valuable ammonia (NH3 ) offers a sustainable and green approach for NH3 synthesis. Here, a Cu3 P@TiO2 heterostructure is rationally constructed as an active catalyst for selective NO2 - -to-NH3 electroreduction, with rich nanosized Cu3 P anchored on a TiO2 nanoribbon array on Ti plate (Cu3 P@TiO2 /TP). When performed in the 0.1 m NaOH with 0.1 m NaNO2 , the Cu3 P@TiO2 /TP electrode obtains a large NH3 yield of 1583.4 µmol h-1  cm-2 and a high Faradaic efficiency of 97.1%. More importantly, Cu3 P@TiO2 /TP also delivers remarkable long-term stability for 50 h electrolysis. Theoretical calculations indicate that intermediate adsorption/conversion processes on Cu3 P@TiO2 interfaces are synergistically optimized, substantially facilitating the conversion of NO2 - -to-NH3 .

9.
BMC Microbiol ; 23(1): 210, 2023 08 05.
Artículo en Inglés | MEDLINE | ID: mdl-37543572

RESUMEN

BACKGROUND: A wide variety of microorganisms, including bacteria, live in the rhizosphere zone of plants and have an impact on plant development both favorably and adversely. The beneficial outcome is due to the presence of rhizobacteria that promote plant growth (PGPR). RESULTS: In this study, a bacterial strain was isolated from lupin rhizosphere and identified genetically as Serratia marcescens (OK482790). Several biochemically and genetically characteristics were confirmed in vitro and in vivo to determine the OK482790 strain ability to be PGPR. The in vitro results revealed production of different lytic enzymes (protease, lipase, cellulase, and catalase), antimicrobial compounds (hydrogen cyanide, and siderophores), ammonia, nitrite, and nitrate and its ability to reduce nitrate to nitrite. In silico and in vitro screening proposed possible denitrification-DNRA-nitrification pathway for OK482790 strain. The genome screening indicated the presence of nitrite and nitrate genes encoding Nar membrane bound sensor proteins (NarK, NarQ and NarX). Nitrate and nitrite reductase encoding genes (NarI, NarJ, NarH, NarG and NapC/NirT) and (NirB, NirC, and NirD) are also found in addition to nitroreductases (NTR) and several oxidoreductases. In vivo results on wheat seedlings confirmed that seedlings growth was significantly improved by soil inoculation of OK482790 strain. CONCLUSIONS: This study provides evidence for participation of S. marcescens OK482790 in nitrogen cycling via the denitrification-DNRA-nitrification pathway and for its ability to produce several enzymes and compounds that support the beneficial role of plant-microbe interactions to sustain plant growth and development for a safer environment.


Asunto(s)
Nitratos , Nitritos , Nitratos/metabolismo , Nitritos/metabolismo , Nitrificación , Serratia marcescens/metabolismo , Desnitrificación , Desarrollo de la Planta , Nitrógeno
10.
Environ Sci Technol ; 57(33): 12546-12555, 2023 08 22.
Artículo en Inglés | MEDLINE | ID: mdl-37535944

RESUMEN

Microbially mediated nitrate reduction coupled with Fe(II) oxidation (NRFO) plays an important role in the Fe/N interactions in pH-neutral anoxic environments. However, the relative contributions of the chemical and microbial processes to NRFO are still unclear. In this study, N-O isotope fractionation during NRFO was investigated. The ratios of O and N isotope enrichment factors (18ε:15ε)-NO3- indicated that the main nitrate reductase functioning in Acidovorax sp. strain BoFeN1 was membrane-bound dissimilatory nitrate reductase (Nar). N-O isotope fractionation during chemodenitrification [Fe(II) + NO2-], microbial nitrite reduction (cells + NO2-), and the coupled process [cells + NO2- + Fe(II)] was explored. The ratios of (18ε:15ε)-NO2- were 0.58 ± 0.05 during chemodenitrification and -0.41 ± 0.11 during microbial nitrite reduction, indicating that N-O isotopes can be used to distinguish chemical from biological reactions. The (18ε:15ε)-NO2- of 0.70 ± 0.05 during the coupled process was close to that obtained for chemodenitrification, indicating that chemodenitrification played a more important role than biological reactions during the coupled process. The results of kinetic modeling showed that the relative contribution of chemodenitrification was 99.3% during the coupled process, which was consistent with that of isotope fractionation. This study provides a better understanding of chemical and biological mechanisms of NRFO using N-O isotopes and kinetic modeling.


Asunto(s)
Comamonadaceae , Nitratos , Nitritos , Dióxido de Nitrógeno , Oxidación-Reducción , Compuestos Orgánicos , Isótopos , Compuestos Ferrosos
11.
Molecules ; 28(9)2023 May 04.
Artículo en Inglés | MEDLINE | ID: mdl-37175275

RESUMEN

Recently, single-atom catalysts (SACs) have attracted wide attention in the field of environmental engineering. Compared with their nanoparticle counterparts, SACs possess high atomic efficiency, unique catalytic activity, and selectivity. This review summarizes recent studies on the environmental remediation applications of SACs in (1) gaseous: volatile organic compounds (VOCs) treatment, NOx reduction, CO2 reduction, and CO oxidation; (2) aqueous: Fenton-like advanced oxidation processes (AOPs), hydrodehalogenation, and nitrate/nitrite reduction. We present the treatment activities and reaction mechanisms of various SACs and propose challenges and future opportunities. We believe that this review will provide constructive inspiration and direction for future SAC research in environmental engineering.

12.
Angew Chem Int Ed Engl ; 62(3): e202213711, 2023 Jan 16.
Artículo en Inglés | MEDLINE | ID: mdl-36418219

RESUMEN

Electrochemical reduction of nitrite (NO2 - ) offers an energy-efficient route for ammonia (NH3 ) synthesis and reduction of the level of nitrite, which is one of the major pollutants in water. However, the near 100 % Faradaic efficiency (FE) has yet to be achieved due to the complicated reduction route with several intermediates. Here, we report that carbon dioxide (CO2 ) can enhance the nitrite electroreduction to ammonia on copper nanowire (Cu NW) catalysts. In a broad potential range (-0.7∼-1.3 V vs. RHE), the FE of nitrite to ammonia is close to 100 % with a 3.5-fold increase in activity compared to that obtained without CO2. In situ Raman spectroscopy and density functional theory (DFT) calculations indicate that CO2 acts as a catalyst to facilitate the *NO to *N step, which is the rate determining step for ammonia synthesis. The promotion effect of CO2 can be expanded to electroreduction of other nitro-compounds, such as nitrate to ammonia and nitrobenzene to aniline.

13.
J Biol Chem ; 296: 100476, 2021.
Artículo en Inglés | MEDLINE | ID: mdl-33652023

RESUMEN

The hydroxylamine oxidoreductase (HAO) family consists of octaheme proteins that harbor seven bis-His ligated electron-transferring hemes and one 5-coordinate catalytic heme with His axial ligation. Oxidative HAOs have a homotrimeric configuration with the monomers covalently attached to each other via a unique double cross-link between a Tyr residue and the catalytic heme moiety of an adjacent subunit. This cross-linked active site heme, termed the P460 cofactor, has been hypothesized to modulate enzyme reactivity toward oxidative catalysis. Conversely, the absence of this cross-link is predicted to favor reductive catalysis. However, this prediction has not been directly tested. In this study, an HAO homolog that lacks the heme-Tyr cross-link (HAOr) was purified to homogeneity from the nitrite-dependent anaerobic ammonium-oxidizing (anammox) bacterium Kuenenia stuttgartiensis, and its catalytic and spectroscopic properties were assessed. We show that HAOr reduced nitrite to nitric oxide and also reduced nitric oxide and hydroxylamine as nonphysiological substrates. In contrast, HAOr was not able to oxidize hydroxylamine or hydrazine supporting the notion that cross-link-deficient HAO enzymes are reductases. Compared with oxidative HAOs, we found that HAOr harbors an active site heme with a higher (at least 80 mV) midpoint potential and a much lower degree of porphyrin ruffling. Based on the physiology of anammox bacteria and our results, we propose that HAOr reduces nitrite to nitric oxide in vivo, providing anammox bacteria with NO, which they use to activate ammonium in the absence of oxygen.


Asunto(s)
Oxidorreductasas/química , Oxidorreductasas/metabolismo , Planctomycetales/metabolismo , Compuestos de Amonio/metabolismo , Bacterias/metabolismo , Catálisis , Dominio Catalítico , Transporte de Electrón/fisiología , Hemo/metabolismo , Hidrazinas/química , Hidroxilamina/química , Hidroxilaminas/química , Óxido Nítrico/metabolismo , Nitritos/metabolismo , Oxidación-Reducción , Tirosina/química , Tirosina/metabolismo
14.
Nitric Oxide ; 125-126: 12-22, 2022 08 01.
Artículo en Inglés | MEDLINE | ID: mdl-35667547

RESUMEN

Cytoglobin is a hemoprotein widely expressed in fibroblasts and related cell lineages with yet undefined physiological function. Cytoglobin, as other heme proteins, can reduce nitrite to nitric oxide (NO) providing a route to generate NO in vivo in low oxygen conditions. In addition, cytoglobin can also bind lipids such as oleic acid and cardiolipin with high affinity. These two processes are potentially relevant to cytoglobin function. Little is known about how specific amino acids contribute to nitrite reduction and lipid binding. Here we investigate the role of the distal histidine His81 (E7) and several surface residues on the regulation of nitrite reduction and lipid binding. We observe that the replacement of His81 (E7) greatly increases heme reactivity towards nitrite, with nitrite reduction rate constants of up to 1100 M-1s-1 for the His81Ala mutant. His81 (E7) mutation causes a small decrease in lipid binding affinity, however experiments on the presence of imidazole indicate that His81 (E7) does not compete with the lipid for the binding site. Mutations of the surface residues Arg84 and Lys116 largely impair lipid binding. Our results suggest that dissociation of His81 (E7) from the heme mediates the formation of a hydrophobic cavity in the proximal heme side that can accommodate the lipid, with important contributions of the hydrophobic patch around residues Thr91, Val105, and Leu108, whereas the positive charges from Arg84 and Lys116 stabilize the carboxyl group of the fatty acid. Gain and loss-of-function mutations described here can serve as tools to study in vivo the physiological role of these putative cytoglobin functions.


Asunto(s)
Globinas , Nitrito Reductasas , Citoglobina/genética , Globinas/metabolismo , Hemo/química , Histidina/genética , Lípidos , Mutación , Óxido Nítrico/metabolismo , Nitrito Reductasas/metabolismo , Nitritos/metabolismo
15.
Vasc Med ; 27(1): 3-12, 2022 02.
Artículo en Inglés | MEDLINE | ID: mdl-34570637

RESUMEN

Endothelium-derived nitric oxide (NO) is a mediator of angiogenesis. However, NO-mediated regulation of vasculogenesis remains largely unknown. In the present study, we show that the inhibition of NO significantly attenuated endothelial migration, ring formation, and tube formation. The contribution of nitric oxide synthase (NOS) enzymes during early vasculogenesis was assessed by evaluating endothelial NOS (eNOS) and inducible NOS (iNOS) mRNA expression during HH10-HH13 stages of chick embryo development. iNOS but not eNOS was expressed at HH12 and HH13 stages. We hypothesized that vasculogenic events are controlled by NOS-independent reduction of nitrite to NO under hypoxia during the very early phases of development. Semi-quantitative polymerase chain reaction analysis of hypoxia-inducible factor-1α (HIF-1α) showed higher expression at HH10 stage, after which a decrease was observed. This observation was in correlation with the nitrite reductase (NR) activity at HH10 stage. We observed a sodium nitrite-induced increase in NO levels at HH10, reaching a gradual decrease at HH13. The possible involvement of a HIF/NF-κB/iNOS signaling pathway in the process of early vasculogenesis is suggested by the inverse relationship observed between nitrite reduction and NOS activation between HH10 and HH13 stages. Further, we detected that NR-mediated NO production was inhibited by several NR inhibitors at the HH10 stage, whereas the inhibitors eventually became less effective at later stages. These findings suggest that the temporal dynamics of the NO source switches from NR to NOS in the extraembryonic area vasculosa, where both nitrite reduction and NOS activity are defined by hypoxia.


Asunto(s)
Óxido Nítrico Sintasa de Tipo III , Óxido Nítrico , Animales , Embrión de Pollo , FN-kappa B/metabolismo , Óxido Nítrico/metabolismo , Óxido Nítrico Sintasa/genética , Óxido Nítrico Sintasa/metabolismo , Óxido Nítrico Sintasa de Tipo II/genética , Óxido Nítrico Sintasa de Tipo II/metabolismo , Óxido Nítrico Sintasa de Tipo III/genética , Óxido Nítrico Sintasa de Tipo III/metabolismo , Nitritos , Transducción de Señal
16.
Environ Res ; 215(Pt 1): 114154, 2022 12.
Artículo en Inglés | MEDLINE | ID: mdl-36037916

RESUMEN

The biochemical reduction of nitrite (NO2-) ions to ammonia (NH3) requires six electrons and is catalyzed by the cytochrome c NO2- reductase enzyme. This biological reaction inspired scientists to explore the reduction of nitrogen oxyanions, such as nitrate (NO3-) and NO2- in wastewater, to produce the more valuable NH3 product. It is widely known that copper (Cu)-based nanoparticles (NPs) are selective for the NO3- reduction reaction (NO3-RR), but the NO2-RR has not been well explored. Therefore, we attempted to address the electrocatalytic conversion of NO2- to NH3 using Cu@Cu2O core-shell NPs to simultaneously treat wastewater by removing NO2- and producing valuable NH3. The Cu@Cu2O core-shell NPs were constructed using the pulsed laser ablation of Cu sheet metal in water. The core-shell nanostructure of these particles was confirmed by various characterization techniques. Subsequently, the removal of NO2- and the ammonium (NH4+)-N yield rate were estimated using the Griess and indophenol blue methods, respectively. Impressively, the Cu@Cu2O core-shell NPs exhibited outstanding NO2-RR activity, demonstrating a maximum NO2- removal efficiency of approximately 94% and a high NH4+-N yield rate of approximately 0.03 mmol h-1.cm-2 at -1.6 V vs. a silver/silver chloride reference electrode under optimal conditions. The proposed NO2-RR mechanism revealed that the (111) facet of Cu favors the selective conversion of NO2- to NH3 via a six-electron transfer. This investigation may offer a new insight for the rational design and detailed mechanistic understanding of electrocatalyst architecture for the effective conversion of NO2- to NH4+.


Asunto(s)
Compuestos de Amonio , Nanoestructuras , Amoníaco/química , Cobre/química , Citocromos c/metabolismo , Indofenol , Rayos Láser , Nitratos/análisis , Nitritos , Nitrógeno , Dióxido de Nitrógeno , Oxidación-Reducción , Oxidorreductasas/metabolismo , Plata , Aguas Residuales , Agua
17.
Chemistry ; 27(45): 11676-11681, 2021 Aug 11.
Artículo en Inglés | MEDLINE | ID: mdl-34008888

RESUMEN

The reaction chemistry of the bis-tetrazinyl pyridine ligand (btzp) towards nitrogen oxyanions coordinated to zinc is studied in order to explore the reduction of the NOx - substrates with a redox-active ligand in the absence of redox activity at the metal. Following syntheses and characterization of (btzp)ZnX2 for X=Cl, NO3 and NO2 , featuring O-Zn linkage of both nitrogen oxyanions, it is shown that a silylating agent selectively delivers silyl substituents to tetrazine nitrogens, without reductive deoxygenation of NOx -1 . A new synthesis of the highly hydrogenated H4 btzp, containing two dihydrotetrazine reductants is described as is the synthesis and characterization of (H4 btzp)ZnX2 for X=Cl and NO3 , both of which show considerable hydrogen bonding potential of the dihydrotetrazine ring NH groups. The (H4 btzp)ZnCl2 complex does not bind zinc in the pincer pocket, but instead H4 btzp becomes a bridge between neighboring atoms through tetrazine nitrogen atoms, forming a polymeric chain. The reaction of AgNO2 with (H4 btzp)ZnCl2 is shown to proceed with fast nitrite deoxygenation, yielding water and free NO. Half of the H4 btzp reducing equivalents form Ag0 and thus the chloride ligand remains coordinated to the zinc metal center to yield (btzp)ZnCl2 . To compare with AgNO2 , experiments of (H4 btzp)ZnCl2 with NaNO2 result in salt metathesis between chloride and nitrite, highlighting the importance of a redox-active cation in the reduction of nitrite to NO.

18.
Ecotoxicol Environ Saf ; 224: 112693, 2021 Aug 23.
Artículo en Inglés | MEDLINE | ID: mdl-34438268

RESUMEN

Biological nitrogen removal is primarily conducted by bacteria and fungi rather than actinomycetes. However, accumulations of nitrite and hydroxylamine could significantly impair the biological nitrogen removal process. A strain of Streptomyces mediolani, termed EM-B2, was isolated from a cow dung fermentation biogas digester. The strain removed more than 99% of ammonium and 78% of total nitrogen in the presence of glucose and under environmental conditions of 30 °C, a carbon/nitrogen ratio of 15, 7.4 mg/L dissolved oxygen and a pH range of 7.5-9.0. Maximal removal rates were 2.29 mg/L/h for ammonium, 1.90 mg/L/h for nitrate and 2.01 mg/L/h for nitrite. The removal efficiencies of hydroxylamine and total nitrogen peaked at 81.48% and 60.38%, respectively. Notably, hydroxylamine and nitrite were never detected during the heterotrophic nitrification and aerobic denitrification. Nitrate rather than nitrite was accumulated from the process of hydroxylamine oxidation. These findings indicate that S. mediolani strain EM-B2 performs heterotrophic nitrification and aerobic denitrification, and can be used to remove hydroxylamine and nitrite from wastewater.

19.
Arch Pharm (Weinheim) ; 354(7): e2000354, 2021 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-33749005

RESUMEN

Coumarins (2H-1-benzopyran-2-one), derivatives that can be isolated from several plants, have been reported for their anticoagulant, antimicrobial, anti-inflammatory, or anticancer activity. Some of these structures are currently approved for the treatment of cardiovascular diseases, as antibiotics or as an anticancer drug. Given the great potential of this structure and the limited number of studies that focus on molecules derived from carbon 8 of the benzopyranone heterocycle, we synthesized in this project 38 coumarin derivatives by substituting carbon 8 of the benzopyran ring with some aromatic and aliphatically substituted piperidines and piperazines. As a few of these structures were already shown to exhibit some carbonic anhydrase (CA) inhibition and as CA enzymes are reported to be closely related to inflammation, the synthesized derivatives were evaluated for their anti-inflammatory activity in vitro. The results indicated that compounds 20 and 31 revealed promising anti-inflammatory activity, as they demonstrated better activity than the reference drugs.


Asunto(s)
Antiinflamatorios/farmacología , Cumarinas/farmacología , Piperazinas/farmacología , Piperidinas/farmacología , Animales , Antiinflamatorios/síntesis química , Antiinflamatorios/química , Cumarinas/síntesis química , Cumarinas/química , Inflamación/tratamiento farmacológico , Inflamación/patología , Ratones , Piperazinas/síntesis química , Piperazinas/química , Piperidinas/síntesis química , Piperidinas/química , Células RAW 264.7 , Relación Estructura-Actividad
20.
Food Technol Biotechnol ; 59(2): 185-193, 2021 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-34316279

RESUMEN

RESEARCH BACKGROUND: The industrial transformation of tropical fruits, and in particular guava, generates a large quantity of by-products that are generally disposed of as organic waste. In these by-products a large quantity of bioactive substances is concentrated, such as carotenoids, which can be used for the partial substitution of nitrites in meat sausages without affecting their physicochemical, colour and conservation characteristics. Although there are some studies in this regard, there is still a lack of research, especially on guava residues, to verify this hypothesis. Therefore, the aim of this study is to investigate the influence of the components of the guava epicarp extract on the physicochemical, textural, colour and sensory properties of frankfurters. EXPERIMENTAL APPROACH: There treatments were investigated (25, 50 and 75% nitrite replacement with guava epicarp flour extract), along with a control treatment without the extract. The physicochemical properties, colour coordinates, and texture parameters were analysed, and a sensory evaluation was also carried out. The treatment that gave the best results was subjected to stability analysis over 30 days. RESULTS AND CONCLUSIONS: The addition of 25% guava epicarp flour extract gave the best results, since it did not affect the colouration of the sausages or their physicochemical and textural properties. Likewise, during the stability analysis over time, the parameters related to fat oxidation were not affected, and final products had a residual nitrite load of (23.6±0.2) mg/kg, lower than the maximum allowed (150 mg/kg). NOVELTY AND SCIENTIFIC CONTRIBUTION: The partial substitution of the nitrites in frankfurters with the carotenoids from the guava epicarp flour added in a mass fraction up to 25% can be a viable alternative to produce sausages with lower content of nitrites, without affecting their colouration or shelf life. This is important for the meat industry, which favours the development of new products using substances of natural origin.

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