Reaction of nitric oxide and nitric oxide + carbon monoxide with amorphous Fe-Co-B alloy powders

The activity of amorphous Fe---Co---B alloy powder was investigated for the decomposition and the reduction of nitrogen monoxide. The transient response technique and a fixed bed reactor were applied to study the interactions of the Fe---Co---B alloy with two gas mixtures: NO + Ar at 353 and 573 K and NO + CO + Ar at 333–573 K. Moessbauer spectroscopy and X-ray photoelectron spectroscopy (XPS) were used to study the state of the initial sample and the samples utilized in both gas mixtures. It is shown that the amorphous Fe---Co---B alloy powder has an activity for the direct decomposition of nitric oxide to nitrous oxide and nitrogen at a high gas space velocity (26 000 h⁻¹). Oxygen from the decomposed nitric oxide poisons the surface for the formation of nitrogen. In the presence of carbon monoxide (a NO + CO + Ar gas mixture) nitric oxide is reduced to nitrous oxide at 333–353 K and fully reduced to nitrogen at 373–573 K. The quantities of the carbon dioxide formed are not equal to the values expected from the stoichiometry of the NO + CO reaction. Probably, the interaction of carbon monoxide with the adsorbed oxygen (left on the surface by the decomposed nitric oxide) enhances the rate of nitric oxide decomposition to nitrous oxide and nitrogen. The rate limiting steps for both reactions of nitric oxide decomposition, as indicated by the transient response data, change with increasing temperature. The data from the Moessbauer spectroscopy and the X-ray photoelectron spectroscopy (XPS) studies have shown that the amorphous Fe---Co---B alloy powder undergoes phase changes under the conditions of both, the NO + Ar and the NO + CO + Ar gas mixtures. Boron migrates to the surface of globules and serves the accumulation of oxygen by the formation of B₂O₃ (or B(OH)₃).     

Electrochemical high-content screening of nitric oxide release from endothelial cells

Release of nitric oxide (NO) is of high importance for regulating endothelial cell functions during vasodilatation, vascular remodeling, and angiogenesis. Thus, a direct and reliable real-time method for NO detection that takes into account time-dependent variations of the NO concentration in the complex reaction within the diffusion zone above the cells is vital for obtaining information about the role of NO in intracellular endothelial signal transduction and its impact on the surrounding cells. In this study, the time course of vascular endothelial growth factor E (VEGF-E) stimulated NO release from transformed human umbilical vein endothelial cells (T-HUVEC) was investigated by means of metalloporphyrin-based NO sensors employed in an electrochemical robotic system. The NO sensor was obtained by electrochemically induced deposition of Ni(II) tetrakis(p-nitrophenylporphyrin) on a 50-microm diameter platinum disk electrode which was integrated, together with a 25-microm diameter platinum disk, in a double-barrel electrode arrangement. The second electrode was used as a guidance sensor for the automatic and highly reproducible positioning of the NO sensor at a known distance from a layer of adherently growing cells by using z-approach curves in the negative feedback mode of scanning electrochemical microscopy (SECM). The electrochemical robotic system allows the fully automated detection of NO with high sensitivity and selectivity to be performed in real time within 96-well microtiter plates. A functional cell assay was established to allow the standardized detection of NO released upon stimulation from T-HUVEC with a sensor positioned at a known distance above the endothelial cells. The overall system was evaluated by automatic detection of NO release from T-HUVEC upon stimulation with VEGF-E after incubation with a variety of drugs that are known to act on different sites in the complex signal-transduction pathway that finally invokes NO release.     

Increased emissions of nitric oxide and nitrous oxide following tillage of a perennial pasture

About 40% of the agricultural land in the European Union (EU) is grassland used for animal production. When grassland is tilled, organically bound carbon and nitrogen are released, providing substrates for nitrifying and denitrifying microorganisms. The aim of this study was to examine the immediate effects of tillage of a perennial grassland carried out on different dates, on the emissions of nitric oxide (NO) and nitrous oxide (N₂O), monitored intensively over a 5-day period, in a humid, dairy farming area of northern Spain. Soil was tilled 12 days and 2 days prior to fertiliser application. Tillage, time of tillage, and N fertiliser application affected NO and N₂O emissions. Tillage 12 days before the start of the flux measurements resulted in higher emissions than tillage one day before, the difference being related to differences in soil mineral N and water-filled pore space (WFPS). Emissions of NO peaked at a WFPS of 50–60%, while N₂O fluxes peaked at 70–90% WFPS. Loss of N was greater as N₂O than as NO. The total loss of N as N₂O plus NO ranged from 0.027 kg N ha^–1 in unfertilised plots to 0.56 kg N ha^–1 in the tilled and N fertilised plot. Thereafter emissions decreased rapidly to low values. The results of this study indicate that tillage of perennial grassland may release large amounts of NO and N₂O, the amounts also depending on moisture conditions and addition of N fertiliser. We suggest that in order to reduce such emissions, application of N fertiliser should not immediately follow tillage of perennial grassland, as there is an extra supply of N from mineralisation of organic matter at this time.     

Modeling of nitric oxide emissions from temperate agricultural soils

Arable soils are a significant source of nitric oxide (NO), most of which is derived from nitrogen fertilizers. Accurate estimates of NO emissions from these soils are essential to devise strategies to mitigate the impact of agriculture on tropospheric ozone production and destruction. This paper presents the implementation of a soil NO emissions submodel within the environmentally-orientated soil-crop model, CERES-EGC. The submodel simulates NO production via the nitrification pathway, as modulated by soil environmental drivers. The resulting model was tested with data from 4 field experiments on wheat- and maize-cropped soils representative of two agricultural regions of France, over three years, and encompassing various climatic conditions. Overall, the model provided accurate predictions of NO emissions, but shortcomings arose from an inadequate vertical distribution of N fertilizer in the soil surface. Inclusion of a 2-cm thick topsoil layer in a ‘micro-layer’ version of CERES-EGC gave more realistic simulations of NO emissions and under-lying microbiological process. From a statistical point of view, both versions of the model achieved a similar fit to the experimental data, with respectively a MD and a RMSE ranging from 1.8 to 6.2 g N–NO ha⁻¹d⁻¹, and from 22.8 to 25.2 g N–NO ha⁻¹d⁻¹ across the 4 experiments. The cumulative NO losses represented 1–2% of NH₄⁺ fertilizer applied in the case of maize crops, and about 1% in the case of wheat crops. The ‘micro-layer’ version may be used for spatialized inventories of NO emissions to improve air quality prediction.     

Reduction of nitric oxide to nitrous oxide by cobalt porphyrins and corrins

The reduction of nitric oxide (NO) to nitrous oxide (N₂O) by dithiothreitol in the presence of cobalt-centered corrin and porphyrin are presented. Reactions were monitored directly using Fourier transform infrared (FTIR) spectroscopy of vapor phase spectra. Reaction rates were two-fold faster for cobalt corrin than cobalt-centered porphyrins. The stoichiometry showed loss of two NO molecules per N₂O generation.     

Fluorescence of 1,2-diaminoanthraquinone and its nitric oxide reaction product within macrophage cells

Nitric oxide (NO) is involved in many biological processes. Aromatic ortho-diamine derivatives are commonly used in the fluorescence imaging of NO in living cells. ortho-diamino (o-diamino) compounds are believed to react with NO in an oxygenated medium leading to the formation of a triazole derivative. One such o-diamino compound, 1,2-diaminoanthraquinone (DAA), is a nontoxic probe for the detection of NO in living tissues and cells. The formation of the DAA triazole derivative (DAA-TZ) upon reaction of DAA with NO/O(2) within cells has not been demonstrated previously. The aim of this study was to confirm that DAA-TZ is the species formed intracellularly when DAA reacts with NO in the presence of oxygen. The chemical synthesis and characterisation of DAA-TZ was performed together with intracellular studies of DAA and DAA-TZ. Raw 264.7 macrophages were loaded with the DAA or DAA-TZ under conditions of no-stimulation or stimulation with interferon-γ and lipopolysaccharide to produce NO. Confocal microscopy was used to image the DAA-loaded macrophage cells. Analysis of the emission spectra allowed precise discrimination of the fluorescence of each species in the macrophage cells, and confirmed the identity of DAA-TZ as the intracellular reaction product between DAA and NO in the presence of oxygen.     

Reduction of nitric oxide with activated PAN fibres

The reductive removal of nitric oxide from flue gases by reaction with polyacrylonitrile-based active carbon fibres (PAN-ACF) activated with sulphuric acid has been studied at 423–632 K, using a circulating flow reactor. Nitric oxide (0.67 mmol) was completely removed via reduction with 1 g activated carbon under optimum conditions in 210 and 60 min at 423 and 623 K, respectively. N₂ was formed as NO was removed. Some oxygen remained on the carbon surface at 423 K, but was desorbed as CO or CO₂ on subsequent heating to 623 K. The bimolecular reaction of NO reduction over PAN-ACF, and the possible active sites of oxygen surface groups are discussed in the light of a kinetic study and a comparison of the fibre activation at different temperatures.     

Characterization of an S-nitroso-N-acetylpenicillamine–based nitric oxide releasing polymer from a translational perspective

Due to the role of nitric oxide (NO) in regulating a variety of biological functions in humans, numerous studies on different NO releasing/generating materials have been published over the past two decades. Although NO has been demonstrated to be a strong antimicrobial and potent antithrombotic agent, NO-releasing (NOrel) polymers have not reached the clinical setting. While increasing the concentration of the NO donor in the polymer is a common method to prolong the NO release, this should not be at the cost of mechanical strength or biocompatibility of the original material. In this work, it was shown that the incorporation of S-nitroso-penicillamine (SNAP), an NO donor molecule, into Elast-eon E2As (a copolymer of mixed soft segments of polydimethylsiloxane and poly(hexamethylene oxide)), does not adversely impact the physical and biological attributes of the base polymer. Incorporating 10 wt% of SNAP into E2As reduces the ultimate tensile strength by only 20%. The inclusion of SNAP did not significantly affect the surface chemistry or roughness of E2As polymer. Ultraviolet radiation, ethylene oxide, and hydrogen peroxide vapor sterilization techniques retained approximately 90% of the active SNAP content and did not affect the NO-release profile over an 18-day period. Furthermore, these NOrel materials were shown to be biocompatible with the host tissues as observed through hemocompatibility and cytotoxicity analysis. In addition, the stability of SNAP in E2As was studied under a variety of storage conditions, as they pertain to translational potential of these materials. SNAP-incorporated E2As stored at room temperature for over six months retained 87% of its initial SNAP content. Stored and fresh films exhibited similar NO release kinetics over an 18-day period. Combined, the results from this study suggest that SNAP-doped E2As polymer is suitable for commercial biomedical applications due to the reported physical and biological characteristics that are important for commercial and clinical success.     

Mechanisms of electrochemical reduction and oxidation of nitric oxide

A summary is given of recent work on the reactivity of nitric oxide on various metal electrodes. The significant differences between the reactivity of adsorbed NO and NO in solution are pointed out, both for the reduction and the oxidation reaction(s). Whereas adsorbed NO can be reduced only to hydroxylamine and/or ammonia, it takes NO in solution to produce N₂O and N₂. From the reduction of NO on a series on stepped single-crystal Pt electrodes, it is concluded that NO_ads reduction is not a structure sensitive process. The protonation of the adsorbed NO is rate-determining; neither the NO adsorption strength nor the NO bond breaking play a significant role in its reduction rate. Whereas adsorbed NO on polycrystalline Pt can only be oxidized to nitrate, in the presence of NO in solution nitrous acid HNO₂ may also be formed, in a potential region where adsorbed NO is otherwise stable. Interestingly, on Pt(1 1 1) and Pt(5 5 4) NO_ads may be oxidized to HNO₂ in a surface-bonded redox couple. Whereas surface oxides appear to catalyze the oxidation of solution NO to HNO₂, the further oxidation to nitrate seems to be inhibited by the presence of surface oxides. Both the reduction and oxidation of solution NO appear to be not very metal-dependent reactions, as they take place with approximately equal rate on all electrode metals studied, including gold. This suggests the involvement of weakly adsorbed intermediates, and the relatively unimportant role of surface-bonded NO in the bulk NO reduction and oxidation activity.     

苯甲酸型低共熔溶剂吸收一氧化氮的性能研究

低共熔溶剂(DESs)已被广泛研究并应用于酸性气体的吸收,本研究发现苯甲酸类DESs能够可逆高效地吸收一氧化氮(NO)。以苯甲酸(BA)、硫脲、尿素和咪唑为氢键供体(HBD),以离子液体为氢键受体(HBA)制备了一系列的DESs。吸收NO的实验结果表明,以氯化四丁基膦(P₄₄₄₄Cl)为HBA和以BA为HBD的DESs表现出较高的NO吸收速率和饱和吸收量。BA/P₄₄₄₄Cl(1∶2)DES在101.3 kPa、303.15 K下,NO吸收量为2.75 mol/mol。热重测试和再生实验的结果表明,BA/P₄₄₄₄Cl(1∶2)DES具有理想的热稳定性和重复使用性。通过FTIR、¹H NMR和高斯模拟计算,探讨了BA/P₄₄₄₄Cl(1∶2)DES对NO的吸收机理,发现NO与BA的含氢氧原子之间存在化学相互作用,且BA的易去质子化性质有利于NO的吸收。     

Effects of molecular weight and degree of acetylation on the release of nitric oxide from chitosan‐nitric oxide adducts

A series of chitosans with different molecular weights and degrees of acetylation (DAs) are reacted with nitric oxide (NO) to form [NONO]^? groups. The effects of molecular weight and DA on NO release are investigated by Griess assay. Heterogeneous reaction of NH₂ groups of chitosan with NO was shown to be influenced greatly by the crystalline form of chitosan. Total NO release exhibited a bell‐shaped distribution at different DAs ranging from 6 to 95%, peaking at about 50%. When DA is held constant, total NO release is directly proportional to the molecular weight. X‐ray diffraction patterns indicate that the total NO release of chitosan‐NO adducts is in general agreement with the intensity of reflections at low Bragg angles (2θ = 8.6°–11.1°), and in turn, a relaxed hydration crystalline form and NO molecules could penetrate this crystal and react with the chitosan molecules. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of gas composition on nitric oxide removal from simulated flue gas with DBD-NPC method

A new method for nitric oxide (NO) removal was developed by combining dielectric barrier discharge (DBD) and negative pulse corona (NPC). The effects of gas composition (O₂, CO₂, and H₂O) on NO removal were investigated with this method, and the effect of alcohols (methanol and ethanol) addition on NO removal was also investigated as well as the reaction mechanisms to enhance the NO removal efficiency. The experimental results showed that O₂, CO₂, and H₂O had obvious inhibition effects on NO removal, and the negative effects were in the following order:O₂ > CO₂ > H₂O. The addition of methanol or ethanol in the reaction system could mitigate the negative effects of O₂, CO₂, and H₂O on NO removal, and also eliminated the production of NO₂. The positive effect of alcohols addition with DBD-NPC denitration method was also validated in the simulated flue gas, in which the NO_x (NO, NO₂) was mainly converted into N².     

Metal-based turn-on fluorescent probes for sensing nitric oxide

Nitric oxide, a reactive free radical, regulates a variety of biological processes. The absence of tools to detect NO directly, rapidly, specifically, and selectively motivated us to synthesize metal-based fluorescent probes to visualize the presence of NO. We prepared and investigated Co(II), Fe(II), Ru(II), Rh(II), and Cu(II) complexes as turn-on fluorescent NO sensors. Our exploration has provided insight into how the interaction of transition-metal centers with nitric oxide can be utilized for NO sensing.     

Anti-Inflammatory Effect of Auranofin on Palmitic Acid and LPS-Induced Inflammatory Response by Modulating TLR4 and NOX4-Mediated NF-κB Signaling Pathway in RAW264.7 Macrophages

Chronic inflammation, which is promoted by the production and secretion of inflammatory mediators and cytokines in activated macrophages, is responsible for the development of many diseases. Auranofin is a Food and Drug Administration-approved gold-based compound for the treatment of rheumatoid arthritis, and evidence suggests that auranofin could be a potential therapeutic agent for inflammation. In this study, to demonstrate the inhibitory effect of auranofin on chronic inflammation, a saturated fatty acid, palmitic acid (PA), and a low concentration of lipopolysaccharide (LPS) were used to activate RAW264.7 macrophages. The results show that PA amplified LPS signals to produce nitric oxide (NO) and various cytokines. However, auranofin significantly inhibited the levels of NO, monocyte chemoattractant protein-1, and pro-inflammatory cytokines, such as interleukin (IL)-1β, tumor necrosis factor-α, and IL-6, which had been increased by co-treatment with PA and LPS. Moreover, the expression of inducible NO synthase, IL-1β, and IL-6 mRNA and protein levels increased by PA and LPS were reduced by auranofin. In particular, the upregulation of NADPH oxidase (NOX) 4 and the translocation of the nuclear factor kappa-light-chain-enhancer of activated B cells (NF-κB) induced by PA and LPS were suppressed by auranofin. The binding between the toll-like receptor (TLR) 4 and auranofin was also predicted, and the release of NO and cytokines was reduced more by simultaneous treatment with auranofin and TLR4 inhibitor than by auranofin alone. In conclusion, all these findings suggested that auranofin had anti-inflammatory effects in PA and LPS-induced macrophages by interacting with TLR4 and downregulating the NOX4-mediated NF-κB signaling pathway.     

Photochemical production of nitric oxide from a nitrosyl phthalocyanine ruthenium complex by irradiation with light in the phototherapeutic window

The photochemical behavior of [Ru(NO)(NO)₂pc] (pc = phthalocyanine) is reported in this paper. In addition to ligand localized absorption bands (λ < 300 nm), the electronic spectrum of this complex in dichloromethane solution was dominated by an intense absorption at 640 nm characterized as Q-bands. Irradiation of [Ru(NO)(NO)₂pc] at 366 and 660 nm led to the production of nitric oxide (NO) as detected by a NO-sensor. NO production by light irradiation at high energy involved excitation of d_π–π^* transition, while a photoinduced electron transfer occurred at long wavelength irradiation. The NO quantum yields varied from 1.4 × 10⁻³ to 2.3 × 10⁻² mol einstein⁻¹, depending on oxygen concentration.     

The Functional Diversity of Nitric Oxide Synthase Isoforms in Human Nose and Paranasal Sinuses: Contrasting Pathophysiological Aspects in Nasal Allergy and Chronic Rhinosinusitis

The human paranasal sinuses are the major source of intrinsic nitric oxide (NO) production in the human airway. NO plays several roles in the maintenance of physiological homeostasis and the regulation of airway inflammation through the expression of three NO synthase (NOS) isoforms. Measuring NO levels can contribute to the diagnosis and assessment of allergic rhinitis (AR) and chronic rhinosinusitis (CRS). In symptomatic AR patients, pro-inflammatory cytokines upregulate the expression of inducible NOS (iNOS) in the inferior turbinate. Excessive amounts of NO cause oxidative damage to cellular components, leading to the deposition of cytotoxic substances. CRS phenotype and endotype classifications have provided insights into modern treatment strategies. Analyses of the production of sinus NO and its metabolites revealed pathobiological diversity that can be exploited for useful biomarkers. Measuring nasal NO based on different NOS activities is a potent tool for specific interventions targeting molecular pathways underlying CRS endotype-specific inflammation. We provide a comprehensive review of the functional diversity of NOS isoforms in the human sinonasal system in relation to these two major nasal disorders’ pathologies. The regulatory mechanisms of NOS expression associated with the substrate bioavailability indicate the involvement of both type 1 and type 2 immune responses.     

Fertilizer-induced nitric oxide emissions from agricultural soils

We summarize and evaluate 23 studies of the effect of fertilizer use on nitric oxide (NO) emission from agricultural soils. To quantify this effect we selected only field-scale studies with duration of at least one complete growing season and excluded studies with a legume as the principle crop. Only 6 studies met the established criteria, resulting in a total of 12 observations of soil/crop/fertilizer combinations, all in temperate areas. For these studies, the amount of NO emitted was linearly related to the amount of fertilizer applied (R² = 0.64) and about 0.5% of applied nitrogen was emitted as NO during the crop growing season. The available data are too limited to separate the effects of fertilizer type, soil type, or crop management.     

Novel drug delivery system for photoinduced nitric oxide (NO) delivery

A hybrid material (AB-1) was obtained by immobilizing photolabile ruthenium nitrosyl complex [Ru(L^SBH)(PPh₃)₂(NO)Cl](ClO₄) (1) into alginate polymer. A controlled release of nitric oxide was observed when a suspension of AB-1 was exposed to visible light. The amount of photoreleased NO from polymeric hybrid material was estimated using Griess reagent assay.     

Reduction of nitric oxide at a flow-through mercury plated nickel electrode

The electrochemical reduction of nitric oxide at a flow-through mercury-plated nickel gauze electrode in sulphuric acid was investigated. The current efficiencies of hydroxylamine, nitrous oxide and of hydrogen formation were determined. The main experimental results are: 1. The ratio between the NH₂OH and N₂O formation depends on the cd and on the flowrate of the electrolyte through the electrode, but does not depend on the H₂SO₄ concentration in the investigated range from 0.25 to 2.0 M and likewise not on the temperature. 2. The rate of the reduction of nitric oxide to NH₂OH and N₂O increases with increasing cd up to a maximum value, thereafter this rate decreases with increasing cd. 3. The ratio between the current efficiency of the NH₂OH formation and the current efficiency of the N₂O formation increases slowly with increasing cathodic potential.It seems that at low cd (much lower than the cd where the rate of the reduction of NO reaches its maximum) the reduction of NO is affected by both the electrochemical parameters and by the transport of NO to the electrode surface. However, at high current densities the reduction is dominated by mass-transport of NO only. NOH is an intermediate for both the NH₂OH and the N₂O formation.