Browsing by Subject "Nitrites"

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    ItemOpen Access
    EPR spectroscopy of nitrite complexes of methemoglobin.
    (Inorg Chem, 2010-07-19) Schwab, David E; Stamler, Jonathan S; Singel, David J
    The chemical interplay of nitrogen oxides (NO's) with hemoglobin (Hb) has attracted considerable recent attention because of its potential significance in the mechanism of NO-related vasoactivity regulated by Hb. An important theme of this interplay-redox coupling in adducts of heme iron and NO's-has sparked renewed interest in fundamental studies of FeNO(x) coordination complexes. In this Article, we report combined UV-vis and comprehensive electron paramagnetic resonance (EPR) spectroscopic studies that address intriguing questions raised in recent studies of the structure and affinity of the nitrite ligand in complexes with Fe(III) in methemoglobin (metHb). EPR spectra of metHb/NO(2)(-) are found to exhibit a characteristic doubling in their sharper spectral features. Comparative EPR measurements at X- and S-band frequencies, and in D(2)O versus H(2)O, argue against the assignment of this splitting as hyperfine structure. Correlated changes in the EPR spectra with pH enable complete assignment of the spectrum as deriving from the overlap of two low-spin species with g values of 3.018, 2.122, 1.45 and 2.870, 2.304, 1.45 (values for samples at 20 K and pH 7.4 in phosphate-buffered saline). These g values are typical of g values found for other heme proteins with N-coordinated ligands in the binding pocket and are thus suggestive of N-nitro versus O-nitrito coordination. The positions and shapes of the spectral lines vary only slightly with temperature until motional averaging ensues at approximately 150 K. The pattern of motional averaging in the variable-temperature EPR spectra and EPR studies of Fe(III)NO(2)(-)/Fe(II)NO hybrids suggest that one of two species is present in both of the alpha and beta subunits, while the other is exclusive to the beta subunit. Our results also reconfirm that the affinity of nitrite for metHb is of millimolar magnitude, thereby making a direct role for nitrite in physiological hypoxic vasodilation difficult to justify.
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    ItemOpen Access
    Pharmacologically augmented S-nitrosylated hemoglobin improves recovery from murine subarachnoid hemorrhage.
    (Stroke, 2011-02) Sheng, H; Reynolds, JD; Auten, RL; Demchenko, IT; Piantadosi, CA; Stamler, JS; Warner, DS

    Background and purpose

    S-nitrosylated hemoglobin (S-nitrosohemoglobin) has been implicated in the delivery of O(2) to tissues through the regulation of microvascular blood flow. This study tested the hypothesis that enhancement of S-nitrosylated hemoglobin by ethyl nitrite inhalation improves outcome after experimental subarachnoid hemorrhage (SAH).

    Methods

    A preliminary dosing study identified 20 ppm ethyl nitrite as a concentration that produced a 4-fold increase in S-nitrosylated hemoglobin concentration with no increase in methemoglobin. Mice were subjected to endovascular perforation of the right anterior cerebral artery and were treated with 20 ppm ethyl nitrite in air, or air alone for 72 hours, after which neurologic function, cerebral vessel diameter, brain water content, cortical tissue Po(2), and parenchymal red blood cell flow velocity were measured.

    Results

    At 72 hours after hemorrhage, air- and ethyl nitrite-exposed mice had similarly sized blood clots. Ethyl nitrite improved neurologic score and rotarod performance; abated SAH-induced constrictions in the ipsilateral anterior, middle cerebral, and internal carotid arteries; and prevented an increase in ipsilateral brain water content. Ethyl nitrite inhalation increased red blood cell flow velocity and cortical tissue Po(2) in the ipsilateral cortex with no effect on systemic blood pressure.

    Conclusions

    Targeted S-nitrosylation of hemoglobin improved outcome parameters, including vessel diameter, tissue blood flow, cortical tissue Po(2), and neurologic function in a murine SAH model. Augmenting endogenous Po(2)-dependent delivery of NO bioactivity to selectively dilate the compromised cerebral vasculature has significant clinical potential in the treatment of SAH.
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    Sensor-mediated granular sludge reactor for nitrogen removal and reduced aeration demand using a dilute wastewater.
    (Water environment research : a research publication of the Water Environment Federation, 2020-07) Bekele, Zerihun A; Delgado Vela, Jeseth; Bott, Charles B; Love, Nancy G
    A sensor-mediated strategy was applied to a laboratory-scale granular sludge reactor (GSR) to demonstrate that energy-efficient inorganic nitrogen removal is possible with a dilute mainstream wastewater. The GSR was fed a dilute wastewater designed to simulate an A-stage mainstream anaerobic treatment process. DO, pH, and ammonia/nitrate sensors measured water quality as part of a real-time control strategy that resulted in low-energy nitrogen removal. At a low COD (0.2 kg m-3  day-1 ) and ammonia (0.1 kg-N m-3  day-1 ) load, the average degree of ammonia oxidation was 86.2 ± 3.2% and total inorganic nitrogen removal was 56.7 ± 2.9% over the entire reactor operation. Aeration was controlled using a DO setpoint, with and without residual ammonia control. Under both strategies, maintaining a low bulk oxygen level (0.5 mg/L) and alternating aerobic/anoxic cycles resulted in a higher level of nitrite accumulation and supported shortcut inorganic nitrogen removal by suppressing nitrite oxidizing bacteria. Furthermore, coupling a DO setpoint aeration strategy with residual ammonia control resulted in more stable nitritation and improved aeration efficiency. The results show that sensor-mediated controls, especially coupled with a DO setpoint and residual ammonia controls, are beneficial for maintaining stable aerobic granular sludge. PRACTITIONER POINTS: Tight sensor-mediated aeration control is need for better PN/A. Low DO intermittent aeration with minimum ammonium residual results in a stable N removal. Low DO aeration results in a stable NOB suppression. Using sensor-mediated aeration control in a granular sludge reactor reduces aeration cost.