The nitrite anion: the key intermediate in alkyl nitrates degradative mechanism.

Alkyl nitrates, _in vivo_, are metabolized to yield nitric oxide, and thiol groups are considered necessary cofactors. This statement is based on studies that underline how these species potentiate hemodynamic responsiveness to nitrates in patients with ischemic heart disease. However, the role of thiols might be mediated by the formation of corresponding S-nitrosothiols, and a redox process is responsible for the nitrates' degradation: an enzyme, probably the cytochrome P450, is involved _in vivo_. Here, we report evidence that, in vitro, no reaction between thiols and alkyl nitrates takes place, but that stronger reducing agents, such as iron (II) derivatives, are necessary: alkoxy radicals and the nitrite anion are the reaction intermediates. The latter, in slightly acidic conditions, for instance mimicking ischemic conditions, is shown to nitrosilate thiols to the corresponding S-nitrosothiols: the real NO suppliers. Therefore, the direct release of NO from nitrates is excluded. Finally, the in vivo role of thiols on depletion and tolerance is also accounted for

Nitrates for the Management of Acute Heart Failure Syndromes, A Systematic Review

© The Author(s) 2016Intravenous nitrates are widely used in the management of acute heart failure syndrome (AHFS) yet with lack of robust evidence to support their use. We therefore sought to analyze all randomized studies that evaluated the effects of nitrates on clinical outcomes in patients with AHFS. In total, 15 relevant trials comparing nitrates and alternative interventions in 1824 patients were identified. All but 3 were conducted before 1998. No trials demonstrated a beneficial effect on mortality, apart from 1 trial reporting a reduction in mortality, which was related to the time of treatment. Retrospective review suggests that there is a lack of data to draw any firm conclusions concerning the use of nitrates in patients with AHFS. More studies are needed to evaluate the safety and efficacy of these agents in the modern era of guideline-directed use of heart failure therapy.Peer reviewedFinal Accepted Versio

Measurements of PAN, alkyl nitrates, ozone, and hydrocarbons during spring in interior Alaska

Measurements of the atmospheric mixing ratios of ozone, peroxyacetylnitrate (PAN), hydrocarbons, and alkyl nitrates were made in a boreal forest ecosystem in the interior of Alaska from March 15 to May 14, 1993. During this period the mixing ratios of PAN, alkyl nitrates, and nonmethane hydrocarbons (NMHCs) generally decreased due to the influence of both meteorology and OH removal. Mean mixing ratios of ozone, PAN, C2 ‐ C6 alkyl nitrates, and total C2 ‐ C5 NMHC during southerly flow periods were 24.4 parts per billion (ppbv), 132.1 parts per trillion (pptv ), 34 pptv, and 8.2 ppbCv, respectively. During a short period of northerly flow, mixing ratios of PAN and total NMHC were approximately 2 times the southerly flow mixing ratios. PAN is correlated with ozone, and alkyl nitrates are correlated with alkanes. PAN and ozone mixing ratios exhibit similar diurnal variations on a number of days with an early morning minimum and afternoon maximum. This is likely due to a diurnal cycle in the boundary layer ‐ free troposphere exchange and loss processes in the boundary layer for both O3 and PAN. Higher molecular weight (mw) hydrocarbons and alkyl nitrates are observed to decrease more quickly than the lower mw hydrocarbons, consistent with removal by OH as the primary loss process

Monitoring the Content of Nitrates in Vegetables and the Influence of the Pickling Technology on the Denitrification Process

The aim of the work was to determine the concentration of nitrites in vegetable products (tomatoes, cucumbers, white cabbage, table beet, carrot, potatoes, onion and green onion, lettuce, spinach and parsley), realized at markets of the cities Ternopil, Kamianets-Podilskyi and Chernivtsi (Ukraine), to separate the distribution of nitrates in vegetables and also to study the influence of lactic microflora on the nitrate content at pickling tomatoes. It was established, that vegetables with the maximum exceed of maximum permissible concentration (MPC) by the nitrate content up to 1,6 times for products of closed soil are realized at markets. For open soil MPC exceed was in average 2,1 times. It was revealed, that most realized samples of tomatoes and leaf salad vegetables have the over-normative exceed of nitrates up to 35 %, and onion – the least one – 20 %. It was established, that nitrates accumulate in different parts of a fruit. In cucumbers, carrot, potato and table beet, the least quantity of nitrates accumulate in the external part of vegetables (near the surface), and the most one – in the central part. At the same time in cabbage and tomatoes, on the contrary, the least quantity – in the central part, the most one – in the area near the base of vegetables (stump). It was established, that at pickling tomatoes with the nitrate content within MPC lactic fermentation takes place with the intensive growth of titrated acidity, the decrease of the nitrate content takes place at this process. Under conditions of pickling tomatoes with the nitrate content two times more than MPC, the pickling process is a bit decelerated, but the nitrate content decreases to the safe level in a finished product. It was established, that vegetables with the nitrates quantity within 1500 mg/kg and more cannot be used in the pickling technology because of the bacteriological influence of nitrates on lactic microflora. Vegetables with such nitrate content must be obligatory condemned

Antarctic polar stratospheric aerosols: The roles of nitrates, chlorides and sulfates

Nitric and hydrochloric acids have been postulated to condense in the winter polar stratosphere to become an important component of polar stratospheric clouds. One implication is that the removal of NO(y) from the gas phase by this mechanism allows high Cl(x) concentrations to react with O3, because the formation of ClNO3 is inhibited. Contributions of NO3 and Cl to the stratospheric aerosol were determined during the 1987 Airborne Antarctic Ozone Experiment by testing for the presence of nitrates and chlorides in the condensed phase. Aerosol particles were collected on four 500 micron diameter gold wires, each pretreated differently to give results that were specific to certain physical and chemical aerosol properties. One wire was carbon-coated for concentration and size analyses by scanning electron microscopy; X-ray energy dispersive analyses permitted the detection of S and Cl in individual particles. Three more wires were coated with Nitron, barium chloride and silver nitrate, respectively, to detect nitrate, sulfate and chloride in aerosol particles. All three ions, viz., sulfates, nitrates and chlorides were detected in the Antarctic stratospheric aerosol. In terms of number concentrations, the aerosol was dominated by sulfates, followed by chlorides and nitrates. An inverse linear regression can be established between nitrate concentrations and ozone mixing ratio, and between temperature and nitrates

Decadal changes in summertime reactive oxidized nitrogen and surface ozone over the Southeast United States

Widespread efforts to abate ozone (O3) smog have significantly reduced emissions of nitrogen oxides (NOx) over the past 2 decades in the Southeast US, a place heavily influenced by both anthropogenic and biogenic emissions. How reactive nitrogen speciation responds to the reduction in NOx emissions in this region remains to be elucidated. Here we exploit aircraft measurements from ICARTT (July–August 2004), SENEX (June–July 2013), and SEAC4RS (August–September 2013) and long-term ground measurement networks alongside a global chemistry–climate model to examine decadal changes in summertime reactive oxidized nitrogen (RON) and ozone over the Southeast US. We show that our model can reproduce the mean vertical profiles of major RON species and the total (NOy) in both 2004 and 2013. Among the major RON species, nitric acid (HNO3) is dominant (∼ 42–45%), followed by NOx (31%), total peroxy nitrates (ΣPNs; 14%), and total alkyl nitrates (ΣANs; 9–12%) on a regional scale. We find that most RON species, including NOx, ΣPNs, and HNO3, decline proportionally with decreasing NOx emissions in this region, leading to a similar decline in NOy. This linear response might be in part due to the nearly constant summertime supply of biogenic VOC emissions in this region. Our model captures the observed relative change in RON and surface ozone from 2004 to 2013. Model sensitivity tests indicate that further reductions of NOxemissions will lead to a continued decline in surface ozone and less frequent high-ozone events

Competitive reaction modelling in aqueous systems. The case of contemporary reduction of dichromates and nitrates by nZVI

In various Countries, Cr(VI) still represents one of the groundwater pollutant of major concern, mainly due to its high toxicity, furthermore enhanced by the synergic effect in presence of other contaminants. As widely reported in the recent literature, nanoscale zero valent iron particles (nZVI-p) have been proved to be particularly effective in the removal of a wide range of contaminants from polluted waters. In this work, experimental tests of hexavalent chromium reduction in polluted groundwater in the presence of nitrate by nZVI-p are presented and discussed. The effect of different nitrate amounts on Cr(VI) reduction mechanism was investigated and the obtained results were successfully interpreted by the proposed kinetic model. nZVI-p produced by the classical borohydride reduction method were added in to synthetic solutions with the initial concentration of Cr(VI) set at 93, 62 and 31 mg L-1 and different nitrate contents in the range 10-100 mg L-1. According to the experimental results, nitrate showed an adverse effect on Cr(VI) reduction, depending on the nZVI/Cr(VI) and Cr(VI)/NO3 - ratio. The proposed kinetic model soundly grasps the competitive nature of the Cr(VI) reduction process when other chemical species are present in the treated solution

Aircraft based four-channel thermal dissociation laser induced fluorescence instrument for simultaneous measurements of NO2, total peroxy nitrate, total alkyl nitrate, and HNO3

A four-channel thermal dissociation laser induced fluorescence (TD-LIF) instrument has been developed for simultaneous measurements of nitrogen dioxide (NO2), total peroxy nitrate (∑PNs), total alkyl nitrate (∑ANs) and nitric acid (HNO3). NO2 is measured directly by LIF at 532 nm, whereas organic nitrates and nitric acid are thermally dissociated at distinct temperatures in the inlet to form NO2, which is then measured by LIF. The concentrations of each dissociated species are derived by the differences in measured NO2 relative to the reference colder inlet channel. The TD-LIF was adapted to fly on board the UK Facility for Airborne Atmospheric Measurements (FAAM) BAe 146-301 atmospheric research aircraft in summer 2010, and to date has successfully flown in five field campaigns. This paper reports novel improvements in the TD-LIF instrumentations, including (1) the use of a single wavelength laser, which makes the system compact and relatively cheap; (2) the use of a single beam laser that allows easy alignment and optical stability against the vibrational aircraft environment; and (3) the optical assembly of four detection cells that allow simultaneous and fast (time resolution up to 0.1 s) measurements of NO2, ∑PNs, ∑ANs and HNO3. Laboratory-generated mixtures of PNs, ANs and HNO3 in zero air are converted into NO2 and used to fix the dissociation temperatures of each heated inlet to test the selectivity of the instrument and potential interferences due to recombination reactions of the dissociated products. The effectiveness of the TD-LIF was demonstrated during the RONOCO aircraft campaign (summer 2010). A chemiluminescence system that was measuring NO2 and a broadband cavity enhanced absorption spectrometer (BBCEAS) that was measuring one of the PNs (N2O5) were installed on the same aircraft during the campaign. The in-flight intercomparison of the new TD-LIF with the chemiluminescence system for NO2 measurements and the intercomparison between ∑PNs measured by the TD-LIF and N2O5 by the BBCEAS are used to assess the performance of the TD-LIF

Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(−)-myrtenol nitrate

Here we report the chemoselective synthesis of several important, climate relevant isoprene nitrates using silver nitrate to mediate a ’halide for nitrate’ substitution. Employing readily available starting materials, reagents and Horner–Wadsworth–Emmons chemistry the synthesis of easily separable, synthetically versatile ‘key building blocks’ (E)- and (Z)-3-methyl-4-chlorobut-2-en-1-ol as well as (E)- and (Z)-1-((2-methyl-4-bromobut-2-enyloxy)methyl)-4-methoxybenzene has been achieved using cheap, ’off the shelf’ materials. Exploiting their reactivity we have studied their ability to undergo an ‘allylic halide for allylic nitrate’ substitution reaction which we demonstrate generates (E)- and (Z)-3-methyl-4-hydroxybut-2-enyl nitrate, and (E)- and (Z)-2-methyl-4-hydroxybut-2-enyl nitrates (‘isoprene nitrates’) in 66–80% overall yields. Using NOESY experiments the elucidation of the carbon–carbon double bond configuration within the purified isoprene nitrates has been established. Further exemplifying our ‘halide for nitrate’ substitution chemistry we outline the straightforward transformation of (1R,2S)-(−)-myrtenol bromide into the previously unknown monoterpene nitrate (1R,2S)-(−)-myrtenol nitrate