Studies on the doubly charged cluster ions of sodium and potassium nitrates by electrospray ionization tandem mass spectrometry

Doubly charged cluster ions, besides singly charged cluster ions, from sodium and potassium nitrates were produced evidently under normal source capillary temperature of 200 degrees C in both positive and negative ion electrospray ionization (ESI) ion trap mass spectrometry. The fragmentation pathways for doubly charged cluster ions were studied in detail using ESI tandem mass spectrometry and two pathways were observed depending on the cluster sizes of alkali metal nitrates. In addition, factors that affect the formation of cluster ions were also interrogated.

Soybean - Corn rotation : efect of the stubble mineralization on the nitrates production and corn yield

p.53-58

Soybean - Corn rotation : efect of the stubble mineralization on the nitrates production and corn yield

p.53-58

Risk of Barrett's oesophagus, oesophageal adenocarcinoma and reflux oesophagitis and the use of nitrates and asthma medications

To investigate the relationship between use of asthma medication and nitrates and risk of reflux oesophagitis, Barrett's oesophagus and oesophageal adenocarcinoma.

Évaluation du risque cancérigène associé à la contamination de l’eau potable de puits municipaux par les nitrates/nitrites dans certaines régions rurales du Québec

La spécialisation des techniques agricoles que nous connaissons ces dernières décennies, particulièrement dans les régions rurales, est à l’origine de l’abus de fertilisants. Ces derniers sont actuellement reconnus comme étant les causes principales de la contamination de l’eau souterraine par les nitrates. Suite à leur ingestion via l’eau potable, les nitrates sont transformés en nitrites par la flore buccale. Une fois dans l’estomac les nitrites réagissent avec certaines amines provenant de l’alimentation pour générer des nitrosamines cancérogènes. L’objectif de notre étude était d’estimer quantitativement l’excès de risque de cancer (ER) pour les populations de sept régions rurales du Québec qui consomme l’eau potable provenant de réseaux municipaux alimentés en eau souterraine. Le territoire à l’étude était caractérisé par une agriculture intensive d’élevage. Les médianes (et 95e centiles) régionales des concentrations de nitrates mesurées dans les réseaux de ces régions étaient de : 0,18 (2,74); 0,48 (10,35); 0,15 (1,28); 0,32 (11); 0,05 (0,76); 0,10 (4,69); 0,09 (2,13) mg N-NO3-/l. Nous avons envisagé un scénario de transformation complète des nitrites et de certaines amines (diméthylamine, diéthylamine, n-butylamine, méthyléthylamine) en nitrosamines spécifiques : N-diméthylnitrosamine (NDMA), N-diéthylnitrosamine (NDEA), N-n-dibutylnitrosamine (NDBA) et N-méthyléthylnitrosamine (NMEA). Pour estimer la concentration de nitrites formés dans l’estomac, nous avons considéré une consommation définie d’eau potable, le volume de l’estomac et un taux de transformation des nitrates en nitrites. Supposant les quantités de nitrites et de chaque amine constantes pendant 1h, nous avons considéré la constante de nitrosation spécifique à chaque amine pour évaluer la dose d’exposition journalière à chaque nitrosamine équivalente formée. Par la suite, la combinaison de cette dose à un estimateur de potentiel cancérogène qhumain spécifique à chaque nitrosamine, nous a permis d’évaluer l’ER associé à chacune d’elles. Globalement l’analyse a démontré que les ER les plus élevés, estimés pour le NDBA, étaient de l’ordre de 10-6, ne contribuant pas de façon significative à une augmentation du risque de cancer pour ces populations.

Alkyl nitrates in outflow from North America over the North Atlantic during Intercontinental Transport of Ozone and Precursors 2004

This paper is based on alkyl nitrate measurements made over the North Atlantic as part of the International Consortium for Research on Atmospheric Transport and Transformation (ICARTT). The focus is on the analysis of air samples collected on the UK BAe-146 aircraft during the Intercontinental Transport of Ozone and Precursors (ITOP) project, but air samples collected on board the NASA DC-8 and NOAA WP-3D aircraft as part of a Lagrangian experiment are also used. The ratios between the alkyl nitrates and their parent hydrocarbons are compared with those expected from chemical theory. Further, a box model is run to investigate the temporal evolution of the alkyl nitrates in three Lagrangian case studies and compared to observations. The air samples collected during ITOP do not appear to be strongly influenced by oceanic sources, but rather are influenced by emissions from the N.E. United States and from Alaskan fires. There also appears to be a widespread common source of ethyl nitrate and 1-propyl nitrate other than from their parent hydrocarbons. The general agreement between the alkyl nitrate data and photochemical theory suggests that during the first few days of transport from the source region, photochemical production of alkyl nitrates, and thus ozone, had taken place. The observations in the more photochemically processed air masses are consistent with the alkyl nitrate production reactions no longer dominating the peroxy radical self/cross reactions. Further, the results also suggest that the rates of photochemical processing in the Alaskan smoke plumes were small.

Extraction and coordination studies of the unexplored bifunctional ligand carbamoyl methyl sulfoxide (CMSO) with uranium(VI) and cerium(III) nitrates. Synthesis and structures of [UO2(NO3)(2)((PhSOCH2CONBu2)-Bu-i)] and [Ce(NO3)(3)(PhSOCH2CONBu2)(2)]

The bifunctional carbamoyl methyl sulfoxide ligands, PhCH2SOCH2CONHPh (L-1), PhCH2SOCH2CONHCH2Ph (L-2), (PhSOCH2CONPr2)-Pr-i (L-3), PhSOCH2CONBu2 (L-4), (PhSOCH2CONBu2)-Bu-i (L-5) and PhSOCH2CON(C8H17)(2) (L-6) have been synthesized and characterized by spectroscopic methods. The selected coordination chemistry of L-1, L-3, L-4 and L-5 with [UO2(NO3)(2)] and [Ce(NO3)(3)] has been evaluated. The structures of the compounds [UO2(NO3)(2)((PhSOCH2CONBu2)-Bu-i)] (10) and [Ce(NO3)(3)(PhSOCH2CONBu2)(2)] (12) have been determined by single crystal X-ray diffraction methods. Preliminary extraction studies of ligand L-6 with U(VI), Pu(IV) and Am(III) in tracer level showed an appreciable extraction for U(VI) and Pu(IV) in up to 10 M HNO3 but not for Am(III). Thermal studies on compounds 8 and 10 in air revealed that the ligands can be destroyed completely on incineration. The electron spray mass spectra of compounds 8 and 10 in acetone show that extensive ligand distribution reactions occur in solution to give a mixture of products with ligand to metal ratios of 1 : 1 and 2 : 1. However, 10 retains its solid state structure in CH2Cl2.

Coordination and extraction studies of an unexplored bi-functional ligand, carbamoyl methyl pyrazole (CMPz) with uranium(VI), lanthanum(III) and cerium(III) nitrates

The bi-functional carbamoyl methyl pyrazole ligands, C5H7N2CH2CONBu2 (L-1), (C5H7N2CH2CONBu2)-Bu-i (L-2), C3H3N2CH2CONBu2 (L-3), (C3H3N2CH2CONBu2)-Bu-i (L-4) and C5H7N2CH2CON(C8H17)(2) (L-5) were synthesized and characterized by spectroscopic and elemental analysis methods. The selected coordination chemistry of L-1 to L-4 with [UO2(NO3)(2)center dot 6H(2)O], [La(NO3)(3)center dot 6H(2)O] and [Ce(NO3)(3)center dot 6H(2)O] has been evaluated. Structures for the compounds [UO2(NO3)(2) C5H7N2CH2CONBu2] (6) [UO2(NO3)(2) (C5H7N2CHCONBu2)-Bu-i] (7) and [Ce(NO3)(3){C(3)H(3)N(2)CH(2)CON(i)Bu2}(2)] (11) have been determined by single crystal X-ray diffraction methods. Preliminary extraction studies of the ligand L-5 with U(VI) and Pu(IV) in tracer level showed an appreciable extraction for U(VI) and Pu(TV) up to 10 M HNO3 but not for Am(III). Thermal studies of the compounds 6 and 7 in air revealed that the ligands can be destroyed completely on incineration. (c) 2007 Elsevier Ltd. All rights reserved.

Gas-Phase Nucleophilic and Elimination Reactions in Simple Alkyl Nitrates

There has been increasing interest in the gas-phase reactivity of alkyl nitrates because of their well-known applications as explosives and because of then role in atmospheric and in marine processes This manuscript describes an experimental study by FT-ICR techniques of the gas-phase reactions of OH(-) and F(-) with methyl and ethyl Innate For methyl nitrate, the main reaction channel is found to be an elimination process promoted by abstraction of an a proton from the methyl group. Nucleophilic displacement of nitrate anion through an S(N)2 process at the carbon center Is also found to he an important reaction channel with methyl nitrate In ethyl nitrate, Ruination of NO(3)(-) is greatly enhanced and this is attributed to the ease of an E2-type elimination process promoted by proton abstraction at the beta position of the ethyl group. Theoretical calculations at the MP2/6-311+G(3df,2p)//MP2/6-31+G(d) level of theory ale consistent with the relative importance of the reaction channels and suggest that these reactions proceed through a double well potential The calculations also predict that nucleophilic attack by OH(-) at the nitrogen center (Sn2@N) is energetically the rueful ad pathway but experiments with (18)OH(-) showed no evidence for this channel. Single-point calculations reveal a strong preference for approach to the emboli center and may explain the lack of reactivity at the nitrogen center. Calculations were also carried out or NH(2)(-) and SH(-) to establish the reactivity pattern to provide a better understanding of environmentally relevant nitrate esters.

Coordination of water to organolead(IV) nitrates: The examples of [PbPh2(NO3)(2)(H2O)(2)] and [PbMe3(NO3)(H2O)]

The compound [PbPh2(NO3)(2)(H2O)(2)] was synthesized and characterized by spectroscopic methods (IR; H-1, C-13 and Pb-207 NMR) and mass spectrometry. An X-ray diffraction study showed that the crystal is a supramolecular tridimensional network of hydrogen-bonded PbPh2(NO3)(2)(H2O)(2) units in which the Pb atom is octacoordinated and adopts a distorted hexagonal bipyramidal geometry, with four O (bidentate nitrate) and two O (water) atoms in equatorial positions and two C-phenyl atoms in axial positions. The crystal of [PbMe3(NO3)(H2O)], obtained as a byproduct in the synthesis of PbMe2(NO3)(2), contains chains of hydrogen-bonded PbMe3(NO3)(H2O) units in which the Pb atom is pentacoordinated with a slightly distorted trigonal bipyramidal environment. In this arrangement the three C-methyl atoms are equatorial and the O atoms from the monodentate nitrate and the water molecule are axial. (C) 2011 Elsevier Ltd. All rights reserved.

Differential effects of captopril and nitrates on muscle sympathetic nerve activity in volunteers

BACKGROUND The sympathetic nervous system (SNS) is an important regulator of cardiovascular function. Activation of SNS plays an important role in the pathophysiology and the prognosis of cardiovascular diseases such as heart failure, acute coronary syndromes, arrhythmia, and possibly hypertension. Vasodilators such as adenosine and sodium nitroprusside are known to activate SNS via baroreflex mechanisms. Because vasodilators are widely used in the treatment of patients with cardiovascular diseases, the aim of the present study was to assess the influence of clinically used dosages of isosorbide dinitrate and captopril on sympathetic nerve activity at rest and during stimulatory maneuvers. METHODS AND RESULTS Twenty-eight healthy volunteers were included in this double-blind placebo-controlled study, and muscle sympathetic nerve activity (MSA; with microelectrodes in the peroneal nerve), blood pressure, heart rate, and neurohumoral parameters were measured before and 90 minutes after the oral administration of 40 mg isosorbide dinitrate or 6.25 mg captopril. Furthermore, a 3-minute mental stress test and a cold pressor test were performed before and 90 minutes after drug administration. Resting MSA did not change after captopril and decreased compared with placebo (P < .05 versus placebo), whereas isosorbide dinitrate led to a marked increase in MSA (P < .05). Systolic blood pressure was reduced by isosorbide dinitrate (P < .05), whereas captopril decreased diastolic blood pressure (P < .05). The increases in MSA, blood pressure, and heart rate during mental stress were comparable before and after drug administration regardless of the medication. During cold pressor test, MSA and systolic and diastolic blood pressures increased to the same degree independent of treatment, but after isosorbide dinitrate, the increase in MSA seemed to be less pronounced. Heart rate did not change during cold stimulation. Plasma renin activity increased after captopril and isosorbide dinitrate (P < .05), whereas placebo had no effect. Endothelin-1 increased after placebo and isosorbide dinitrate (P < .05) but not after captopril. CONCLUSIONS Thus, captopril suppressed MSA despite lowering of diastolic blood pressure but allowed normal adaptation of the SNS during mental or physical stress. In contrast, the nitrate strongly activated the SNS under baseline conditions. These findings demonstrate that vasodilators differentially interact with the SNS, which could be of importance in therapeutic strategies for the treatment of patients with cardiovascular diseases.