Probing the protonation and reduction of heptavalent neptunium with computational guidance.

Influence of pH on the speciation and stability of heptavalent neptunium is poorly understood although it is frequently invoked in the literature to explain experimental observations. The present study employs Density Functional Theory (DFT) methodology to assess the thermodynamic feasibility of protonation reactions for the Np(VII) anion complex and the impact on its reduction to Np(VI). This theoretical framework is then explored experimentally through the titration and systematic protonation of Np(VII) in solution and solid-state samples while monitoring them spectroscopically.

Synthesis, characterization, and density functional theory investigation of (CHN)[NpOCl] and Rb[NpOCl(HO)] chain structures.

The actinyl tetrachloro complex [An(V/VI)OCl] tends to form discrete molecular units in both solution and solid state materials, but related aquachloro complexes have been observed as both discrete coordination compounds and 1-D chain topologies. Subtle differences in the inner sphere coordination significantly influence the formation of structural topologies in the actinyl chloride system, but the exact reasoning for these variations has not been delineated. In the current study, we present the synthesis, structural characterization, and vibrational analysis of two 1-D neptunyl(V) chain compounds: (CHN)[NpOCl] (Np-Gua) and Rb[NpOCl(HO)] (Np-Rb).

Insights into the Mechanism of Neptunium Oxidation to the Heptavalent State.

Neptunium can exist in multiple oxidation states, including the rare and poorly understood heptavalent form. In this work, we monitored the formation of heptavalent neptunium [Np(VII)O(OH)] during ozonolysis of aqueous MOH (M=Li, Na, K) solutions using a combined experimental and theoretical approach. All experimental reactions were closely monitored via absorption and vibrational spectroscopy to follow both the oxidation state and the speciation of neptunium guided by the calculated vibrational frequencies for various neptunium species.

Three-Dimensional Noncovalent Interaction Network within [NpOCl] Coordination Compounds: Influence on Thermochemical and Vibrational Properties.

Noncovalent interactions (NCIs) can influence the stability and chemical properties of pentavalent and hexavalent actinyl (AnO) compounds. In this work, the impact of NCIs (actinyl-hydrogen and actinyl-cation interactions) on the enthalpy of formation (Δ) and vibrational features was evaluated using Np(VI) tetrachloro compounds as the model system. We calculated the Δ values of these solid-state compounds through density functional theory+ thermodynamics (DFT+ T) and validated the results against experimental Δ values obtained through isothermal acid calorimetry.

The effect of acute ingestion of a large dose of alcohol on the hemostatic system and its circadian variation.

Background And Purpose: Heavy binge drinking may trigger the onset of embolic stroke and acute myocardial infarction, but the underlying mechanisms are unclear. The effects of binge drinking on the hemostatic system and its circadian variation have not been investigated. We investigated the effects of an acute intake of a large dose of alcohol (1.

Analysis of novel hydroperoxides and other metabolites of oleic, linoleic, and linolenic acids by liquid chromatography-mass spectrometry with ion trap MSn.

Linoleate is oxygenated by manganese-lipoxygenase (Mn-LO) to 11S-hydroperoxylinoleic acid and 13R-hydroperoxyoctadeca-9Z,11E-dienoic acid, whereas linoleate diol synthase (LDS) converts linoleate sequentially to 8R-hydroperoxylinoleate, through an 8-dioxygenase by insertion of molecular oxygen, and to 7S,8S-dihydroxylinoleate, through a hydroperoxide isomerase by intramolecular oxygen transfer. We have used liquid chromatography-mass spectrometry (LC-MS) with an ion trap mass spectrometer to study the MSn mass spectra of the main metabolites of oleic, linoleic, alpha-linolenic and gamma-linolenic acids, which are formed by Mn-LO and by LDS. The enzymes were purified from the culture broth (Mn-LO) and mycelium (LDS) of the fungus Gaeumannomyces graminis.

Nitric oxide is not increased in alcoholic brain.

Nitric oxide (NO) metabolites nitrite and nitrate were measured in the cerebrospinal fluid in 12 alcohol-dependent subjects and in 16 healthy controls. The amounts of NO metabolites in alcoholics were not different from those in the controls. The results suggest that NO is not a major factor responsible for brain damage in these patients.

Transformation of subcutaneous nitric oxide into nitrate in the rat.

Following its addition to arterialized blood in vitro, nitric oxide (NO) is transformed into nitrate in the erythrocytes. Inhaled NO is similarly transformed into nitrate in the blood in vivo. These observations suggest that nitrate is a universal end-metabolite of NO, i.

Thromboxane metabolite excretion in patients with hand-arm vibration syndrome.

As chronic exposure to hand-held vibrating tools may cause endothelial injury, a subsequent sustained platelet activation with the increased release of vasoconstricting thromboxane A2 (TxA2) could be of pathophysiological importance in vibration-induced Raynaud's phenomenon. Therefore, the aim of this study was to elucidate whether or not hand-arm vibration syndrome is accompanied by increased endogenous TxA2 biosynthesis. The study involved 64 men, aged 23-61 years, stratified according to the exposure to vibrating tools, the presence of Raynaud's phenomenon, and smoking habit.

Effect of nicotine infusion in humans on platelet aggregation and urinary excretion of a major thromboxane metabolite.

The objective of this study was to evaluate further a possible role of nicotine as a stimulator of platelet aggregability and platelet arachidonic acid metabolism in vivo. In six healthy, non-smoking males, platelet aggregability was assessed by filtragometry and impedance aggregometry before, during and after an intravenous infusion of nicotine at two different doses (0.25 and 0.

Dietary cholesterol induces transient changes in plasma nitrate levels in rabbits that are correlated to microcirculatory changes.

Dietary treatment of rabbits with 1% cholesterol resulted in a transient rise in their plasma nitrate levels. After 3 weeks of treatment the nitrate levels were about 50% higher than those of the controls (p<0.005).

Conversion of inhaled nitric oxide to nitrate in man.

1. Nitric oxide (NO) is potentially useful as a selective vasodilator drug in infants and adults with pulmonary hypertension. In vitro and in vivo observations demonstrate that NO may be converted to nitrate in the blood, to be further excreted into the urine.

Increased urinary excretion of a major thromboxane metabolite in early alcohol withdrawal.

Urinary excretion of 2,3-dinor-thromboxane B2 as a marker of in vivo thromboxane A2 (TxA2) biosynthesis was measured in six alcoholics 1 and 14 days after the cessation of heavy drinking using gas chromatography/mass spectrometry. Six non-alcoholic healthy volunteers served as controls. One day after alcohol withdrawal the excretion of the dinor metabolite was significantly higher (P < 0.

Metabolism and excretion of nitric oxide in humans. An experimental and clinical study.

Despite the increasing insight in the clinical importance of nitric oxide (NO), formerly known as endothelium-derived relaxing factor (EDRF), there is limited information about the metabolism and elimination of this mediator in humans. We studied the degradation of NO in healthy subjects inhaling 25 ppm for 60 minutes and in patients with severe heart failure inhaling 20, 40, and 80 ppm in consecutive 10-minute periods. In other healthy subjects, the renal clearance of NO metabolite was measured.

Maintained hyperexcretion of thromboxane A2 metabolite in healthy young cigarette smokers: results from a prospective study in randomly sampled males with stable smoking habits.

Although several studies have identified cigarette smoking as a factor increasing platelet formation of thromboxane A2 (TxA2), no prospective data on this issue have been presented in a defined population with stable smoking habits. Therefore, we analysed the relation between smoking habits and urinary excretion of the 2,3-dinor metabolites of thromboxane A2 (Tx-M) and prostacyclin (PGI-M) in 87 males, randomly sampled from a population of 18-19-year-old men, at two different occasions separated by 31-49 months. The daily cigarette consumption among the smokers was unchanged between the study occasions (11 vs.

Tobacco use and urinary excretion of thromboxane A2 and prostacyclin metabolites in women stratified by age.

Background: Activated platelets have been implicated in both acute thrombus formation and atherogenesis. Because smoking is a risk factor for cardiovascular disease in men and women and male smokers have biochemical evidence of increased platelet activation, we found it of interest to study whether smoking augments platelet activity in women as well.

Methods And Results: Data on smoking habits and a urinary sample were obtained from 125 healthy female nonsmokers and an equal number of smokers, stratified by age in five groups from 18 to 59 years old.

2,3-Dinor metabolites of thromboxane A2 and prostacyclin in urine from healthy human subjects: diurnal variation and relation to 24h excretion.

1. Urinary levels of the 2,3-dinor metabolites of thromboxane A2 (2,3-dinor-thromboxane A2, Tx-M) and prostacyclin (2,3-dinor-6-keto-prostaglandin F1 alpha, PGI-M) are frequently analysed as indices of platelet and endothelial activity and interaction in vivo. Despite this, little is known about the possible diurnal variations in urinary Tx-M and PGI-M in healthy human subjects, and how the urinary levels of Tx-M and PGI-M in single samples reflect their respective 24 h excretion rates.

Dependence of the metabolism of nitric oxide (NO) in healthy human whole blood on the oxygenation of its red cell haemoglobin.

Plasma or whole venous or arterialized blood from healthy human donors was incubated with NO (50-300 microM), and the resulting formation of methaemoglobin (MetHb), nitrosyl haemoglobin (HbNO), and plasma nitrite and nitrate were measured. In plasma, NO was converted to nitrite and nitrate in a ratio of 5:1. In arterial blood (O2 sat.

Effects of exercise and ethanol ingestion on platelet thromboxane release in healthy men.

We studied the effects of repeated bicycle exercises and ethanol ingestion (1.5 g/kg) on platelet aggregation and thromboxane (TxB2) release in 10 healthy male volunteers. After a bicycle exercise performed in the morning, the adenosine diphosphate (ADP)-induced platelet aggregation and the aggregation-associated thromboxane release were found to be decreased in fasting men.

Relation between tobacco use and urinary excretion of thromboxane A2 and prostacyclin metabolites in young men.

Background: Cigarette smoking is a risk factor for cardiovascular disease. The present study addressed the effect of tobacco use on the formation of two eicosanoids, thromboxane A2 and prostacyclin, which have been implicated in both acute and chronic cardiovascular disorders.

Methods And Results: In 577 randomly sampled 18-19-year-old men, the urinary excretion of the 2,3-dinor metabolites of thromboxane A2 and prostacyclin (Tx-M and PGI-M, respectively) was analyzed and related to the subjects' self-reported use of tobacco.

Release of endothelial mediators and sympathetic transmitters at different coronary flow rates in rabbit hearts.

1. The release of three endothelial mediators, namely, endothelial-derived relaxing factor (EDRF), prostacyclin (PGI2) and endothelin, and of two sympathetic neurotransmitters, noradrenaline and neuropeptide Y (NPY), from resting or sympathetically stimulated rabbit Langendorff hearts was investigated at normal or elevated coronary flow. The sympathetic nerves to the hearts were stimulated at 5 Hz for 30 s and the cardiac effluent was analysed for nitrite (metabolite of EDRF) with electron paramagnetic resonance spectrometry, for 6-keto-PGF1 alpha (metabolite of PGI2) with gas chromatography/mass spectrometry, for endothelin- and NPY-like immunoreactivity with radioimmunoassay, and for noradrenaline and purines with liquid chromatography.

Non-invasive assessment of the cardiovascular eicosanoids, thromboxane A2 and prostacyclin, in randomly sampled males, with special reference to the influence of inheritance and environmental factors.

1. We studied, in a random sample of 385 nonsmoking men born in 1968-1969 and 31 men born in 1913 or 1923, whether inheritance and environmental factors influenced platelet activity and vessel wall prostacyclin formation, as reflected non-invasively by the urinary excretion of the 2,3-dinor-metabolites of thromboxane A2 (2,3-dinor-thromboxane B2, Tx-M) and prostacyclin (2,3-dinor-6-keto-prostaglandin F1 alpha, PGI-M), respectively. 2.

Paired analysis of thromboxane and prostacyclin metabolites in urine from healthy mothers and their children.

Eicosanoids have been implicated in the adaptation of the fetal to the neonatal circulation, but biochemical support for an activation of their synthesis in relation to birth has not been presented. We addressed this by assessing in pairs the excretion of two metabolites of thromboxane A2, 11-dehydro-TxB2 (dTx) and 2,3-dinor-TxB2 (Tx-M), and one metabolite of prostacyclin, 2,3-dinor-6-keto-PGF1 a (PGI-M), in the first voided urine from 13 healthy term neonates and in the immediate pre-delivery urine from their respective mothers. The excretion of dTx was higher (p less than 0.