Isotopic Exchange of Hydrogen between the Fluids of the Hydrocarbon Fields

It is presented the isotopic exchange of hydrogen in natural gas, crude oil, and underground water. The general behaviour of the isotopic exchange occuring in a system with a large number of components is given. A good agreement between the calculated and the experimental isotopic distribution factors is obtained in the case of the isotopic exchange of hydrogen between methane and underground water. The deuterium concentration of the crude oil samples inserts between the values obtained for methane and underground water. This fact is due to the presence of the isotopic exchange between these fluids.     

Einsatz von deuterierten Molekülen zur Bestimmung von Selbstdiffusionskoeffizienten bei der Zweikomponentenadsorption in Zeolithen unter Anwendung der NMR-Meßtechnik

The nmr pulsed field gradient technique is an efficient tool for measuring molecular self-diffusion in sorplion systems. Applying alternatively perdeutcrated substances, in this way for the first lime the self-diffusion coefficients of the individual components at mullicomponent adsorption could be measured. Examples of self-diffusion results for mixtures of water, ammonia and liydrocarbons adsorbed on different types of zeolites are given.     

Numerical simulation of fueling pellet ablation and transport in the EAST H-mode discharge

To understand the effect of injected deuterium (D) pellets on background plasma, the ablation of D pellets and the transport of D species in both atomic and ionic states in the EAST device are simulated using a modified dynamic neutral gas shield model combined with the edge plasma code SOLPS-ITER. The simulation results show that there is a phenomenon of obvious atomic deposition in the scrape-off layer (SOL) after pellet injection, which depends strongly on the injection velocity. With increasing injection velocity, the atomic density in the SOL decreases evidently and the deposition time is relatively shortened. Possible effects for triggering of edge localized modes (ELMs) by D and Li pellets are also discussed. With the same pellet size and injection velocity, the maximum perturbation pressure caused by D pellets is obviously higher. It is found that the resulting maximum perturbed pressure is remarkably enhanced when the injection velocity is reduced from 300 m/s to 100 m/s for a pellet with a cross section of 1.6 mm, which indicates that the injection velocity is important for ELM pacing. This work can provide reasonable guidance for choosing pellet parameters for fueling and ELM triggering.     

Reactivation of Promoted Nickel Catalysts for Deuterium Exchange between Hydrogen and Water in the Vapour Phase

Binary promoted nickel – chromium oxide and ternary promoted nickel – chromium oxide – aluminium oxide mixed catalysts were prepared for use in the present study. The catalysts were prepared by co-precipitation of the corresponding metal nitrates as carbonates followed by calcination in nitrogen atmosphere at 350 °C and reduction in hydrogen atmosphere at 320 °C. To prevent spontaneous oxidation of the catalysts, bidistilled water was added followed by heating of the catalyst mixtures at about 110 °C in hydrogen atmosphere for few hours. Deactivation of catalysts was studied by measurements of the variation of their activities with the time of contact of the reacting gas mixtures with the catalyst surface in the reaction chamber. It was found that while the catalytic activity of ternary catalysts for the isotopic exchange of deuterium between hydrogen and water vapour was higher than that of the binary one, the loss in activity of the former teas faster than the latter. Reactivation of the catalysts were carried out at different temperatures between 110–160°C in hydrogen atmosphere. Catalytic activity measurements indicated that higher temperatures are better for the reactivation process.     

Enantiospecific C?H Activation Using Ruthenium Nanocatalysts

The activation of C H bonds has revolutionized modern synthetic chemistry. However, no general strategy for enantiospecific C H activation has been developed to date. We herein report an enantiospecific C H activation reaction followed by deuterium incorporation at stereogenic centers. Mechanistic studies suggest that the selectivity for the α‐position of the directing heteroatom results from a four‐membered dimetallacycle as the key intermediate. This work paves the way to novel molecular chemistry on nanoparticles.     

Isentropic Compression of Substances Using Ultra‐High Magnetic Field: Zero Isotherms of Protium and Deuterium in Pressure Range up to ∼5 Mbar

Experiments on isentropic compression of a substance using a high magnetic field pressure are described. Their goal is building of a zero isotherm in a multi‐megabar pressures range. A method of the pressure and density determination of the compressed substance based on radiographic data obtained in the experiment is presented. The results of the experiments with solid (in initial state) protium and deuterium are presented. The densities that correspond to more than seventeen‐fold compression are reached. Obtained experimental points are compared with extrapolation of a curve that is built in the experiments using anvil cells and with the results of several ab‐initio calculations (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Site‐Selective and Metal‐Free Aliphatic CH Oxidation Enabled Synthesis of [5,24,25‐D3]‐(25S)‐Δ7‐Dafachronic acid

Steroid hormones play significant roles in both worms and mammalians. (25S)‐Δ⁷‐Dafachronic acid (Δ⁷‐DA, 1 ) is a member of the dafachronic acid hormonal series that regulates both development and lifespan of C. elegans. Despite its importance, effective tools for the illumination of its mode of action are lacking. Herein, we report an efficient synthesis of trideuterated Δ⁷‐DA, [5,24,25‐D3]‐(25S)‐Δ⁷‐dafachronic acid ([D₃]‐Δ⁷‐DA, 2 ), as a useful chemical tool for subsequent biological studies. Key steps for this bioinspired synthesis approach include site‐selective aliphatic C?H oxidation mediated by methyl(trifluoromethyl)dioxirane (TFDO), and the iridium/phosphine‐oxazoline‐catalyzed late‐stage asymmetric deuterium reduction.     

Isotopieeffekte Bei Autoxydationen,VI: Vergleieh der Thermo-Oxydativen Stabilität von Normalem und Deuteriertem PVC

Es wird die Synthese von deuteriertem PVC beschrieben. Die bei 180°C in Sauerstoffatmosphäre durchgeführten Stabilitätsmessunen werden im Vergleich zu den am normalen PVC erhaltenen Werten diskutiert und die IR-Spektren der thermooxydative beanspruchten Proben zur Deutung des Abbaumechanismus herangezogen.     

Miller–Urey Spark-Discharge Experiments in the Deuterium World

We designed and conducted a series of primordial-soup Miller-Urey style experiments with deuterated gases and reagents to compare the spark-discharge products of a “deuterated world” with the standard reaction in the “hydrogenated world”. While the deuteration of the system has little effect on the distribution of amino acid products, significant differences are seen in other regions of the product-space. Not only do we observe about 120 new species, we also see significant differences in their distribution if the two hydrogen isotope worlds are compared. Several isotopologue matches can be identified in both, but a large proportion of products have no equivalent in the corresponding isotope world with ca. 43 new species in the D world and ca. 39 new species in the H world. This shows that isotopic exchange (the addition of only one neutron) may lead to significant additional complexity in chemical space under otherwise identical reaction conditions.     

Revealing the metabolic sites of atazanavir in human by parallel administrations of D‐atazanavir analogs

Atazanavir (Reyataz^®) is an important member of the HIV protease inhibitor class. Because of the complexity of its chemical structure, metabolite identification and structural elucidation face serious challenges. So far, only seven non‐conjugated metabolites in human plasma have been reported, and their structural elucidation is not complete, especially for the major metabolites produced by oxidations. To probe the exact sites of metabolism and to elucidate the relationship among in vivo metabolites of atazanavir, we designed and performed two sets of experiments. The first set of experiments was to determine atazanavir metabolites in human plasma by LC‐MS, from which more than a dozen metabolites were discovered, including seven new ones that have not been reported. The second set involved deuterium labeling on potential metabolic sites to generate D‐atazanavir analogs. D‐atazanavir analogs were dosed to human in parallel with atazanavir. Metabolites of D‐atazanavir were identified by the same LC‐MS method, and the results were compared with those of atazanavir. A metabolite structure can be readily elucidated by comparing the results of the analogs and the pathway by which the metabolite is formed can be proposed with confidence. Experimental results demonstrated that oxidation is the most common metabolic pathway of atazanavir, resulting in the formation of six metabolites of monooxidation (M1, M2, M7, M8, M13, and M14) and four of dioxidation (M15, M16, M17, and M18). The second metabolic pathway is hydrolysis, and the third is N‐dealkylation. Metabolites produced by hydrolysis include M3, M4, and M19. Metabolites formed by N‐dealkylation are M5, M6a, and M6b. Copyright © 2013 John Wiley & Sons, Ltd.