Identification of a series of C25-C40 acyclic isoprenoid hydrocarbons in crude oils

The identification of acyclic isoprenoid hydrocarbons in organic extracts of geological samples and particularly in petroleum deserves a great interest from the biological origin of the sedimentary organic matter and the understanding of geochemical processes.     

Sandwich structures at oil-water interfaces under alkaline conditions

Equilibrium liquid crystal (LC) layer on an interface between crude oils and water was observed at high pH. This layer is composed mainly of sodium naphthenates produced in situ at the water/oil interface. Transient LC layer was also evolved at the interface of aqueous phase of sodium hydroxide solutions and oleic phase of naphthenic acid (NA) solutions as result of a chemical reaction between NaOH and NA. This chemical reaction causes transport process resulting in a disturbance of the interface. Optical observation of this interface disturbance reviled that the interface covered with LC shows considerably lower flexibility as compared to LC free interface. The LC layer eventually dissolves in the water phase at low oil-to-water ratio, while at high oil-to-water ratio it can form an equilibrium phase, which spreads spontaneously at the oil-water interface.     

Thermodynamic parameters for the molecular inclusion reaction of dulcin with beta-cyclodextrin. spectrofluorimetric determination of dulcin

The inclusion of dulcin in alpha- and beta-cyclodextrin has been studied by fluorescence spectroscopy. To quantitatively describe complex formation between the beta-cyclodextrin and dulcin, an association constant of 290 M(-1) at 21 degrees was obtained. The thermodynamics associated with the complex formation between dulcin and beta-cyclodextrin in aqueous solution has been studied. The obtained value of DeltaG(0) = -13.7 kJ/mole at 21 degrees , together with DeltaH(0) = -33.6 +/- 2.3 kJ/mole and DeltaS(0) = -67.2 +/-8.3 Jmole(-1) K(-1) indicate that dulcin has a very marked tendency to associate with beta-cyclodextrin in water. The inclusion complex of dulcin in beta-cyclodextrin has been used to determine dulein in the range 0.13-5 mug/ml the method has been applied to determine dulcin in soft drinks.     

Degradation of ²-O-4 lignin model and related compounds by the ascomyceteChrysonilia sitophila (TFB 27441 strain)

Growth of the ascomyceteChrysonilia sitophila during degradation of lignin model dimers and monomers was compared to a glucose control. An inhibition of growth by Cα-carbonyl monomers and stimulation by β-O-4 lignin model and vanillyl alcohol were observed. A comparison of the degradation by this ascomycete with the basidiomycetePhanerochaete chrysosoporium showed similarities in relation to the type of degradation caused.     

Properties and analytical applications of the heteropolymolybdates of phosphorus, arsenic, silicon and germanium-IV Determination of phosphomolybdic and silicomolybdic acids via the molybdenum content, with phenylfluorone

Procedures are proposed for the determination of phosphorus and silicon in the ppM range, by extraction of phosphomolybdic and silicomolybdic acids with organic solvent, decomposition of the complex and spectrophotometric determination of its molybdenum content.     

Complex study of nickel skeleton catalysts: V. Study of novel non-pyrophoric nickel skeleton catalysts by derivatograph

The structure and properties of non-pyrophoric skeleton catalysts prepared from NiSi, NiAlSi, NiMg and NiZn alloys have been studied—apart from other thermal methods—by means of the derivatograph.Our experimental results have contributed to the explanation of the non-pyrophoric behaviour of these catalysts. We demonstrated that the desorption of the hydrogen content in our catalysts is not accompanied by the oxidation of active nickel. This oxidation takes place only at higher temperatures, above 200°C, at a rate proportional to the amount of active nickel.Other constituents of the catalysts (adsorbed water, hydroxide content) were also determined from the experimental data. The outstandingly high Mg(OH)₂ content of the NiMg catalyst indicates that its structure is dissimilar: Mg(OH)₂ also acts as support for the catalyst.     

Isotope gas analysis of tritium-labelled organic compounds based on pyrolytical decomposition

Summary A procedure has been developed for the activity measurement of tritium-labelled organic compounds in the gas phase. The organic compounds are pyrolysed in hydrogen carrier gas at 1150° and the decomposition products are swept through a carbon packing in accordance with the principle of the oxygen determination developed byUnterzaucher andBürger. The radioactive gas mixture obtained from the sample is swept by the hydrogen carrier gas flowing continuously through the reactor into a proportional counter tube, after the addition of propanebutane counter gas. By closure of the counter tube at a suitable moment, the radioactive gas is quantitatively trapped in the counter tube. The activity is measured in the limited proportional region. No memory effect occurs. The preparation of the sample requires 12 minutes; the relative standard deviation of analysis is <0.5%.

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Zusammenfassung Ein Verfahren zur Aktivitätsbestimmung bei tritium-markierten organischen Verbindungen in der Gasphase wurde ausgearbeitet. Die organischen Substanzen werden in Wasserstoff als Trägergas bei 1150° pyrolysiert. Die Zersetzungsprodukte werden wie bei der Sauerstoffbestimmung nachUnterzaucher bzw.Bürger über eine Kohleschicht geleitet. Das radioaktive Gas-gemisch aus der Probe gelangt mit dem kontinuierlich strömenden Trägergas in ein Proportionalzählrohr, nachdem Propan-Butan-Zählgas zugesetzt wurde. Man schließt das Zählrohr im richtigen Augenblick, um das radioaktive Gas quantitativ zu erfassen. Die Aktivität wird im Proportionalbereich gemessen. Ein Memory-Effekt tritt nicht auf. Die Vorbereitung der Probe beansprucht 12 Minuten. Die relative Standardabweichung ist kleiner als 0,5%.

     

A non local density functional calculation of the diamagnetic susceptibilities and other electronic properties of noble gases and closed-shell ions

The non local weighted-density approximation (WDA) to the exchange-correlation potentialV _xc (r) is used to compute electron densities, ionization potentials and electron affinities of several atoms and ions. Especial care is taken in calculating and discussing 〈r ²〉 in noble gas atoms. Good results are obtained for all those quantities, but it is critical that the WDA is applied in such a way that it preserves the correct larger behaviour ofV _xc (r). A comparison of the calculated electron density with that of the Hartree-Fock method shows the effects of coulomb correlation. The density rearrangements upon the introduction of correlation agree qualitatively with the results of Configuration-Interaction calculations     

Crystal structure of 1-[N-2-aminoethyl)-aminopropyl]silatrane

The crystal structure of 1-[N-(2-aminoethyl)aminopropyl]silatrane has been determined by x-ray diffraction at room temperature. The Si←N bond distance (2.165(2) Å) is in the range observed for other 1-X-propylsilatranes (X = CN, OH, SH, Cl and SCN). The structure is partially disordered: the silatrane moiety displays a disorder that is typical for silatranes and the aminoethyl group terminating the planar chain linked to silicon is rotationally disordered.     

Thermal properties of tetrahydroperparine derivatives

The thermal behaviour of tetrahydroperparine (THP) and its derivatives with various acids has been investigated. The acid is liberated from the formate derivative basically in two steps, while the other aliphatic acids are released quantitatively before the thermal decomposition of the THP molecule. The thermoanalytical curves, electrical conductivity data measured in the molten phase, and infrared spectra prove that while part of the formic acid is hydrogen-bonded the other part is bound ionically in the molecule. It may be assumed that the marked biological activity of the compound can be explained by this difference in the nature of the bonds.