Kinetic study of n-heptane oxidation

The oxidation of n-heptane has been studied in a jet-stirred flow reactor in the temperature range 950–1200 K at atmospheric pressure for a wide range of fuel-oxygen equivalence ratios (0.2 to 2.0). A chemical kinetic reaction mechanism developed from previous studies on smaller hydrocarbons and extended to C₆ and C₇ species was used to reproduce the experimental data. Good agreement between computed and measured concentrations of major chemical species was obtained for the entire range of experimental conditions. Sensitivity analyses were carried out to identify the reactions having the greatest influence on the modeling results. The major reaction paths for n-heptane consumption and for the formation of the main products have been identified. In addition n-heptane ignition delays behind a reflected shock wave measured by other investigators were used to validate the present reaction mechanism at higher temperature and pressure.     

Temperature dependence of the rate constants for reactions of the carbonate radical with organic and inorganic reductants

Rate constants have been measured by pulse radiolysis for the reactions of the carbonate radical, CO₃^·?, with a number of organic and inorganic reactants as a function of temperature, generally over the range 5 to 80°C. The reactants include the substitution-inert cyano complexes of Fe^II, Mo^IV, and W^IV, the simple inorganic anions SO₃^2?, ClO₂^?, NO₂^?, I^?, and SCN^?, several phenolates, ascorbate, tryptophan, cysteine, cystine, methionine, triethylamine, and allyl alcohol. The measured rate constants ranged from less than 10⁵ to 3 × 10⁹ M^?1 s^?1, the activation energies ranged from ?11.4 to 18.8 kJ mol^?1, and the pre-exponential factors ranged from log A = 6.4 to 10.7. The activation energies for the metal complexes and inorganic anions generally decrease with increasing driving force for the reaction, as expected for an outer sphere electron transfer. For highly exothermic reactions, however, the activation energy appears to increase, probably reflecting the temperature dependence of diffusion. For many of the organic reactants, the activation energies were low and independent of driving force, suggesting that the oxidation is via an inner sphere mechanism.     

The inclusion of electrostatic and dispersion interactions into potentials of mean torque for solutes dissolved in uniaxial liquid crystal solvents

A potential of mean torque is derived for a solute at infinite dilution in a uniaxial liquid crystal solvent, which contains terms originating from the dispersion interaction, and the electrostatic interaction between quadrupole moments on both molecules. It is shown that the electrostatic term is non-zero only if the solute-solvent vectors are distributed with lower than spherical symmetry. If this distribution has cylindrical symmetry then both the electrostatic and dispersion terms in the potential of mean torque are shown to depend on order parameters for the orientational distribution of the solute-solvent vectors, as well as on the order parameters of the solvent molecules.     

Subchronic oral toxicity (six months) of carboxyethylgermanium sesquioxide [(HOOCCH2CH2Ge)2O3]n in rats

After briefly renewing toxicological data on germanium compounds, the authors report on the subchronic oral toxicity of carboxyethylgermanium sesquioxide in rats. During six months, male and female animals received 1 g kg^?1. day^?1. No particular toxic symptoms, and no behaviour problems except a small decrease of body weight in male rats, at the end of the six-month experimentation period, were observed. A significant decrease of erythropoiesis and some significant changes in leucocyte ratios were demonstrated. The main marked effect was a moderate renal dysfunction characterized by a tubular disease with the presence of cylinders, swelling of tubulus cells and flocculus deposits. Germanium urinary excretion was constant and linked to the received dose. Six months later, no preferential accumulation in organs was evident.     

Determination of tributyltin oxide in coastal marine sediments and mussels by electrothermal atomic absorption spectrometry

We have devised a new method for bis(tributyltin)oxide (TBTO) determination in marine sediments and mussels. This technique involves an n-hexane/methylene chloride mixture extraction and extract purification with a sodium hydroxide wash in order to eliminate interfering compounds. TBTO is then extracted again by nitric acid and converted into an inorganic tin species; the analysis has been effected using Zeeman graphite furnace-atomic absorption spectrophotometry. The method detection limit for the matrices examined is 0.004 μg TBTO g^?1 (wet weight) and is sufficient for the analysis in real samples. The percentage recovery of TBTO from sediments and mussels samples is higher than 85% and 95% respectively. This method has been applied to TBTO level determination in sediments and mussels (Mytilus galloprovincialis) sampled in the harbour area in Taranto, where mussel culture activities are much developed; the TBTO levels obtained in sediments and mussels were in the range 15-47 ng g^?1 (wet weight) and 11-30 ng g^?1 (wet weight) respectively. Such values are comparable with those found in other harbour areas in the Mediterranean Sea.     

Certification of the sulphur content of three rapeseed reference materials

Summary The sulphur content of three rapeseed reference materials has been certified on the basis of measurements made by inductively coupled plasma-optical emission spectroscopy, isotope-dilution mass spectrometry and ion chromatography. Their suitability for the calibration of x-ray fluorescence spectrometers used for measuring sulphur in rapeseed samples was established.     

Study on reproductive endocrinology of human placenta (III)--Hormonal regulation of progesterone production by trophoblast tissue of first trimester.

The effect of hormones on progesterone secretion by 6-8 week human trophoblast tissue cultured in serum-free medium has been investigated. GnRH at low concentration (10(-10)-10(-8) mol/L) stimulated progesterone secretion, while high dose (10(-6)-10(-5) mol/L) produced inhibitory effect. The progesterone secretion could be significantly decreased by addition of anti-hCG antiserum or monoclonal anti-hCG IgG in a dose- and time-dependent manner. Various concentrations of TRH, PGE2, PGF2 alpha, testosterone and estradiol were found to be ineffective. These data indicate clearly that progesterone production by human trophoblast tissue at early gestation stage is under the modulation of GnRH and hCG.     

Total surface areas of Group IVA organometallic compounds: Predictors of toxicity to algae and bacteria

There is a high correlation between molecular surface area (TSA) of triorganotin and triorganolead compounds and their toxicity towards a bacterium (Escherichia coli) and an alga (Selenastrum capricornutum). Parallel attempts to correlate other Group IVA organometals incorporating silicon or germanium were unsuccessful. It was further demonstrated, however, that a high correlation was obtainable between certain series of compounds with the same organic substituent but different metal centers involving all Group IVA elements. In both instances, the inability to obtain a quantitative structure-activity relationship (QSAR) for all systems studied appears to be a function of the solubility of the compounds. While organotin TSA values have been found to correlate well with their toxicities toward various organisms, this study clearly suggests that this type of QSAR can be readily extended to include other organometal systems, provided that there is no solubility problem and the toxicity is a function of the hydrophobicity of the organometal compounds.     

Synthesis of 1-(3-alkyl-2,3-dideoxy-D-pentofuranosyl)uracils with potential anti-HIV activity.

1-(3-Alkyl-2,3-dideoxy-alpha,beta-D-erythro-pentofuranosyl)uracils and 1-(3-alkyl-2,3-dideoxy-alpha,beta-D-threo-pentofuranosyl)uracils have been prepared from (E)-4,5-di-O-acetyl-2,3-dideoxy-aldehydo-D-glycero-pent-2-enose by a Michael addition reaction of the appropriate organocopper reagent followed in subsequent order by glycosidation of the resulting 3-alkyl-4,5-diacetoxypentanal with methanolic hydrogen chloride, protection with p-methoxybenzoyl chloride, and trimethylsilyl triflate catalyzed coupling with 2,4-di-O-(trimethylsilyl)uracil. The nucleosides were deprotected by treatment with 33% methylamine in absolute ethanol and separated by reversed-phase HPLC.