Reactions of the nitrate radical with a series of reduced organic sulphur compounds in air

A 480 L evacuable reaction chamber, equipped with FT-IR spectroscopy on-line and ion chromatography off-line, has been used to study the gas phase reaction between the nitrate radical, NO₃, and the reduced organic sulphur compounds CH₃CH₂SH, (CH₃CH₂)₂S, (CH₃CH₂)₂S₂, and CH₃CH₂SCH₃ in air. The products CH₃CH₂SO₃H, SO₂, H₂SO₄, CH₃CHO, and CH₃CH₂ONO₂ were identified and quantified in the reactions of the first three compounds, CH₃CH₂SH, (CH₃CH₂)₂S, and (CH₃CH₂)₂S₂. The reaction products were CH₃CH₂SO₃H, CH₃SO₃H, SO₂, H₂SO₄, CH₃CHO, and CH₂O in the reaction of CH₃CH₂SCH₃. On the basis of identified reaction products and intermediates observed in the infrared spectra, mechanisms are proposed for the reactions between the NO₃ radical and the four reduced organic sulphur compounds. The results of this study, together with those from previous experiments performed in this laboratory on CH₃SCH₃, CH₃SH, and CH₃SSCH₃ lead to the conclusion that all these species, in the reaction with the NO₃ radical, follow a similar degradation mechanism producing SO₂, H₂SO₄, R? SO₃H, R? CHO, and R? CH₂ONO₂, as the main reaction products. The inital step of the reaction of NO₃ with R? S? R and R? S? H type (R = CH₃, CH₂CH₃) reduced organic sulphur compounds was found to be H-atom abstraction, probably after the formation of an initial adduct. For the reaction between NO₃ and R? S? S? R type compounds, evidence for an addition-decomposition reaction, as the initial steps, was obtained. R? S·, R? S(O)·, and R? S(O)₂· appear to be formed as intermediates in all the reactions. © John Wiley & Sons, Inc.     

Solubility diagrams of the potassium iodide-water-N,N-dimethylformamide and iodine-iodide-water-N,N-dimethylformamide systems at 25°C

The solubility diagrams of the potassium iodide-water-N,N-dimethylformamide (DMFA) and iodine-iodide-water-N,N-dimethylformamide systems were studied at 25°C by the method of sections. The systems are characterized by three-phase equilibria of the peritonic and eutonic types, respectively. Potassium iodide in the I₂-KI-/H₂O-DMFA (95: 5 wt %)/ system was found to salt in crystalline iodine. The selected composition of the H₂O-DMFA mixed solvent possessed a higher iodine-solving ability compared with pure mixture components.     

X-ray photoelectron spectroscopy characterization of composite TiO2–poly(vinylidenefluoride) films synthesised for applications in pesticide photocatalytic degradation

X-ray photoelectron spectroscopy (XPS) was adopted for the analytical characterization of composite titanium dioxide–poly(vinylidenefluoride) (TiO₂–PVDF) films developed for applications in the photocatalytic degradation of pollutants.

The composites were deposited on glass substrates by casting or spin coating from TiO₂–PVDF suspensions in dimethylformamide (DMF). XPS data on the TiO₂–PVDF surface composition were used to optimize preparation conditions (composition of the TiO₂/PVDF suspension, deposition technique) in terms of titanium dioxide surface amount and film stability.

The use of spin-coating deposition and the increase of TiO₂ amount in the DMF suspensions were found to improve the titanium surface content, although high TiO₂/PVDF ratios led to film instability. PVDF–TiO₂ films were also used in preliminary photocatalytic degradation tests on isoproturon, a phenylurea herbicide, under solar UV irradiation; the results were compared to direct photolysis to evaluate the catalytic efficiency of immobilized TiO₂ and the role played by the PVDF film during the degradation process.     

Aerodynamics of ski jumping: experiments and CFD simulations

The aerodynamic behaviour of a model ski jumper is investigated experimentally at full-scale Reynolds numbers and computationally applying a standard RANS code. In particular we focus on the influence of different postures on aerodynamic forces in a wide range of angles of attack. The experimental results proved to be in good agreement with full-scale measurements with athletes in much larger wind tunnels, and form a reliable basis for further predictions of the effects of position changes on the performance. The comparison of CFD results with the experiments shows poor agreement, but enables a clear outline of simulation potentials and limits when accurate predictions of effects from small variations are required.     

Analysis of iron storage proteins in chicken liver and spleen tissues in comparison with human liver ferritin by Mössbauer spectroscopy

Summary Characterization of iron storage proteins in liver and spleen from normal chicken and chicken with lymphoid leukemia in comparison with human liver ferritin were considered by M?ssbauer spectroscopy (preliminary results). Small differences in M?ssbauer hyperfine parameters for both normal and lymphoid leukemia chicken liver and spleen were observed. The value of quadrupole splitting for human liver ferritin was higher than those for chicken tissues. A decrease of iron content in lymphoid leukemia chicken tissues was also found, however, the reason of this fact (pathology or feeding) was not clear yet.     

Some nucleophilic substitution reactions of s-triazolo[1,5-c]pyrimidines

Nucleophilic substitution of 5-methylthio- and 5-cyanomethylthio-7-amino-s-triazolo[1,5-c]pyrimidines has been carried out using sodium hydroxide, ammonia, hydrazine hydrate, and four amines. The cyanomethyl group is particularly reactive under these conditions and 5-cyanomethylthiotriazolopyrimidine can be used to functionalize this heterocycle.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 382–385, March, 1992.