Chlorine nitrate photolysis by a new technique: very low pressure photolysis

Very low pressure photolysis (VLPØ) of chlorine nitrate was performed in a quartz Knudsen cell. The light source was a 2500 W high-pressure xenon lamp, and a modulated molecular-beam mass spectrometer was used to monitor the concentration of ClONO₂ and photolysis products. Because of the low pressures used (? 10^?3 torr) and the short residence time in the cell (≈1 s), secondary reactions were unimportant and the primary products could be directly identified. The primary photolysis products (λ ≈ 2700 Å) are atomic chlorine and NO₃ free radical. Chlorine atoms were identified both by the appearance of Cl₂ (wall recombination product; the walls were not poisoned) and by HCl produced when C₂H₆ was added to the cell. Nitrate free radical was directly identified as a mass peak at m/e = 62, as well as by chemical titration with nitric oxide: NO₃ + NO → 2NO₂. It was verified by direct tests that the peak at m/e = 62 did not arise from possible HNO₃ contamination or from N₂O₅, a possible secondary product. This titration reaction was used to measure quantitatively a lower limit to the primary quantum yield, φ ? 0.5 ± 0.3. This represents a lower limit because of the unknown extent of the secondary photolysis of NO₃ under our conditions. We believe this to be the first observation using mass spectrometry of the NO₃ free radical. The quantum yield for atomic chlorine is φ = 1.0 ± 0.2. N₂O was used to test for O(¹D) according to the reaction, O(¹D) + N₂O → products; none was observed. Triplet oxygen, O(³P) was observed to the extent of ≈ 10% by the reaction O(³P) + NO₂ → NO + O₂, but this yield can also be due to the photolysis of NO₃ free radical produced in the primary step. We conclude that the predominant reaction pathway is

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Spectra and structure of organogermanes: Part XX. Infrared and Raman spectra of (CH3)3GeNCO and (CH3)3GeNCS

The infrared and Raman spectra of gaseous and solid (CH₃)₃ GeNCO and solid (CH₃)₃GeNCS have been recorded over the frequency range 20–4000 cm^?1 . The Raman spectra of the liquids have also been recorded. Assignments of the normal modes have been made on the bases of band types, Raman depolarization values, and characteristic frequencies. Spectral data indicate that (CH₃)₃ GeNCO is non-linear in all phases and that (CH₃)₃GeNCS has a linear or quasi-linear heavy atom skeleton in the fluid phases.     

Hormone-receptor interactions. Carboranylalanine (Car) as a phenylalanine analogue: reactions with chymotrypsin.

In order to test the effects of the replacement of phenylalanine by carboranylalanine (Car) in biological ligand-acceptor interactions, Z · Ala-Ala-Car · OH (1) and Ac · Car · OEt (2) were synthesized and their reactions with chymotrypsin studied. The two compounds proved to be good inhibitors with K(i) values of 3 · 10^?4M (1) and 8.6 · 10⁴M (2) ; the K(i) of Z · Ala-Ala-Phe · OH (1a) is 1 · 10^?3M . The inhibition constants were determined by a new photolytic technique, inhibition of photoaffinity labelling by Z · Ala-Ala-Phe(pN₃) · OH. Ac · Car · OEt is not hydrolysed by chymotrypsin. The findings indicate that the carboranyl group can interact with the ‘phenyl recognition site’ of the enzyme to produce the binding that is characteristic of aromatic amino acid residues. However, some kind of distortion in the region of the ‘mechanistic site’ must be postulated in order to account for the failure of hydrolysis. Some possible effects of the replacement of aromatic amino acids by Car in peptide hormones on hormone-receptor interactions are discussed.     

Bestimmung von Spurenelementen in Staubproben durch Röntgenfluorescenzanalyse mit Radionuklidanregung unter besonderer Berücksichtigung der Matrixeffekte

The analysis of dust samples by X-ray fluorescence using Cd-109 as X-ray source is described. For calibration silica gel standards are used. The correction for matrix effects is carried out by means of the Compton peaks. Besides the elements K, Ca, Ti, Fe, Rb, Sr, Y, Zr, which may be considered to be natural components of the ground, the elements Cr, Mn, Ni, Cu, Zn, Br and Pb are determined in the dust samples.     

A volumetric determination of arsenic and antimony in mixed manganese arsenide,antimonide and phosphide compounds

A procedure is described for the titrimetric determination, of arsenic and antimony without separation. Total combined arsenic and antimony were determined by reduction with tin(II) chloride and titration with permanganate; antimony is found by selective reduction with mercury(I) chloride and titration with permanganate. A precision of 0.1–0.2% was obtained for total combined arsenic and antimony, and approximately 1% for antimony alone (small amounts in the presence of large amounts of arsenic). The procedure was developed for and applied to the analysis of synthesized compounds of the type MnAs_1-xP_x and MnAs_1-ySb_y.     

Thermogravimetric analysis of polycarbonates and polythiocarbonates from diphenols with methyl groups

The thermal behaviour of polycarbonates and polythiocarbonates derived from biphenols with methyl groups in the aromatic rings was studied by dynamic thermogravimetry. The thermal degradation temperatures (TDT) were determined, showing that polythiocarbonates are more stable than the corresponding polycarbonates. The kinetic parameters of the thermal decomposition were determined by using the Arrhenius relationship, and showed two steps for the degradation of the polycarbonates, the first being a zero-order process and the second having first-order kinetics; the steps were associated with two different reaction mechanisms. Polythiocarbonates degraded according to first-order kinetics.     

Calorimetric and diffractometric study of the lowest room-temperature transition of polytetrafluoroethylene

Through differential scanning calorimetry and wide angle x-ray scattering, the room-temperature transitions of native (never melted) polytetrafluoroethylene have been investigated. The independence of the transitions, and in particular of the lowest one, on the heating kinetics, seems to suggest that also this transition is a true crystal-crystal transition.     

Uptake of thorium ions from aqueous solutions by a molecular sieve (13X type) powder

The adsorption of thorium(IV) ions on molecular sieve (13X type) powder from aqueous solutions has been studied as a function of shaking time pH, thorium ion concentration and temperature. The conditions of maximum adsorption of thorium ions obeys Langmuir and D-R isotherms over the entire concentration range studied. Thermodynamic quantities such as H, G and S have been calculated fromK _D values determined at various temperatures. The results show endothermic heat of adsorption, but negative free energy value indicates that the process of thorium adsorption on molecular sieve powder is favored at high temperature. The influence of various cations and anions on thorium(IV) ion adsorption was examined. A wavelength dispersive X-ray fluorescence spectrometer was used for measuring the thorium ion concentration in solutions.     

Alkaloids ofThalictrum isopyroides

Summary 6,7-Dimethoxy-2-methyl-1,2-dihydroisoquinolin-1-one and the new aporphine base 9-hydroxy-1,2,3,10-tetramethoxyaporphine, which has been called thalisopynine, have been isolated fromThalictrum for the first time.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnyk Soedinenii, No. 4, pp. 472–474, July–August, 1978.     

Absorption and fluorescence spectroscopy of rhodamine 6G in titanium dioxide nanocomposites

A comparison has been made between the spectroscopic properties of the laser dye rhodamine 6G (R6G) in mesostructured titanium dioxide (TiO(2)) and in ethanol. Steady-state excitation and emission techniques have been used to probe the dye-matrix interactions. We show that the TiO(2)-nanocomposite studied is a good host for R6G, as it allows high dye concentrations, while keeping dye molecules isolated, and preventing aggregation. Our findings have important implications in the context of solid state dye-lasers and microphotonic device applications.