Dynamic stability of carbonyl ylides

The non- and fluorine-substituted singlet carbonyl ylides are studied by using ab initio MCSCF calculations. The thermodynamic stability of the carbonyl ylides and the intramolecular stability to isomerization or fragmentation reaction coordinates is demonstrated in terms of the topological structure of the ab initio potential energy surfaces. The allylic resonance is found to be dynamically unstable, considering out-of-plane vibrational mode. The instability is studied by the symmetries of the low-lying excitations out of the MCSCF wave function.     

Direct measurements of HOx radicals in the marine boundary layer: testing the current tropospheric chemistry mechanism

OH and HO(2) radicals, atmospheric detergents, and the reservoir thereof, play central roles in tropospheric chemistry. In spite of their importance, we had no choice but to trust their concentrations predicted by modeling studies based on known chemical processes. However, recent direct measurements of these radicals have enabled us to test and revise our knowledge of the processes by comparing the predicted and observed values of the radical concentrations. We developed a laser-induced fluorescence (LIF) instrument and successfully observed OH and HO(2) at three remote islands of Japan (Oki Island, Okinawa Island, and Rishiri Island). At Okinawa Island, the observed daytime level of HO(2) agreed closely with the model estimates, suggesting that the photochemistry at Okinawa is well described by the current chemistry mechanism. At Rishiri Island, in contrast, the observed daytime level of HO(2) was consistently much lower than the calculated values. We proposed that iodine chemistry, usually not incorporated into the mechanism, is at least partly responsible for the discrepancy in the results. At night, HO(2) was detected at levels greater than 1 pptv at all three islands, suggesting the presence of processes in the dark that produce radicals. We showed that ozone reactions with unsaturated hydrocarbons, including monoterpenes, could significantly contribute to radical production.     

Unexpected, drastic effect of triflic acid on oxidative diacetoxylation of iodoarenes by sodium perborate. A facile and efficient one-pot synthesis of (diacetoxyiodo)arenes

An easy, safe, and effective method for preparing (diacetoxyiodo)arenes from iodoarenes is presented. Addition of trifluoromethanesulfonic acid (triflic acid) as a promoter causes a drastic increase in the yield of (diacetoxyiodo)arenes in the reaction of iodoarenes with sodium perborate. The reaction of the iodoarenes with sodium perborate in acetic acid in the presence of triflic acid at 40-45 degrees C efficiently generates the corresponding (diacetoxyiodo)arenes in high yields within short time.     

Atomic absorption spectrometry of traces of tri- and hexavalent chromium

Summary Atomic absorption spectrometry combined with extraction is described for the determination of tri- and hexavalent chromium. The chromium diethyldithiocarbamate chelate was used for chromium (VI), whereas hydroxyquinolate or thenoyltrifluoroacetonate chelate for chromium(III). The method is rapid and precise.

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Zusammenfassung Extraktion und darauffolgende Messung der Atomarabsorption wurden zur Bestimmung von drei- und sechswertigem Chrom verwendet. Die Chelatverbindung mit Diäthyldithiocarbamat wurde für Chrom(VI), der Chelatkomplex mit Hydroxychinolin oder Thenoyltrifluoraceton für Chrom(III) verwendet. Das Verfahren ist rasch und genau.

     

Spectroscopic study of atomization processes and inter-element effects on the flame emission of chromium and iron in an air—acetylene flame

Emission spectroscopy is applied for characterization of reactions occurring in air—acetylene flames normally used for atomic absorption spectrometry. Inter-element effects on the emissions of chromium and iron are discussed. Two atomic emission lines with different upper energies and a molecular emission line of the diatomic oxide MO are compared for determination of the excitation temperature and the degree of atomization in fuel-rich and lean flames. The reductive power of the fuel-rich flame is essential for atomization of chromium salts. Inter-element effects by iron can be attributed to the formation of refractory oxides, and to mutual catalytic oxidation.     

ACTION SPECTRUM FOR PHOTOREACTIVATION OF ULTRAVIOLET-INDUCED MORPHOLOGICAL ABNORMALITY IN SEA URCHIN EGGS

Abstract An action spectrum was obtained for photoreactivation (PR) of morphological abnormality arising from ultraviolet (UV)-irradiation of sea urchin sperm. The wavelength dependence of PR was measured by the restoration of the formation of normal pluteus larvae after the exposure of fertilized eggs to various fluences of monochromatic PR light (313 to 500 nm). The PR action spectrum showed a maximum around 365 nm and a secondary peak somewhere above 400 nm. High PR activity beyond 400 nm wavelengths may reflect an advantageous or adaptational ability to cope with harmful effects of solar UV radiation.     

The system BaOGeO2 at high pressures and temperatures,with special reference to high-pressure transformations in BaGeO3, BaGe2O5, and Ba2Ge5O12

Phase relations in the system BaOGeO₂ were investigated in the pressure range 20–70 kbar in the temperature range 750–1200°C. Several new phases were identified in this system: an atmospheric phase of BaGe₂O₅ (monoclinic BaGe₂O₅ I), two high-pressure phases of BaGe₂O₅ (monoclinic BaGe₂O₅ II and tetragonal BaGe₂O₅ III), and a high-pressure phase of Ba₂Ge₅O₁₂. The phase boundary curve between BaGe₂O₅ II and BaGe₂O₅ III was preliminarily determined as P(kbar) = 7.7 + 0.047T (°C). The high-pressure phases of BaGeO₃, which were previously reported by Y. Shimizu, Y. Syono, and S. Akimoto (High Temp.-High Pressures2, 113 (1970)) in the pressure range 15–95 kbar, were interpreted to be not single-phase materials but complicated mixtures of more than two phases in the system BaOGeO₂. X-Ray powder diffraction data for the new compounds synthesized in this study are given.