Electron emission from naphthacene crystal due to the impact of argon and krypton metastable atoms

Energy distributions of electrons emitted from polycrystalline naphthacene due to the impact of metastable argon or krypton atoms were measured. The energy distribution peaks, except for large peaks appearing near zero eV, correspond to the kinetic energies estimated from photoelectron spectra on the assumption that the excitation energies of the metastable atoms are transferred to the electrons in the valence bands. The results are interpreted as the occurrence of Penning ionization (Auger de-excitation) on the naphthacene surface.     

Phenol synthesis by liquid-phase oxidation of benzene with molecular oxygen over iron-heteropoly acid

The phenol synthesis by liquid-phase oxidation of benzene with molecular oxygen over iron-heteropoly acid (HPA) system was studied. When iron salts were used with H₃PW₁₂O₄₀, the highest activity was obtained. Spectroscopic studies showed that the state of the iron ion was changed after interaction with heteropoly acid (HPA) while the Keggin structure of HPA remained. The acidic nature of HPA activated benzene to form cationic species. Insoluble iron ion-exchanged heteropoly acid was obtained by partial ion exchange method, which also showed high activity on oxidation of benzene with molecular oxygen. The effects of reaction conditions were studied and the mechanism of deactivation was discussed. For the regeneration of catalytic activity, the addition of -ascorbic acid as a reducing agent was suggested.     

Catalytic properties of Hf?Eu oxide fine crystalline powders. Isomerization of n-butenes

Catalytic properties of a series of HfO₂–Eu₂O₃ fine crystalline powders were examined by the isomerization of n-butenes. HfO₂ pretreated at 873 K showed a high activity. It decreased with the addition of the Eu component. The product distributions are discussed on the basis of the acid-base properties.

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HfO₂–Eu₂O₃ -. HfO₂, 873 K, . Eu. - .

     

Electron emission from surfaces of alkali halides under the impact of metastable helium and neon atoms

Energy distributions of the electrons ejected from the evaporated film surfaces of LiF, LiCl, LiBr, NaF and NaCl by the impact of metastable He and Ne atoms have been measured. The observed distribution curves have two distinct structures: one peak is identified as the valence band structure caused by Penning ionization, while the other peak is ascribed to scattered electrons. The positions of the valence band peaks are shifted to lower ionization energy from the corresponding photoelectron peaks (by 0.1–1.5 eV depending on the substance). In contrast to the photoelectron spectra, the structure attributable to conduction bands appears only very weakly. The relative intensity of the peak caused by scattered electrons is either strong or weak depending on the combination of the metastable atom and the sample. The interpretation of this observation is that the scattered electron peak is enhanced when the energy of the metastable atom exceeds twice the band gap energy, i.e. when the electron—electron scattering of Penning electrons in the solid is feasible.     

Complexes of diphenylarsinic acid and phenylarsonic acid with thiols: a 1H and 13C NMR study

The high toxicity of diphenylarsinic acid, found in ground water and well water as a probable consequence of the inappropriate disposal of warfare agents, prompted us to study the reaction, monitored by 1H and 13C NMR spectroscopy, of the compound and its monophenyl analogue, phenylarsonic acid, with cellular thiols as represented, in particular, by glutathione. Glutathione reduced the phenylarsenic acids to trivalent forms and complexed them: diphenylarsinic acid to a monoglutathione adduct and phenylarsonic acid to a diglutathione adduct. The complexes were characterized by 1H and 13C NMR spectroscopy and mass spectrometry. The NMR spectra showed the diastereotopic nature of the two phenyl groups in the diphenylarsinic acid-glutathione compound, and of the two glutathione residues in the phenylarsonic acid-diglutathione complex. The stereochemistry of thiol compounds of phenylarsonic acid was further explored by 1H and 13C NMR spectroscopy of the L-cysteine complex. The diphenylarsinic acid-glutathione complex was stable below pH 12 but at higher pH the complex dissociated into diphenylarsinous acid and reduced glutathione. The released diphenylarsinous acid then oxidized to diphenylarsinic acid with a half-life of about 7 h at pH 13 and at room temperature.     

Compounds structurally related to tamoxifen as openers of large-conductance calcium-activated K+ channel

We found that a variety of compounds containing partial structures of tamoxifen showed activity as chemical modulators of large-conductance calcium-activated K+ channels (BK channels).     

Meson loop effect on high density chiral phase transition

We test the stability of the mean field solution in the Nambu-Jona-Lasinio model in a semi-quantitative manner. For stable solutions with respect to both the σ and π directions, we investigate effects of the mesonic loop corrections of 1/N _c , which correspond to the next-to-leading order in the 1/N _c expansion, on the high density chiral phase transition. The corrections weaken the first order phase transition and shift the critical chemical potential to a lower value. At N _c = 3, however, instability of the mean field effective potential prevents us from determining the minimum of the corrected one.      

Effect of supports on copper Catalysts for Methanol Synthesis from CO2 + H2

Methanol was synthesized from carbon dioxide and hydrogen over various supported copper catalysts. A support was selected from the viewpoint of its acid-base properties. Acid supports showed high selectivity but low activity. Neutral and basic supports produced only carbon monoxide. Amphoteric supports showed high activities. Among them, TiO₂ supports suppressed the reverse water gas shift reaction (CO formation). The role of supports was discussed on the basis of in situ infrared results.     

Theoretical analysis of Lewis basicity based on local electron-donating ability. Origin of basic strength of cyclic amines

It has been experimentally established that the proton affinities (PA), as well as the solution basicities (pK(BH)(+)), of aziridine derivatives are much smaller than those of the corresponding pyrrolidines and piperidines, though the basic strength of azetidines is close to those of pyrrolidines and piperidines. A simple idea of dependence of the basic strength on bond angles seems to be invalid. Because the basicity of cyclic amines is a fundamental property in organic chemistry, we revisited this topic in order to clarify quantitatively the intrinsic origin of the strength of Lewis basicity of the relevant amines, in particular, based on the local electron-donating ability of the amine nitrogen atoms evaluated in terms of the localized reactive hybrid orbital (RHO) concept. In the cases of representative N-substituents such as hydrogen, methyl, and phenyl groups, the electron-donating energy level of the nitrogen center, obtained by maximizing a kind of superdelocalizability, was shown to be correlated with the magnitudes of experimental and calculated gas-phase proton affinities. The present results strongly support the view that the C-N-C bond angle, i.e., angle strain, in the cyclic amines is not the major source of the difference in strength of basicity of these amines, but rather, the degree of pyramidalization around the nitrogen atom has a significant impact on the electron-donating ability of the nitrogen lone-pair orbital.     

Effect of acid-base properties on copper catalysts for hydrogenation of carbon dioxide

Acidic or basic components as co-catalysts were added to the Cu-based catalysts for hydrogenation of CO₂. Effects of acid-base properties on the catalytic activity and methanol selectivity are discussed.