Redox features of β-VOPO4 catalyst using tracer and laser Raman spectroscopy

The oxygen ions of the β-VOPO₄ catalyst were exchanged with an tracer by a reduction–oxidation method and by a catalytic oxidation of but-1-ene using ₂. The bands at 992 and 900 cm⁻¹ were more shifted to lower frequencies than those at 1076 and 1002 cm⁻¹. Applying the correlation between the Raman bands and stretching vibrations in the literature, the exchanged oxygen species were estimated. The results suggest that the P–O–V vacancies corresponding to 992 and 900 cm⁻¹ were responsible for reoxidation and the V=O oxygen corresponding to the 1002 cm⁻¹ band of β-VOPO₄ was not. The (VO)₂P₂O₇ was oxidized to β-VOPO₄ by O₂ above 823 K. The insertion position of oxygen was determined at the bands at 992 and 900 cm⁻¹ of β-VOPO₄ using ₂, which is the same as the exchanged position.     

Fluorescence and Laser photolysis studies on 1,2,4,5-tetracy anobenzene CT complexes in micellar solutions

CT complexes of 1,2,4,5-tetracyanobenzene were formed in the inner part of neutral micelles and in the surface region of ionic ones. The excitation of the CT absorption band of these complexes gives broad and structureless CT fluorescence spectra, their lifetimes being relatively short (≈10 ns). Micellar effect upon ionic photodissociation was observed, and their quantum yeild is smaller than that obtained in acetonitrile. These results are quite different from those on another typical excited CT system of pyrene and N,N-dimethylaniline.     

Enantioselectively catalyzed oxidation of 3,4-dihydroxy-l-phenylalanine by N-lauroyl L or D-histidine-Cu(II) complex in CTABr micelles.

In order to investigate the enzyme model reaction the oxidation of 3,4-dihydihydroxy-L-phenylalanine(L-DOPA) was carried out using optically active catalyst, N-lauroyl L or D-histidine-Cu(II) complex(L or D-LauHis-Cu(II)), showing appreciable enantioselectivity in the presence of the mixed micelles with CTABr.     

Preparation of New Photosensitive ZrO2 Gel Films Using Hydroxyl-Substituted Aromatic Ketones as Chemical Modification Reagents and their Patterning

ZrO₂ gel films were prepared from zirconium tetra-n-butoxide chemically modified with one of hydroxyl-substituted aromatic ketones and 1′-hydroxy-2′-acetonaphthone, by the sol-gel method. The obtained gel film showed an absorption band, characteristic of the π-π* transition of chelate ring, at around 410 nm. The band was shifted to longer wavelength region than those for the gel films using β-diketones. The reason is thought that the hydroxyl-substituted aromatic ketone has π-electron system to form the condensed chelate ring. The absorption band associated with the chelate ring gradually decreased in intensity with UV-irradiation using a high pressure mercury lamp. This indicates that the chelate ring dissociates by the UV-irradiation and that the gel film exhibits photosensitivity. Utilizing the photosensitivity, fine patterns (about 1 μm) could be fabricated by UV-irradiation through a mask and leaching.     

Continuum mixing and coupled channel effects inc\bar c andb\bar b quarkonium

We apply the unitarized quark model to heavy \(c\bar c\) and \(b\bar b\) quarkonium and study mass shifts and mixings induced by hadronic coupled channel effects. In particular, we study the two-meson continuum mixing in the quarkonium wave functions. It is found that the continuum component is 2–20% in the \(c\bar c\) and \(b\bar b\) states, measured as the squared sum of two-meson amplitudes \((D\bar D,D\bar D^ * + cc,D^ * \bar D^ * ,F\bar F,F\bar F^ * + cc,F^ * \bar F^ * for c\bar c)\) . It is the largest for states near or above the first threshold. These continuum mixings reduce the predicted radiative widths by 5–30%. The mass shifts of theP andF wave \(q\bar q\) states are similar to those ofS andD wave states previously studied. The computed resonance mixing matrices are explicitly given, enabling future calculations of relativistic effects, QCD effects, etc., to include also the coupled channel effects.     

Studies on reactions of the N-phosphonium salts of pyridines. XIII. Direct polycondensation reaction of carbon dioxide or disulfide with diamines under mild conditions

Polyureas of high molecular weight were obtained by the direct polycondensation reaction of carbon dioxide with diamines at 40°C for several hours under a pressure of carbon dioxide (below 30 atm) by use of diphenyl phosphite in pyridine. Optimal temperature and pressure were 40°C and 20 atm of carbon dioxide. The polycondensation reaction was also affected by solvents and type and amounts of tertiary amines. Pyridine was most effective as tertiary amine and solvent as well. Of the phosphorous compounds used, triaryl phosphites and diphenyl phosphite were most effective, but trialkyl phosphites failed to give polymer. The reaction was assumed to proceed via a carbamyl N-phosphonium salt of pyridine formed by dephenoxylation of phosphites. Similarly, polythioureas were prepared by heating a mixture of carbon disulfide, diamines, and diphenyl phosphite in pyridine at 40°C for 6 hr under nitrogen.