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Technology.     

Use of LINbO3 for Design of Device-type Catalysts with Activity Controllable Functions

A poled ferroelectric LiNbO₃ single crystal with high spontaneous polarization was employed as a catalyst support, and the static and dynamic effects of the polar substrate surfaces on the adsorptive and catalytic properties of thin film catalysts deposited were shown. For the static effect, it was demonstrated that the surface conductivity of copper and metal-free phthalocyanine films increased by the adsorption of NO gas, to a larger extent, when the substrate was the negative polar surface, compared to the positive one. The role of the polar substrates is explained In terms of a band bending model. For the dynamic effect, the Rayleigh surface acoustic wave generated on the LiNbO₃ substrate was shown to enhance the catalytic activity for ethanol oxidation on Cu and Ag thin film catalysts deposited on the propagation path. It is proposed that the catalyst activation is mainly due to an electric Held produced. The use of poled LiNbO₃ is suggested to be effective for the development of a device-type catalyst with activity controllable functions.     

The Direct Synthesis of β-hydroxy-acids by Lithium Naphthalene and Acetic Acid

Lithium naphthalene reacts with acetic acid to give α-anion of lithium acetate. The reaction of this anion with various ketones gives the corresponding β-hydroxy-acids in good yield.     

Crystalline complex between poly(γ-methyl l-glutamate) and dimethyl phthalate

The crystalline complex between poly(γ-methyl l-glutamate) (PMLG) and dimethyl phthalate (DMP) has been formed in films cast from a solution in dichloroethane. It has the stoichiometry of 1 mol of DMP to three or four residues of PMLG and shows two definite characteristics in X-ray diffraction patterns; one is the large hexagonal unit cell with the edge of around 28 Å and another the ‘extra’ 5.07 Å meridional reflection which can not be interpreted by a PMLG α-helical conformation. The structural examination for the films with various DMP contents is carried out by X-ray, viscoelastic, and d.s.c. measurements and the following structure is proposed for the crystalline complex. Four PMLG are associated to form a group which is hexagonally packed and DMP molecules, located in the gaps between groups, form a specific favourable helical structure along PMLG chains in which the van der Waals stacking of benzene rings of DMP is significant.     

Stereochemistry and mechanism of the hydrogenation of dialkyl cyclohexenes

In order to investigate the steric effect of the substituents to determine the product distribution, disubstituted cyclohexenes were hydrogenated over several transition metal catalysts. Some cyclohexenes which have two large substituents at the vicinal carbon atoms, at least one of which is trigonal, were not hydrogenated over Raney Ni at all but were hydrogenated over Pt catalyst under our experimental conditions. Presumably, the stereoselectivity depends on the competitive operation of the torsional angle strain and the catalyst hindrance with substituents. In the hydrogenation over Pd catalyst, thermodynamically more stable products were dominant at the standard condition but at high substrate to catalyst ratio the less stable products were slightly preferred. No appreciable stereoselectivity was observed in the hydrogenation of 1,4-disubstituted cyclohexenes.     

Hydrothermal Formation of Hydroxyapatite Layers on the Surface of Type-A Zeolite

Type-A zeolite evenly covered with hydroxyapatite thin layers was prepared using hydrothermal treatment at 120°C for 8 h under autogenous pressure. The hydroxyapatite needlelike nanocrystals, 100–200 nm in diameter and 30 nm in thickness, were grown under the reaction between discharged Ca²⁺ ions from type-A zeolite and PO₄³⁻ ions in (NH₄)₃PO₄ solution. The preferential orientations of the c -axis of hydroxyapatite crystals perpendicular to a zeolite surface were observed using transmission electron microscopy. The crystal structure of type-A zeolite was not destroyed under the reaction, but the surface morphology was changed only with complete covering of scaly hydroxyapatite particles.     

Determination of fatty acid composition by gas chromatography: II. Analysis with use of flame ionization detector

In this study known mixtures of four or five fatty acid methyl esters were analyzed collaboratively by gas chromatography with flame ionization detectors. The experimental data was treated statistically to examine inter- and intralaboratory scattering. More-over the effect of the use of correction factors was investigated. Even if only the specific analytical values that scattered a little were chosen, the averages of such values did not always approach the actual values. In some laboratories a sort of regularity was observed in the deviation of analytical values from real values throughout the analyses of four samples. The application of correction factors to the analytical values obtained by these laboratories resulted in a considerable decrease of interlaboratory scattering and deviation from the real values. When a constant amount of sample was injected, intralaboratory scattering was decreased, whereas interlaboratory scattering was not. Injection of large sample sizes caused deviation. From this collaborative study it was recommended that 0.5–1.0 μl of 20% solution be injected. Presented at the JOCS-AOCS Joint Meeting, Los Angeles, April 1972.     

Structural characterization of 1,2-polybutadiene by 13C-n.m.r. spectroscopy: 2. Sequence distribution of 1,2-unit in hydrogenated polybutadienes

The configurational sequences of 1,2-unit in a series of hydrogenated syndiotactic 1,2-polybutadienes were determined in relation to the sequence distribution of 1,2- and 1,4-units on the basis of the ¹³C-n.m.r. signal assignment of the methyl carbons. The observed triad distributions of 1,2- and 1,4-units and configurational distributions of the 1,2-unit are in good agreement with the calculated distributions from transition probabilities. The number average sequence lengths of the 1,2-unit and the 1,2-unit in the racemic addition are 5.7 to 8.0 and 4.1 to 5.4, respectively. From the extrapolation of the plot of the number average sequence length against the crystallinity of the starting 1,2-polybutadienes, the minimum sequence length for crystallization is estimated to be 3.7 for the 1,2-unit in the racemic addition.