bluuebunny/crossref_metadata_2025 huggingface dataset:
The Dielectric Constant of 1,4-Dioxane
Authors: Yasumi Masasi , Shirai Michio
Published: July 2006

The dielectric constant of pure dioxane was measured in the liquid and the solid state.

The dielectric constants of dioxane solutions dissolved in various solvents were also measured.

Using Clausius-Mosotti relation, the molecular polarization of dioxane was computed. The computed value was dependent neither upon the state (solid liquid, solution) nor upon the temperature, and agreed almost exactly with the value obtained from the measurement for the gaseous substance.

The difference between the molecular polarization and the electronic polarization is ca. 4 cc. It seems natural to attribute this value to atomic polarization.
Antituberculous Compounds. V. 1-Thiocarbamyl-3-methyl-5-phenyl-2-pyrazoline, 1-thiocarbamyl-3-methyl-5-(4-nitrophenyl)-2-pyrazoline, and Related Compounds
Authors: Nishimura Tamio
Published: July 2006

The preparation is described of 3-methyl-5-phenyl-2-pyrazoline,3-methyl-5-(4-nitrophenyl)-2-pyrazoline and their 1-phenyl, thiocarbamyl, N-phenylthiocarbamyl,N-benzoylthiocarbamyl, formyl, and acetyl derivatives which were to be tested for antituberculous activity.
Solvent Effects on Ion Exchange Equilibria. Part II
Authors: Sakaki Tomohiko
Published: July 2006

The effect of the addition of non-electrolytes to the ion exchange system has been studied. It has been found that the dielectric constant of the solution gives a profound effect on the ion exchange equilibrium and that in the case of lower concentrations of alcohol a linear relationship exists between the apparent free energy change and the reciprocal of the dielectric constant. A working equation has been proposed to account for the relationships between the free energy change, dielectric constant, ionic species and valency of exchangeable ion.
The Ultra-violet Absorption Spectrum of Pyridine N-oxide
Authors: Ito Mitsuo , Hata Norisuke
Published: July 2006

The near ultra-violet absorption spectrum of pyridine N-oxide was measured in solution and vapor, and we concluded from the considerations of solvent effect, oscillator strength and the feature of vapor spectrum that the two of the four absorption regions are due to the excitation of the non-bonding electron, the others due to the excitation of π-electron. From the spectral behavior of pyridine N-oxide, it is also concluded that the pyridine N-oxide molecule forms hydrogen bond with alcohol or water molecule in vapor and solution state.
Studies on the Electronic Structures of 2,5-Dichloroaniline and 2,5-Dichloronitrobenzene by Their Pure Quadrupole Spectra
Authors: Negita Hisao , Yamamura Hitoshi , Shiba Haruo
Published: July 2006

The pure quadrupole spectra of 2,5-dichloroaniline and 2,5-dichloronitrobenzene were observed at room temperature (292°K), and the effects of electron releasing or attracting power of amino- and nitro-group in the benzene ring were compared with each other. On the other hand, a linear relation between resonance absorption frequencies due to Cl35 and Hammett’s σ of the substituents in these compounds was found, and Hammett’s σ of o-amino-group was assumed to be −0.26. We are indebted to Prof. T. Ichikawa and Prof. D. Nakae for their generarity in granting us the use of their facilities, and to Prof. T. Kawano for the loan of the frequency meter.
Reactions of Chloromethylpolysiloxanes with Thiourea
Authors: Nozakura Shunichi
Published: July 2006

Chloromethylmethylpolysiloxane (I), 3-chloromethylheptamethyltrisiloxane (II) 3,5-di(chloromethyl)octamethyltetrasiloxane (III) and chloromethylpolysiloxane (IV) were reacted with thiourea in absolute alcohol to give silicon-containing thiuronium chlorides.

Although in the case of (II) the corresponding thiuronium chloride was isolated an extensive fission and recombination of siloxane bonds took place in every case.

Silicon-carbon bond in the thiuronium chloride derived from (I) was easily cleft by the treatment with an aqueous alkali to give three-dimensional methylpolysiloxane. In a similar manner the thiuronium chloride derived from (IV) gave silicic acid with aqueous alkali.

The fission of silicon-carbon bonds in the silicon-containing thiuronium salts was facilitated by the electron-attracting substituents on the silicon atom.
Phototropy of New Photosensitive Complexes between a Fluorescent Pigment and SH-Compounds
Authors: Fujimori Eiji
Published: July 2006

The absorption maximum of all pigment-SH compound complexes shifted to a longer wave length range than that of the pigment itself. Although in protein and glutathione the absorption maximum was at 520 mμ from the beginning, in cysteine and thioglycolic acid it was in a shorter wave length range than 520 mμ and shifted to 520 mμ after some photochemical reaction. These complexes with their absorption maxima in a shorter wave length range than 520 mμ fluoresced more weakly than the original pigment, while those at 520 mμ showed the almost complete disappearance of fluorescence. Before these SH-compounds combined with the pigment, its fluorescence was partly instantaneously quenched by them. Both complexes of different spectra showed a phototropy ; i. e., bleaching in light and regeneration in darkness. The regeneration reaction was thermal: its velocity was parallel to the molecular weight of the SH-compound in these SH-compounds used in the present experiment. The degree of regeneration was low in protein but about 100 % in cysteine and thioglycolic acid. The concentration of protein influenced the degree of regeneration but not the velocity of regeneration. This phototropy was discussed from the point of view of an ·S-R free radical and pigment radicals.
Alkylalkoxypolysiloxanes. V. Lower Members of Vinylmethoxypolysiloxanes with One to Five Silicon Atoms
Authors: Okawara Rokuro , Sakiyama Minoru
Published: July 2006

(1) Vinylmethoxypolysiloxanes have been prepared by the reaction of sodium bicarbonate with partially methanolyzed vinyltrichlorosilane.

(2) Distribution of the lower members was determined with regard to the composition of the partially methanolyzed product.

(3) Linear vinylmethoxypolysiloxanes containing from one to five silicon atoms have been prepared and characterized.

(4) Vinylmethoxycyclopolysiloxanes were found between the plateaus of linear polymer but they could not be accurately characterized.
Studies on A. C. Polarography. III. Reversible Wave
Authors: Okuda Mitsuko , Tachi Isamu
Published: July 2006

The d. c. and a. c. components of the electrolytic current observed a. c. polarographically, i. e. the Fournier’s and Breyer’s polarograms, are investigated experimentally for the reversible electro- reductions of cadmium and thallous ions. The result of the experiment shows convincingly the essential legitimacy of our theoretical conclusion.
Studies on DNP-Protamines by Means of the Absorption Spectra
Authors: Hashimoto Chieko
Published: July 2006

1) DNP-Derivatives of amino compounds gave the characteristic spectral absorption curves, according to the states of the amino groups combined with the DNP-group. It was found, that 2,4-dinitroaniline as a primary amine, DNP-monoamino acids in the case of secondary amine and DNP-proline in that of tertiary amine gave respectively the absorption spectra with different absorption maxima and absorption coefficients (cf. Table I and Fig. 1).

2) The absorption curve of DNP-clupeine was of the similar shape to DNP-derivatives in the states of secondary amines, while that of DNP-salmine in those of tertiary amines. From this fact the difference between the N-terminal residues of clupeine and salmine molecules was evidently recognized, that of the former being monoamino acid while that of the latter proline.

3) By comparing the absorption of DNP-protamine with the molecular absorption coefficient of the corresponding DNP-amino acid which occupies the N-terminal residue in the molecule, the molecular weights of DNP-derivatives of clupeine and salmine were estimated. Both clupeine and salmine were shown to have the molecular weights of the same order, 6,000–7,000.
Sterols and Other Unsaponifiable Substances in the Lipids of Shell Fishes, Crustacea and Echinoderms. XVI. Reinvestigation of Hitodesterol and its Identity with α-Spinasterol
Authors: Toyama Yoshiyuki , Takagi Toru
Published: July 2006

1. A fraction having m.p. 167–168°C and consisting mainly of hitodesteryl acetate was separated from the steryl acetate mixture of Asterina pectinifera. Hitodesterol was found to have an ethylenic linkage between C–7 and C–8. Among the products of ozonolysis of hitodesteryl acetate, l-ethylisopropylacetaldehyde was identified in the form of its 2,4-dinitrophenylhydrazone. Hence hitodesterol has been found to be a Δ7,22-sterol of the C29-series and identical with α-spinasterol.

2. Among the products of ozonolysis of a lower melting steryl acetate fraction, the presence of a small amount of methylisopro-pylacetaldehyde besides ethylisopropylacetal-dehyde was indicated. Hence it appears that a C28-sterol having at least an ethylenic linkage between C–22 and C–23, possibly of Δ7,22-type, is also present in a lesser amount in the unsaturated sterol components of Asterina pectinifera.
Studies on Dimethylglyoximato cobalt (III) Complexes. III. Direct Evidence for the Planar Coördination of Two Dimethylglyoximate Ions in Bis-(dimethylglyoximato)-cobalt (III) Complexes
Authors: Nakahara Akitsugu
Published: July 2006

Infrared absorption spectra of bis- and tris-(dimethylglyoximato)-cobalt(III)-complex were measured. Some discussions concerning the O-H stretching band of the former complex were given, and they reached the conclusion that the band at 1725 cm−1. corresponds to the band at 1775 cm−1 of the bis-(dimethylglyoximato)nickel (II) and is characteristic of the planar bis-(dimethylglyoximato)-complexes.
A Note on the Measurement of the Absorption Coefficient in Infra-red Region. Influence of the Thickness of Layer on the Measurement of Absorption Coefficient
Authors: Yasumi Masasi
Published: July 2006

The transmission coefficient of a thin layer of carbon tetrachloride is calculated according to the exact formula and compared with the value calculated by simple Beer’s rule.

The usual transmission method which is based upon the Beer’s law is inadequate to the absorption coefficient of highly absorbing substances such as carbon tetrachloride.
Diffusion of Hydrocarbon, Alcohols and Esters through the Aqueous Solutions of Cationic Detergent
Authors: Okuyama Haruhiko
Published: July 2006

(1) Urea, fructose and potassium chloride which are completely soluble in water, diffuse in the TMDA solution at about the same rate as in water notwithstanding the fact that the former has higher viscosity than the later.

(2) The diffusion coefficient of hexane is in a fairly good coincidence with the difference of the calculated diffusion coefficient from X-ray data between more and less swollen micelles.

(3) The diffusion of alcohols and esters is generally governed by their solubility in water. From the concentration gradient curves of diffusion, they are considered to diffuse on two different mechanisms, one as the single molecule and the other as the complex group associated with the detergent micelles.

(4) The equilibrium between solute in micelles and in water is rather slower processwhen the mechanical disturbance or convection is absent in the solution.

(5) The anomalies reported on the solubi-lization of dimethylphthalate is not observed in these diffusion experiments.
Studies on Several Phosphates from the View-point of Analytical Chemistry. V. An Electro-Chromatography on Several Meta- and Poly-phosphates labelled with P32
Authors: Shinagawa Mutsuaki , Takanaka Junichi , Kiso Yoshiyuki , Tsukiji Aiko , Matama Y\={o}ko
Published: July 2006

1) Several phosphate ions can be separated by the present electro-chromatographic method. This method of separation is a vast improvement over the paper chromatography.

2) The smaller the number of phosphorus atoms contained in a phosphate ion, the greater the migration rate of ion in the case of chain ionic structure. Trimetaphosphate ion which has ring ionic structure showed the greatest migration rate among all of them.

3) The test by means of prussian blue was more distinct in electro-chromatography than in paper chromatography.
The Role of Ethylene Glycol and Polyethylene Glycol in the Freeze-Thaw Stability of Synthetic Latex
Authors: Okamura Seizo , Motoyama Takuhiko
Published: July 2006

The freeze-thaw stability of synthetic latices obtained by the emulsion polymerisation of styrene, methyl methacrylate, methyl acrylate, vinyl acetate and acrylonitrile has been measured at the freeze-thaw cycles of −17.5°C and room temperature. It is found that the addition of ethyleneglycol and poly-ethyleneglycol into the latices increases the stability. The freezing point depression and the electrophoretic mobility of stabilized latices indicate the adsorption of stabilizing additives on the emulsion particles. Finally the adsorption of ethylene glycol and polyethylene glycol on the emulsion particles is determined directly. In consideration of these experimental results the freeze-thaw stability seems to be attained by the adsorption of additives on the emulsion particles.
Polarographic Behavior of Nitroammonocarbonic Acids in Aqueous Media. II. Nitroguanidine
Authors: Namba Keiho , Suzuki Kyoichi
Published: July 2006

1) The relationships of pH–E1⁄2 (vs. S.C.E.) and of pH–il of nitroguanidine under the dropping mercury electrode were studied.

2) From results about the influence of the effective height of mercury reservior and temperature upon il, it was found that il will follow the diffusion law, and that the Ilkovi\u{c} equation is applicable in this case.

3) Although the electron number consumed for reduction (n) was calculated by assuming a diffusion coefficient these were insufficient in discussion of reduction mechanism. Further investigation will be necessary.
On the Relation between the Hydrogen Overpotential and the Magnetic Susceptibility of Copper-Nickel Alloys
Authors: Oikawa Mitsuru
Published: July 2006

Experiments were carried out on the relation between the hydrogen overpotential and the electronic structure of nickel-copper alloys.

We can classify these alloys into two groups, depending upon whether or not they contain more nickel than 60 atomic per cent., that is whether they have positive holes or not in their d-band.

The hydrogen overpotential of nickel rich alloys (more than 60 atomic percentages of nickel) is rather low because of their small activation energy caused by the large adsorption energy due to the strong bond between metal d-orbital and H-atom. For copper rich alloys the hydrogen overpotentials are high and are almost identical owing to the extinction of positive holes.
Studies on the Cooking Mechanism of Wood. Xl. On the Amount of B-group, and the Reactivity with Thioglycolic Acid
Authors: Mikawa Hiroshi , Sato Koichiro , Takasaki Chizuko , Ebisawa Kiyo
Published: July 2006

B-group of lignin reacts with thioglycolic acid. Total amount of the sulphonatable groups of lignin is about 0.6/CH3O, the amount of B-group being consequently 0.3–0.35/CH3O. Higher S/CH3O values reported in the literature may be due to the presence of nonacidic “ excess sulphur ”.
The State of Metal Ion in Aqueous Solutions and Its Surface Chemical Effects. I. Cobalt lon-Stearic Acid Monolayer Interaction
Authors: Matuura Ryohei , Kimizuka Hideo
Published: July 2006

The presence of aggregates of cobalt ion in the alkaline solution of 10−3 mol./l. CoCl2 was shown by the measurement of self-diffusion coefficients. Large expansion and high rigidity of the stearic acid monolayer caused by cobalt ion in the alkaline solution were accounted for by the interaction of stearate ion in the monolayer with the aggregates of cobalt ion in the solution, resulting in the formation of two-dimensional network structure in the film. This idea was confirmed by the effect of aging of the substrate solution and also by the action of complex-forming agents such as ammonium oxalate and sodium citrate on the monolayer-ion interaction.
Studies on Fused Iron Catalyst for Alcohol Synthesis by Hydrogenation of Carbon Monoxide. III. Function of Copper in the Catalyst
Authors: Uchida Hiroshi , Ichinokawa Hideo , Ogawa Kiyoshi
Published: July 2006

Among the fused iron catalysts for the syntheses from water-gas, those containing Al2O3 and K2O as principal promoters behaved differently from those containing SiO2, MgO, and K2O as such. With the former, it was well known that the products rich in oxygenates were obtained when the synthesis could be carried out at low temperatures. In the present study, an addition of copper has proved to bring about an increase in oxygenates with a simultaneous decrease of the activity. A marked effect of copper on the yield of alcohols has already been realized at the addition of 0.25% of CuO into the catalyst, while no further remarkable effect has been easily observed with its increasing amounts. The observations of microscopic structures, such as the area, the chemisorption of CO2, and CO showed also considerable changes at this amount of addition. An excess amount of copper is liable to segregate along the grain boundaries and hence seems to contribute little for the promotion.

By the addition of Al2O3 together with SiO2 besides the usual promoters such as CaO, K2O etc., a catalyst of the high activity, though of short durability, was obtained. In the product obtained with this catalyst at low temperatures, oxygenates have been extremely small, while those obtained by the additional operation at higher temperature are greater in amount.

A particular promoting action, quite different from that of Al2O3, has been ascribed, to SiO2.
Chemical Studies on Charoninsulfuric Acid
Authors: Egami Fujio , Asahi Tadashi , Takahashi Noriko , Suzuki Sakaru , Shikata Shogo , Nisizawa Kazutosi
Published: July 2006

We have obtained charoninsulfuric acid free from glycogen (or similar glucans) and confirmed that it is a mixture of glucan polysulfates with different sulfur contents. The desulfated product (charonin) was decomposed by Schweitzer’s reagent into two parts, Fractions A and B. From Fraction A, which is insoluble in water and gives a blue color reaction with I2-KI-H2SO4, glucose (after hydrolysis by sulfuric acid), cellobiose (after hydrolysis by Irpex-cellulase) and octaacetylcellobiose (after acetolysis) were obtained. From Fraction B, which is soluble in water and gives a red iodine reaction, glucose, cellobiose and maltose (after hydrolysis by amylases) were obtained. This fraction consumed periodate as expected from 1,4′-glucoside glucan. From these results, this glucan (charonin) may be regarded as having both cellulose and amylose structure. Moreover it was found by analysis of various charoninsulfuric acids that a close relation existed between the sulfur content of charoninsulfuric acid and the constitution of glucan, i.e. the less the sulfur content was, the less was the cellulose structure.
Reduction of Acetophenone by an Electrolytic Method Using Raney Nickel as Catalyst
Authors: Sakurai Buhei , Arai Toshio
Published: July 2006

The catalytic reduction of acetophenone by electrolysis using Raney nickel in weak alkaline solution with lead or copper cathode was studied and methylphenylcarbinol was prepared.
Hydrogen Bonding Effect on the Fluorescence of π-Electron System
Authors: Mataga Noboru , Kaifu Yozo , Koizumi Masao
Published: July 2006

1. The absorption and fluorescence spectra of α-, β- naphthols and related compounds were measured in various mixed solvents in connection with the hydrogen bonding phenomena. The observed spectral shifts of absorption and fluorescence spectra, which were almost the same (∼30 Å), could be solely attributed to the hydrogen bonding effect.

2. It was found that the fluorescence intensity becoms stronger by hydrogen bonding when dioxane and acetic acid esters other than ethylchloroacetate are used as the proton acceptors. In the case of β-naphthol, it was established that the rate of inner quenching is decreased by hydrogen bonding. When ethylchloroacetate was used as a proton acceptor, fluorescence quenching was observed, which is also to be attributed to hydrogen bonding.

3. For β-naphthol, the measurement of the relative intensity established the fact that a new and different equilibrium state of hydrogen bonding, which shifts somewhat toward association, is reached during the life time of the excited state.

4. The mechanism of hydrogen bonding was discussed on the basis of the theory of electron migration, and it was concluded that the observed extra-stabilization of the hydrogen bond in the excited state as compared to the ground state, is mainly due to the increase of electron migration in the former state.
Theoretical Analysis of Polarographic Waves. II. Reduction of Complex Metal Ions
Authors: Matsuda Hiroaki , Ayabe Yuzo
Published: July 2006

Under the assumption that the electrolytic reduction of the complex metal ions at the dropping mercury electrode follows the mechanism expressed by Eqs. (3) and (4), the general expression of the current-voltage curve has been derived by solving the corresponding diffusion problem with the same accuracy as the Ilkovic equation, and the special two cases corresponding to the reversible and irreversible electron transfer process have been discussed in some detail. Moreover, as an example of the application of the present theory, the irreversible reduction of the ammonia-nickel complex ion has been analysed by the aid of the experimental data given by K. Morinaga. A fairly good agreement between the experimental data and the theoretical results has been obtained, and it has been found that the species Ni(NH3)2++ participates in the electron transfer process with the forward rate constant equal to 10−16.8 cm./sec. and the transfer coefficient equal to 0.71.
The Structure of Surface-denatured Protein. VII. The Activity and the Shape of the Surface-denatured Pepsin Molecule
Authors: Imahori Kazutomo
Published: July 2006

(1) The molecular weight, the size and the shape of the pepsin molecule on the substrates of pH 2 and 3 were determined. The molecule on the substrate of pH 3 (its isoelectric point) was of rather a round shape, but the molecule on pH 2 had a far more elongated shape.

(2) The enzymatic activity of the surfacedenatured pepsin molecule on the solutions of various pHs was determined. The roundshaped molecule on the substrate of pH 3 was the most active, but the elongated molecule on pH 2 retained less activity.
Study on ZnO-Cr2O3 Catalyst. I Electrical Conductivity of Zinc Oxide in Oxygen and Hydrogen
Authors: Uchida Hiroshi , Ogino Yoshisada
Published: July 2006

With the evacuated zinc oxide, there has been found, in an intermediate range of temperatures from 100° to 500°C, a linear relation between log R and 1/T, from which an activation energy of 0.025 eV. has been evaluated.

From the results of the measurement of adsorption a molecular adsorption and an adsorption with dissociation seemed to take place on the evacuated oxide at an earlier and a subsequent stage of oxygen adsorption respectively. The more detailed results from the conductivity measurements revealed that the adsorption with dissociation took place consecutively in the earlier stage in which the molecular adsorption was predominant.

At temperatures below 200°C, the conductivity decreases accompanied by hydrogen adsorption, while it increases at higher temperatures. The adsorption kinetics as the rate of change of the conductivity is given by expressions similar to those in the oxygen adsorption.

The adsorption of oxygen as well as hydrogen accompanied by the conductivity decrease may be explained in terms of two different kinds of sites, on which the molecular adsorption and the adsorption with dissociation take place respectively. The interstitial zinc atom pair suggested by P. H. Miller being employed for the site of the latter adsorption, a quantitative interpretation is available for the rate and the equilibrium of the adsorption associating with the conductivity.
Studies on the Cooking Mechanism of Wood. XV. Mannich Reaction on Lignin Model Compounds and the Estimation of the Amount of the Simple Guaiacyl Nucleus in Thiolignin
Authors: Mikawa Hiroshi , Sato Koichiro , Takasaki Chizuko , Ebisawa Kiyo
Published: July 2006

Mannich reactions on many lignin model compounds revealed that 1) model compounds of type (I) give without exception Mannich base with substituent at fifth position in very high yield, 2) those of type (II) do not react, 3) carboxyl group having phenolic hydroxyl group to its para position is split off as carbon dioxide and dimethylaminomethyl group is introduced to the same position, 4) methylol group having phenolic hydroxyl group to its para position reacts with dimethylamine resulting in the formation of dimethylaminomethyl group at the same position, 5) other groups remain intact even when phenolic hydroxyl group exists in para position, and 6) no reaction occurs when the phenolic hydroxyl group is etherified.

By applying the Mannich reaction with dimethylamine on thiolignin, it has been concluded that about 25–40% of the phenolic hydroxyl group of thiolignin belongs to the simple guaiacol nucleus of type (I) having no C–C bond at its fifth position, admitting some uncertainty concerning the amount of carboxyl group having free phenolic hydroxyl group in its para position.
Studies on the Cooking Mechanism of Wood. XVI. On the Mechanism of Kraft Cooking
Authors: Mikawa Hiroshi , Sato Koichiro , Takasaki Chizuko , Ebisawa Kiyo
Published: July 2006

1. Hydrogen sulphide cooking of α-guaiacyl propanol (VI) gave bis(1-(4-hydroxy-3-methoxyphenyl)-1-propyl) monosulphide (VIII) and disulphide (VII).

2. Vanillyl monosulphide was decomposed with alkali at 130°. Vanillin, vanillyl alcohol and the secondary products from vanillyl alcohol were identified.

3. The mechanism of the kraft cooking process was discussed and a new mechanism was proposed.
Absorption Spectra of Co(III) Complexes. II. Redetermination of the Spectrochemical Series
Authors: Shimura Yoichi , Tsuchida Ryutaro
Published: July 2006

The visible and ultra-violet absorption spectra of many cobaltic ammine, oxalato, carbonato and amino-acido complexes have been determined in solution.

The spectrochemical series for the ligands of Co(III) complexes has been redetermined.
Cyanoethylation of Trichlorosilane. II. α-Addition
Authors: Nozakura Shunichi , Konotsune Shiro
Published: July 2006

Contrary to the case of β-cyanoethylation, α-cyanoethylation of trichlorosilane was found to take place in an autoclave in the presence of either pyridine or platinized asbestos.

In the reactions in sealed glass tubes, on the other hand, stainless steel and pyridine, mono- and tetrapyridine nickel chloride, and nickel chloride pyridine hydrochloride complex were effective for the α-addition. An ionic mechanism was suggested for the α-cyanoethylation.

The structural proof of α-cyanoethyltri-chlorosilane was given from the comparison of the physical constants and chemical behaviour of it to those of the β-isomer. α- Cyanoethyl-triethoxysilane and -trimethyl- Silane were prepared from α-cyanoethyl-trichlorosilane and characterised.
The State of Metal Ion in Aqueous Solutions and its Surface Chemical Effect. II. Uptake of Metal Ions from Aqueous Solutions by Stearic Acid Monolayer
Authors: Sasaki Tunetaka , Muramatsu Mitsuo
Published: July 2006

It has been attempted to determine the binding ratio of strontium and cobalt atoms in the monolayer of stearic acid spread on aqueous strontium and cobalt solutions, respectively, containing radioactive cations.

The number of strontium atoms bound to one molecule of stearic acid increased with increasing pH of substrate solution as well as concentration of strontium ion in it. Tentative explanation was made by assuming interaction between strontium and stearate ions. A theoretical formula based on ioniza-tions of stearic acid, strontium hydroxide, and strontium stearate proved to support the validity of this presumption.

A similar explanation was also made for interaction between monolayer of stearic acid and substrate solution containing cobaltous chloride of pH less than 6.5, where the monolayer showed no expansion but rather a small condensation, while the number of bound Co atoms per one molecule of stearic acid increased with increasing pH up to 0.5. At pH 7–9, remarkably expanded and compressible films were obtained and the binding ratio reached a maximum value of unity. Films thus formed were considered to consist of stearate ions and polymer ions of cobalt which may exist as aggregates in the solution. Co-existing ammonia used as a pH-adjusting agent of the solution of cobaltous chloride resulted in exaggeration of these effects. It might be attributed to co-ordination of ammonia molecules towards Co atoms.
Geochemical Investigations of Volcanoes in Japan. XXXII Residual Magmatic Waters in Cavities of Trachyandesitic Basalt in Imari District, Saga Prefecture, Japan
Authors: Iwasaki Iwaji , Kokubu Nobuhide , Katsura Takashi
Published: July 2006

1) The nature of the residual magmatic waters in the cavities of the trachyandesitic basalt in Imari district is described with the nature of their mother rocks and druse minerals.

2) From the definition of the real magmatic state, temperature, and chemical properties of many kinds of magmatic waters are discussed, and the residual magmatic waters are distinguished from the magmatic waters derived directly from lava lakes. It is concluded that the magmatic waters are not always juvenile.

3) The formation of the various kinds of the primary hot springs are discussed from the definition of hot springs and the various kinds of the magmatic waters.

4) Chemical nature of the primary hydrosphere and the primary atmosphere in the initial stage of their formation are discussed from the chemical properties of the magmatic waters and volcanic gases.

5) The important properties of the magmatic substances in the cavities of the volcanic rocks are discussed from the standpoint of the distribution of the magmatic substances in the cavities.
Detection of 103mRh in the “ Bikini Ashes ”
Authors: Kimura Kenjiro , Ikeda Nagao , Yoshihara Kenji
Published: July 2006

103mRh having very short half-life (57 m) and very low energy in electron conversion (0.034 MeV) was searched for and detected in the “ Bikini Ashes”. It was separated from the ashes by the method using the cation exchange resin, Dowex-50, and its activity was measured by the 2π Q-gas flow counter.

The radionuclides detected in the ashes are briefly summarized in a table.
Infrared Spectra of Charoninsulfuric Acid, Chondroitinsulfuric Acid, and Some Related Polysaccharides
Authors: Nakanishi Koji , Takahashi Noriko , Egami Fujio
Published: July 2006

The infrared spectra of charoninsulfuric acid and related carbohydrates have been measured and the results support previous chemical evidences. The work has been ex-tended to a few polysaccharide sulfates, and a tentative assumption as to the distribution of sulfate groups within the polysaccharide chain is Presented.

Chondroitinsufuric acid from shark cartilage has been shown to be identical with the Chondroitinsulfuric acid from bovine nuclei pulposi; a comment on the 820 cm−1 sulfate band is made.
Introduction of Side Chains into Polyglycine Dispersed on Solid Surface. I
Authors: Akabori Shiro , Okawa Kenji , Sato Mikio
Published: July 2006

1) Polyglycine dispersed on the surface of kaolinite was prepared by the polycondensation of N-carboxylic anhydride or glycine ester on kaolinite.

2) It was concluded that a part of glycyl residues in polyglycine dispersed on kaolinite

was easily converted to seryl or threonyl residues by the condensation with formaldehyde or acetaldehyde.

3) The condensation occurred not only at amino terminal glycyl residues but also at non-terminal glycyl residues.
Addition of Trichlorosilane to Acetylene and to Vinyltrichlorosilane
Authors: Nozakura Shunichi
Published: July 2006

The addition reactions of trichlorosilane and acetylene in an autoclave were carried out in the presence of platinized asbestos or of pyridine. In the case of the former catalyst, 1,2-di(trichlorosilyl)ethane was obtained exclusively. In the case of the latter, on the other hand, the principal product proved to be a mixture of 1,2- and 1, 1-di(trichlorosilyl)-ethane.

The addition of trichlorosilane to vinyltri-chlorosilane in the presence of tetrapyridine nickel(II) chloride in glass tubes also led to the formation of a mixture of two isomers. Therefore, it might be considered that the reaction processes in the autoclave in the presence of pyridine was reproduced by the reactions in glass tubes. This situation seems to be analogous to that in the case of cyanoethylation of trichlorosilane which was previously reported.
Notes on the Geochemistry of Germanium
Authors: Onishi Hiroshi
Published: July 2006

Chondrites have uniform germanium contents: the average of 18 samples is 10.6 ppm. Ge, with the range 9.0–12.4 ppm.

The common igneous rocks do not differ greatly in germanium content as shown by the averages: granitic rocks 1.3 ppm., intermediate rocks 1.5 ppm., basalts and diabases 1.3 ppm., gabbros 1.2 ppm., and ultramafic rocks 1.0 ppm. The average for the lithosphere or the crustal rocks may be taken as 1.5±0.5 ppm. Ge.

Shales contain 2 ppm. Ge. Oceanic red clay also contains the similar amount. The germanium content of sedimentary materials seems to be somewhat higher than that of igneous rocks because of the possible escape of germanium in hydrothermal and volcanic emanations.
Structure of Pristimerin and Celastrol
Authors: Nakanishi Koji , Kakisawa Hiroshi , Hirata Yoshimasa
Published: July 2006

Part structure (I) has been presented for pristimerin on grounds of chemical and spectroscopic evidences. Celastrol (tripterine) has been shown to be demetylated pristimerin, hence (I’).
Lateral Order Distribution of Native Cellulose
Authors: Tsuda Yoshizo , Mukoyama Sadataka
Published: July 2006

To obtain the lateral order distribution of native cellulose fibers the fractional dissolution method, the D.P. method and the moisture regain method were adopted. Among these three methods the fractional dissolution method gives the most correct distribution. The other methods give somewhat different distribution curves, the meanings of which were discussed. The structural difference between wood pulp and linters pulp is due to the difference in the degrees of perfection of crystalline regions, whereas no difference between sulfate pulp and sulfite pulp is observed in their crystalline regions.

One might conclude that the fractional dissolution method is the best method to obtain the lateral order distribution inboth native and regenerated cellulose fibers.
Exchange Reaction between Deuterium and Ammonia on Synthetic Ammonia Catalysts Promoted Singly, Doubly, and Triply
Authors: Uchida Hiroshi , Todo Naoyuki
Published: July 2006

The tendencies observed of the experimental rate (γ) in the exchange reaction are represented by the following equation

γ=kp_D_2^1/2(1+ap_NH_3).

In the equation a is the equilibrium adsorption constant in Langmuir’s isotherm. The value of a varies according to both the reaction temperature and the promoter composition which causes different extents of the covering by potash on the surface after reduction.

The apparent activation energies in the exchange reaction are in a range of 15.3 to 12.8 kcal./mol. and the energy for the singly promoted catalyst is remakably smaller than the others. Whereas the energies for the doubly promoted and triply promoted catalysts persisted unchanged independently of the varying initial pressures of ammonia, the one for the singly promoted catalyst tended to decrease with the increasing initial pressure of ammonia.

The comparison of the rate in the exchange reaction with the one in ammonia synthesis, both being based on a definite extent of iron surface, reveals no parallel relation existing between them, namely the catalyst (the singly promoted catalyst) having the highest activity in the exchange reaction has a very low activity for the ammonia synthesis.
Magnetic Susceptibility of Erythrocruorin from the Blood of an Ark-Shell
Authors: Kubo Masaji , Kobayashi Takehiro , Kishita Michihiko
Published: July 2006

The magnetic susceptibility of an aqueous solution of erythrocruorin from an ark-shell known as Anadara inflata (Reeve) was measured by a Gouy magnetic balance at 15°C in deoxygenated and in oxygenated state. On the plausible assumption that oxygenated erythrocruorin contains no unpaired electrons, the magnetic moment per one iron atom of this respiratory pigment in deoxygenated state was calculated to be equal to 4.96 Bohr magnetons. This corresponds closely to the presence of four unpaired electrons per heme and to almost complete quenching of orbital moments. For this reason, the erythrocruorin bears a remarkable resemblance to hemoglobins of vertebrates in so far as its magnetic properties are concerned.
Synthesis of Polycysteine
Authors: Sakakibara Shumpei , Tani Hisaya
Published: July 2006

The synthesis of polycysteine via S-thiophenyl-l-cysteine was described. S-thiophenyl-l-cysteine was prepared from benzenesulfenyl chloride and l-cysteine hydrochloride in absolute alcohol and its chemical properties were studied. This amino acid was polymerized by the N-carboxy anhydride method in ethyl thioglycolate containing an active sulfhydryl group, and it was confirmed by the studies of infrared spectra of these substances that the resultant polymer was polycysteine contaminated with diketopipera-zine. Pure polycysteine was isolated by treating this polymer with thioglycolic acid and methanol. The benzoyl derivative and ethylester hydrochloride of S-thiophenyl-l-cysteine were prepared.
Studies on the Synthesis of Massoi-lactone and its Homologues. Part II. Synthesis of Nonyn-1-ol-4-carboxylic acid-1-lactone (Massoi-lactone)
Authors: Abe Shigehiro , Sato Kikumasa
Published: July 2006

The Massoi-lactone (nonyn-1-ol-4-carboxylic acid-1-lactone), the main component of the essential oil of Massoi-bark was synthesized from n-hexanal and propargyl bromide.
Reaction of Hydrogen Peroxide with Titanium (IV) at Different pH Values
Authors: Mori Motoshichi , Shibata Muraji , Kyuno Eishin , Ito Syu
Published: July 2006

Reaction of hydrogen peroxide with titanium(IV) has been investigated over the range of pH 0 to 13. Below pH 2 this reaction gives orange-colored ion-species, [Ti(OH)2(H2O)(H2O2)]2+ or (TiO2·-aq)2+. In the range of pH 3 to 6 formation of a yellow species is observed and its chemical formula is presumed to be [Ti(OH)3(H2O2)]+. Existence of a species different from the above is indicated by the pale yellow color observed in the region of pH 7 to 9. This species is very unstable unless a large excess of hydrogen peroxide is present, and its chemical formula is presumed to be [Ti(OH)3(OOH)]0. At higher pH values (10<pH), the reaction mixture is colorless, and presumably contains [Ti(OH)2(O2)2]2−. All the tentative formulae of these species are based on the composition of isolated salts, the absorption spectra of the solutions etc. A solution containing [Ti(OH)2(H2O)(H2O2)]2+ remains unchanged but a solution containing [Ti(OH)3(H2O2)]+ gives a yellow precipitate TiO(OH)(OOH), and one containing [Ti(OH)3(OOH)]0 or [Ti(OH)2(O2)2]2− gives a pale yellow compound (Remark: Graphics omitted.) at room temperature or more quickly when heated on a water-bath. The precipitation reaction of (Remark: Graphics omitted.) is taken advantage of in a new volumetric analysis suited for determination of titanium in quantities of the order of 10 mg.
The Action of Hydrogen Bromide and Oxygen on Various Ethenoid Compounds. II
Authors: Takahasi Makoto
Published: July 2006

(1) The reaction of diphenylethylene, atropic acid, and styrene with the mixture of hydrogen bromide and oxygen were studied. In the case of diphenylethylene, diphenylbromomethane, ω-bromoacetophenone, diphenylethylene dibromide, phenol and carbon dioxide were obtained as reaction products. A reaction mechanism was proposed to explain how these compounds were produced.

(2) In the case of atropic acid, a large amount of α-hydroxy-β-bromohydratopic acid and a small amount of ω,ω-dibromoaceto phenone and of carbon dioxide were obtained. A consideration on the mechanism of the formation of these products was given on the basis of the identified products and their semiquantitative estimation.

(3) Addition of hydrogen bromide to atropic was carried out under various conditions. No reversal of the direction of addition of hydrogen bromide was observed contrary to the previous reference.

(4) The reaction of styrene with the mixture of hydrogen bromide and oxygen added an example yielding a phenolic substance ia the reaction.
Studies on Antibiotics and Related Substances. III. Oxazolidines Derived from Some α-Hydroxy Schiff Bases and a Synthesis of Dl-threo-1-p-Nitrophenyl-2-amino-1,3-propanediol
Authors: Suami Tetsuo , Umezawa Sumio
Published: July 2006

1) When Erlenmeyer’s β-phenylserine ethyl ester was reduced with Raney nickel catalyst, Dl-threo-1-phenyl-2-benzylideneamino-1, 3-propanediol (a Schiff base) was obtained as a main product. The structure was demonstrated by means of its infrared and ultraviolet absorption spectra.

2) It was found that Dl-threo-1-phenyl-2-benzylideneamino-1, 3-propanediol gave Dl-threo-N-acetyl-2-phenyl-4-(α-hydroxybenzyl) oxazolidine on acetylation with acetic anhydride.

3) The condensation products of Dl-threo-1-phenyl-2-amino-1, 3-propanediol and Dl-threo-1-p-nitrophenyl-2-amino-1, 3-propanediol with benzaldehyde, o-, m- and p-nitrobenzaldehyde were prepared and acetylated to give corresponding oxazolidine derivatives, which failed to hydrolyze under Kunz’s conditions. Infrared and ultraviolet absorption spectra of some of these compounds were observed. Acetylated derivatives failed to show the characteristic absorption of (Remark: Graphics omitted.) bond in the 1660–1610 cm−1 region.

4) Dl-Chloramphenicol was synthesized from Dl-threo-N-acetyl-2-phenyl-4-(α-hydroxybenzyl)oxazolidine.
Studies on Antibiotics and Related Substances. IV. Synthesis of Dl-threo-β-Cyclohexylserine and Dl-threo-2-Dichloroacetamido-1-cyclohexylpropane-1,3-diol
Authors: Umezawa Sumio , Oguma Yoshihisa
Published: July 2006

(1) When the N-acetyl ethyl ester of Erlenmeyer’s phenylserine was reduced with hydrogen over Raney nickel catalyst, ethyl Dl-threo-N-acetyl-β-cyclohexylserinate was obtained in crude yields as high as 86.8 %. Subsequent hydrolysis with dilute hydrochloric acid afforded Dl-threo-β-cyclohexylserine, which gave hexahydrobenzaldehyde by periodate oxidation.

(2) Raney nickel reduction of ethyl Dl-threo-β-cyclohexyl-serinate afforded Dl-threo-2-amino-1-cyclohexylpropane-1, 3-diol. The aminoalcohol was converted into Dl-threo-2-dichloroacetamido-1-cyclohexylpropane-1,3-diol, a chloramphenicol analogue.
ON THE OXIDATION OF FERROUS HYDROXIDE IN SODIUM HYDROXIDE SOLUTION BY MEANS OF AIR
Authors: Miyamoto Susumu
Published: July 2006

(1) The velocity of the oxidation of ferrous hydroxide by means of air was studied. The rate of the oxidation was independent of the quantity of ferrous hydroxide present in the reacting vessel, and the values of the velocity constants were almost the same as those of the velocity constants of the oxidation of sodium sulphite or stannous hydroxide under the same conditions.

(2) The effect of temperature was small.

(3) Sodium hydroxide decreases the velocity of the oxidation, the mechanism of which will be explained by the considerations that the oxidation velocity thus measured is no other than the dissolution velocity of oxygen under the conditions above described, and that sodium hydroxide decreases the dissolution velocity of oxygen into the solution.
ON THE DECOMPOSITION OF CARBON MONOXIDE IN THE PRESENCE OF REDUCED NICKEL
Authors: Horiba Shinkichi , Ri Taikei
Published: July 2006

An improved apparatus for the investigation of contact catalysis was described.

The decomposition of carbon monoxide in the presence of reduced nickel is a monomolecular reaction in the vicinity of 230°C.
ELECTRODE POTENTIAL OF NICKEL. PART II. EFFECT OF OCCLUDED HYDROGEN ON THE ELECTRODE POTENTIAL OF NICKEL
Authors: Murata Kwanji
Published: July 2006

1. A prolonged cathodic polarization of the nickel electrode in dilute acid and in an atmosphere of hydrogen did not cause any increse, but rather a slight decrease in the initial value of the electromotive force of the cell, Ni | SiSO4 (0.05 M.) | KCl (0.1 N.), Hg2CL2| Hg. The effect of hydrogen produced in the metals of the iron group by cathodic polarization, i.e. of making the metals less noble as found by previous investigators, was not be repeated in the case of reduced nickel powder. The slight diminution in the initial value of the electromotive force is supposed that it may be the effect of a trace of the free acid which might have remained in the cell, owing to the difficulty of the replacing it.

2. The potentials of the nickel electrode in an atmosphere of nitrogen, and of nitrogen mixed with a little hydrogen were measured. As a result of these series of experiments the conclusion is reached that the occluded hydrogen in nickel has no effect upon the true electrode potential. But, it was observed that in the case of an electrode which has been once affected by oxygen, the effect of hydrogen is very remarkable, and. the electrode returns to its active state even at a low temperature.

3. For the measurement of the potential of nickel electrode, the complete exclusion of oxygen is the essential requirement.
CRYOSCOPIC STUDIES ON THE TRANSITION POINTS OF THE COMPOUNDS OF ORGANIC SOLVENTS WITH SALTS. I
Authors: Osaka Hajime
Published: July 2006

1. The lowering of the transition point, at which NaI·3CH3COCH3 loses acetone, by the dissolution of foreign substances has been studied and the molecular depression referred to 100 gr. of acetone has been determined as 24.0. The transition point has been also determined as 25.5°C. The method may be regarded as the cryoscopy using acetone with an artificially elevated melting point and can be used practically for the molecular weight determination.

2. A similar study has been carried out with HgCl2·CH3COCH3. The molecular depression has been determined as 24 and the transition point as 20.7°C. This system shows, however, some inaccuracy so that it can hardly be applied to the practical cryoscopy.

The writer wishes to express his hearty gratitude to Prof. M. Katayama, under whose kind guidance this work has been carried out.
ON THE OXIDATION OF SODIUM SULPHITE IN SODIUM CARBONATE SOLUTION WITH AIR
Authors: Miyamoto Susumu
Published: July 2006

(1) The oxidation velocity of sodium sulphite in sodium carbonate solution of various concentrations was observed. The oxidation velocity was independent of the concentration of sodium sulphite under the condition of the present experiment, and the velocity constant was expressed as a linear function of the concentration of sodium carbonate approximately, when CNa2CO3 is greater than about 0.02 normal.

(2) The effect of temperature was small.

(3) The dissolution velocity of oxygen into sodium carbonate solution of various concentrations was obtained indirectly.
ON THE OXIDATION OF THE MIXTURE OF STANNOUS HYDROXIDE AND SODIUM SULPHITE IN SODIUM CARBONATE SOLUTION WITH AIR
Authors: Miyamoto Susumu
Published: July 2006

1. The oxidation of the mixture of sodium sulphite and stannous hydroxide in sodium carbonate solution was studied.

2. It was observed that the reaction is an example of negative induced reaction; the oxidation of stannous hydroxide has an inhibiting action on the oxidation of sodium sulphite.

3. The mechanism of the reaction was discussed.