bluuebunny/crossref_metadata_2025 huggingface dataset:
Irreversible Photobleaching of the Solution of Fluorescent Dyes. II. Photobleaching of the Alcoholic Solution of Eosine in Vacuo
Authors: Imamura Masashi , Koizumi Masao
Published: July 2006

Photobleaching of eosine in methanol, ethanol, isopropanol and n-butanol in vacuo was investigated and it was concluded that the primary process is the dehydrogenation of alcohols by the metastable excited eosine molecule. In the presence of oxygen, the photobleaching is suppressed completely, but the sensitized photoöxidation of alcohol takes place.

When a small amount of oxygen is added to the evacuated alcoholic solution of eosine, the induction period appears, after which the photobleaching proceeds with almost the same rate as that in the evacuated state. Both the quantum yield for the consumption of oxygen during the induction period (γ) and that of the photobleaching in vacuo (k) were determined and the ratio γ/k was found to be ca. 3. This result and the reaction products detected (aldehyde in vacuo, acid and hydrogen peroxide in the presence of oxygen) were satisfactorily explained by the mechanism proposed by Bolland and Cooper. Further results somewhat important from the general standpoint of photobleaching of dye are :

(1) The lifetime of the intermediate to be attacked by oxygen (which is most probably DH·) is not less than 10−2-10−3 sec.

(2) The quantum yield for the primary process of the photobleaching D→D*→Dt(+RH)→DH·(+R·) in pure ethanol is ca. 10×10−4 at 20°C.

(3) In pure ethanolic solution, the decomposition of dye by the interaction between DH· and R· practically does not occur.
Irreversible Photobleaching of the Solution of Fluorescent Dyes. III. Photoreaction of Eosine in the Aqueous Alcoholic Solutions under Evacuated State
Authors: Imamura Masashi , Koizumi Masao
Published: July 2006

The photoreaction of eosine has been studied in ethanol-water mixture in vacuo. Irradiated solution showed a gradual spectral shift towards shorter wavelengths. Analyzing the spectra and applying the chemical method, it was found that the spectral shift is due to the production of uranine.

The rate of disappearance of eosine increases with rising concentration of ethanol until 20 vol. per cent, at which it reaches its maximum and constant value, which is the same as that in pure ethanol.

The primary processes of the aerobic photo-bleaching of eosine in aqueous solution were discussed and it was concluded that the process must be

D^t+O_2→D···O_2\xrightarrow\mathitH2O···prod. (iii)
The Solubility of Silver Bromate in Tetrahydrofuran- Water Mixed Solvents
Authors: Koizumi Ei , Miyamoto Hiroshi
Published: July 2006

To investigate the relation between the solubility of inorganic salts and the dielectric constants of solvents, the solubility of silver bromate in tetrahydrofuran-water mixed solvent was determined at 20°, 25° and 30°C, respectively. The logarithm of solubility is almost reciprocally proportional to the dielectric constant of the solvent in the region of the higher dielectric constant. But no linear relation was found in that of the lower dielectric constant of tetrahydrofuran-water mixed solvent.

Also, the solvation radius of silver bromate was calculated applying the above-mentioned data. The solvation radius is about 1 Å at each temperature.
THE DETERMINATION OF THE VAPOUR PRESSURES OF SODIUM AND POTASSIUM CHLORIDES
Authors: Horiba Shinkichi , Baba Hideo
Published: July 2006

The vapour pressures of NaCl and KCl up to the temperature of 1250°C. were statically determined.

The heats of vapourisation and of dissociation of these salts were calculated from the values of their vapour pressures and the order of the value of the dissociation constant of NaCl in gaseous state was given.
THE PRECIPITATION OF THE GOLD AND THE SILVER FROM THEIR DILUTE SOLUTIONS
Authors: Yasuda Mataichi
Published: July 2006

It has been pointed out that the metallic alloy of manganese and lead is suitable to fish the gold from its very dilute solution such as sea water. The method of preparation and the composition of the alloy have been described. The efficiency of its action has been studied.
APPLICATION OF AN ELECTROMAGNETIC FORCE TO “THERMOBALANCE”
Authors: Shibata Zen-ichi , Fukushima Masaji
Published: July 2006

The present writers have applied an electromagnet to the “thermo-balance” to remove the previous defects and succeeded in elevating its sensibility to that of the chemical balance. To determine its accuracy, the decomposition curves of the following five compounds have been determined: calcium carbonate, copper sulphate, cadmium sulphate, barium chloride and Mohr salt.
COLORIMETRIC DETERMINATION OF SULPHURIC ACID
Authors: Yamazaki Junzô
Published: July 2006

1. Sulphate is precipitated by benzidine hydrochloride and on resulting precipitate of filtrate the amount of benzidine is determined colorimetrically. From that value, the amount of sulphate is calculated.

2. “Rapid method” is given, which is simple in execution and does not take much time. The purification of benzidine for this method is also given.

3. The methods are applied on urine analyses and seem to be useful especially in clinical works.

4. In ordinary method 2–2.5 mg. H2SO4 per 10 c.c. can be determined; in rapid method 1–1.5 mg. per 5 c.c. is necessary.

5. When any hindering substances are absent, the accuracy of the results always lies within the range of accuracy of colorimetry. In conclusion, the author wishes to express his sincere thanks to Prof. T. Soda for his kind guidance during the work.
THE EFFECT OF GELATINE ON THE POLYMORPHIC TRANSFORMATION OF MERCURIC IODIDE
Authors: Sameshima Jitsusaburo
Published: July 2006

The mercuric iodide containing gelatine shows hysteresis on the transition temperature, i.e. it is necessary to heat considerably higher than 127°C. to transform the red modification into the yellow one, and on the contrary, the yellow one remains unchange for indefinite length of time at the room temperature. In this case gelatine act as a protecting colloid in a solid phase.

A lecture demonstration has been described of showing the behavior of the protected suppercooled mercuric iodide.

The transformation of mercuric iodide of metastable form to that of stable one is accelerated by the light energy.
STUDIES ON THE BROMINATION OF TETRA-ETHYL DICARBOXY-GLUTACONATE AND REMARKS ON THE CONSTITUTION OF THE GLUTACONIC ACIDS
Authors: Urushibara Yoshiyuki
Published: July 2006

By the action of bromine,on tetraethyl dicarboxyglutaconate, tetraethyl α-bromodicarboxyglutaconate was obtained as the final product. When the tetraethyl α- bromodicarboxyglutaconate was saponified by means of hydrochloric acid, the product was α-chloroglutaconic acid. According to the result of this investigation, it was concluded that, when one carries out the saponification of a derivative of glutaconic acid, the constitution of the product cannot be deduced from the starting substance. Uncertainty in J. F. Thorpe’s theory of the normal form was pointed out.
SUPPLEMENTARY STUDIES ON THE NITRILE-ESTERS OF THE DICARBOXYGLUTACONIC ACID
Authors: Urushibara Yoshiyuki
Published: July 2006

The table shows the outlines of synthetical studies made by the present author and others in regard to the nitrile-esters of dicarboxyglutaconic acid. The water of crystallisation which is present in some of the sodium compounds is omitted. The configurations of those written in molecular formulae are not yet known. As to the constitution of those written in the formula (……)2H2O, see this journal, 2 (1927), 29. The details will be found in the following places: (Remark: Graphics omitted.).
Studies on Crystals of Metallic Tris-ethylenediamine-complexes. II. The Crystal Structure of Sodium d-Tris-ethylenediamine-cobalt(III) Chloride Hexahydrate, 2d-[Co en3]Cl3·NaCl·6H2O
Authors: Nakatsu Kazumi , Shiro Motoo , Saito Yoshihiko , Kuroya Hisao
Published: July 2006

The preparation of two mixed salts, 2d-[Co en3]Cl3·NaCl·6H2O and 2l-[Co en3] Cl3·NaCl·6H2O is described. The space group is P3, with one formula unit in a cell of dimensions: a=11.47±0.03 Å, c=8.06±0.02 Å. However, the structure has the pseudo space group P63. By evaluating the functions ρ(XY) and ρ(YZ), projections of the structure on two crystal-lographic planes were obtained. A kind of twinned structure was proposed to get a better agreement between the observed and calculated intensities. The structure shows very close resemblance to that of d,l-[Co en3]Cl3·3H2O. A sodium ion is octahedrally surrounded by six water molecules, with Na ···O distances of 2.62 Å. The whole structure is ionic consisting of the ions [Co en3]3+,[Na(H2O)6] and Cl−.
Studies on the Intramolecular Hydrogen Bond in Conjugated Systems by the Measurements of Dipole Moments. II. Salicylaldehyde and o-Hydroxyacetophenone
Authors: Eda Bunzo , Ito Kazuo
Published: July 2006

Dipole moments of 4-chloro-2-hydroxybenzaldehyde, 5-chloro-2-hydroxybenzaldehyde, 5-methyl-2-hydroxybenzaldehyde, p-chloroacetophenone, p-nitroacetophenone and 5-chloro-2-hydroxyacetophenone were measured in benzene solutions. Their values are 2.31D, 1.37D, 3.32D, 2.40D, 3.29D and 1.79D, respectively. The components of the dipole moments of salicylaldehyde and o-hydroxyacetophenone, which were evaluated from the components of the moments of phenol, benzaldehyde and acetophenone, do not agree at all with the components that satisfy the observed moments of salicylaldehyde and o-hydroxyacetophenone and their derivatives. The magnitudes of the discrepancies are about 1.1D in the x-direction for salicylaldehyde, about 2.3D in the x-direction for o-hydroxyacetophenone, and almost 0.0D in the y-direction for both compounds. It was concluded that the charge migration was caused from the hydroxyl oxygen to the carbonyl oxygen by the intramolecular hydrogen bonding.
Electronic States of para-Benzoquinone. I. Calculation of the Energy Levels by a Semi-empirical Molecular Orbital Method Neglecting Configuration Interaction
Authors: Anno Tosinobu , Matubara Ikuo , Sadô Akira
Published: July 2006

A semi-empirical MO method proposed by Pariser and Parr was extended, taking account of the non-bonding electrons at the heterotoms explicitly as well as π-electorns. The electronic states of p-benzoquione were calculated neglecting cinfiguration insteractions.
Studies on the Organic Phosphorescence. III. Quenching by Some Gases and Vapors
Authors: Kato Shunji
Published: July 2006

The quenching action of some gases and vapors upon the phosphorescence of silica gel-trypaflavine phosphor was investigated. The gases which have more or less quenching effects are O2>NO>SO2, styrene>ether, dioxane, cyclohexene, 2-ethyl-1-hexene, methyl methacrylate, and the gases with no effects (when the quantities are not too large) are N2, Ar, H2, methane, n-hexane, propyrene, benzene, acetone, methanol and water.

The influence of quenching gases on the decay curve of phosphorescence were accurately examined and by analysing them on the basis of the scheme proposed in the preceding paper, it was established that in general S′ is not affected while both T and M state are appreciably affected. Furthermore, it was found that T→S′ transition is not promoted in general.

The quenching actins of O2 and NO were interpreted to be of kinetic type.
Polymorphism of Bis-β-hydroxyethyl Terephthalate
Authors: Miyake Akihisa
Published: July 2006

It is found that bis-β-hydroxyethyl terephthalate shows polymorphism, and there exist at least four different modifications. From the infrared spectra of these modifications, differences between the molecular forms are elucidated to some extent. These differences occur mainly from the difference in configuration of the side chain attached to the benzene ring.
Note on the Polymerization of Dyes in Solution
Authors: Mataga Noboru
Published: July 2006

The effect of concentration on the absorption spectra of DAA and BDAA in various organic solvents was studied in the concentration range from 10−6 to 10−2mol./l. Contrary to Levshin’s opinion, DAA forms polymers higher than dimer very easily in some organic solvents, and the association tendency of DAA is greater than that of BDAA.

Further, the association of these molecules is very sensitive to the solvents used. The association tendency and the spectral shift due to dimerization or polymerization have no correlation with the oscillator strengths of monomeric bands of these molecules, and this is true also for the various dye ions in aqueous solution.
An Electron Diffraction Investigation of the Molecular Structure of 1,4-Dichlorobutyne. I. Determination of Bond Distances and Angles
Authors: Kuchitsu Kôzo
Published: July 2006

The structure of 1,4-dichloro-2-butyne was investigated by means of the sector-microphotometer method of electron diffraction. The following values were obtained: C≡C: 1.214Å, C–C: 1.470±0.025Å, C–Cl: 1.796±0.015Å, and <C–C–Cl: 111°±2°. The C–Cl distance was found to be longer than that in carbon tetrachloride, 1.766±0.01Å.
lonization Potentials of Some Organic Molecules. IV. Troponoid Compounds
Authors: Higasi Keniti , Nozoe Tetsuo , Omura Itiro
Published: July 2006

First ionization potentials are obtained for the four substances: tropolone (a) 9.86, (b) 9.83; tropone (a) 9.68, (b) 9.69; 2-aminotropone (a) 9.43, (b) 9.50; cyclohexanone (a) 9.91, (b) 9.83 (units being eV.). Classification symbols, (a) and (b), denote that the measurement was made either by the method of critical slope or by the linear extrpolation method. These results are consistent with the conclusions from other physical data under certain conditions.
Dielectric Investigation on Coals. II. Mixture of Coal Powder and Paraffin Wax
Authors: Higasi Keniti , Miyasita Isao , Ozawa Yasutomo
Published: July 2006

A new method using powdered coal and paraffin wax was proposed for measuring the dielectric constant of coal concerned. In order to check the validity of this method, experiments were conducted on five coal specimens for which direct determination of dielectric constant had been made by the writers. Special attention was paid to the choice of a mixture formula and also to the influence of the electric conductivity upon the dielectric constant. It was concluded then that the present method could reproduce the dielectric constant of the coal with the fair precision of ± 10%.

The microwave measurement on one specimen reveals that all the dipoles in coal are completely inhibited from rotation at this frequency.
Dielectric Investigation on Coals. IV. Notes on Dipole Moment
Authors: Higasi Keniti , Higasi Yosie , Miyasita Isao
Published: July 2006

If coal be regarded as a supercooled liquid, a basis will be provided for determining the dipole moment of coals. Further uncertainty as to choosing a proper equation for liquids is dispelled by the fact that the Onsager equation gives for coal almost the same magnitude of dipole moment as obtained by the Debye equation.

After discussion focussed on the values of the ordinary and optical dielectric constants, dipole moments are evaluated for 19 coal specimens including four samples of foreign origin.

Brown coals are found to have a moment near to that of one O–H group. The polarity of bituminous coal is in general too small to be distinguishable from zero. These results are consistent with the observations on the frequency dependence of dielectric constant and loss factor of these coals.
Cyclopolysiloxanes from Cohydrolysis of Dimethyldichlorosilane with Methyldichlorosilane and Ethyldichlorosilane
Authors: Okawara Rokuro , Takahashi Ukiko , Sakiyama Minoru
Published: July 2006

1) Cyclotetrasiloxanes having D′ and D, and D* and D units have been prepared and characterized.

2) Methylhydrocyclopolysiloxanes D′n (n=4–7) and ethylhydrocyclopolysiloxanes D*n (n=3–6) have also been prepared and characterized. The erroneous assignment given to the latter compounds have been corrected.

3) Triethylcyclotrisiloxane D*n, the first member of D*3 was found to be an unstable compound.
Separation of Fission Products by Liquid-Liquid Extraction with Cupferron-Chloroform
Authors: Kiba Toshiyasu , Kanetani Mitsue
Published: July 2006

In order to separate rapidly the radioactive strontium and cesium from the solution containing gross fission products and other non-radioactive metallic ions, cupferron-chloroform extraction was attempted. By changing the acidity of the aqueous solution from 1n hydrochloric acid to pH 4, and by performing extractions in each stage, the strontium and the cesium could remain in the aqueous phase, while the other could be removed into the organic phase. The radioactive strontium may be extracted in the organic phase by the following extraction with TTA-hexone at pH 8.
Electron Diffraction Investigation on Tropone
Authors: Kimura Katsumi , Suzuki Satoshi , Kimura Masao , Kubo Masaji
Published: July 2006

The electron diffraction photographs of tropone in the gaseous state were taken with an τ2-sector. The data of the scattered intensity was analyzed by means of the radial distribution method as well as by the correlation method. The investigation of the molecule has led to the conclusion that the molecule assumes an essentially co- planar structure having a regular heptagon ring. The most probable values for the bond distances are: C—C=1.405±0.005Å, C=O=1.26±0.02Å and C···H=1.09±0.03Å.
Mutual Solubilities of Some Hydrocarbon Oils and Liquid Ammonia. I. Solubility Data
Authors: Ishida Kiyoharu
Published: July 2006

In order to obtain the quantitative knowledge on the solubility relations for liquid ammonia systems, mutual solubilities of aromatic hydrocarbons and liquid ammonia were determined at the several temperatures near the critical solution temperature, and data for other hydrocarbons were mainly obtained at 20° and 0°C. These results were presented in tables and a figure.
The Infrared Spectra of Ethoxy- and Methylethoxy-polysiloxanes
Authors: Okawara Rokuro
Published: July 2006

1) The infrared spectra of the lower members of ethoxy-, and mathylethoxy-polysiloxanes measured in the rock salt region are discussed.

2) Up to 1200 cm−1, the common bands near 960 and 1160 cm−1 are certainly to be connected with the grouping (Si)OC2H5.

3) Moreover, characteristic bands of (Si)OC2H5 group appear near 840 cm−1 in ethoxy end-blocked dimethylpolysiloxanes and near 790 cm−1 in ethoxypolysiloxanes.
Alkylalkoxypolysiloxanes. VI. Lower Members of Cyclic Methyl-, and Ethyl-ethoxypolysiloxanes
Authors: Okawara Rokuro , Minami Gi-ichi , Oku Zensaburo
Published: July 2006

1) Methyl- and ethyl-ethoxydichlorosilane were hydrolyzed with considerable dropping rate using pyridine as an acid acceptor.

2) Methyl- and ethyl-ethoxycyclotrisiloxane have been prepared and characterized. The former was found to be an unstable compound.

3) Methyl- and ethyl-ethoxycyclotetrasiloxane have been prepared and characterized.

4) Some brief data of infrared absorption spectra of those compounds have been presented.
Studies on the Synthesis of Metal Complexes. III. Synthesis of Ethylenediamine-carbonato, Ammine-oxalato and Ethylenediamineoxalato Series of Cobalt (III) Complexes
Authors: Mori Motoshichi , Shibata Muraji , Kyuno Eishin , Hoshiyama Koji
Published: July 2006

Three series of cobalt(III) complexes were systematically synthesized from the green solution of potassium tricarbonatocobaltate(III) by means of successive substitution of carbonate by other groups:

 i) Blue-K[Co en(CO3)2]·H2O,

Violet-K[Co en(CO3)2]·H2O,

[Co en2CO3]Cl·H2O, [Co en3]Cl3·3H2O

 ii) Blue-K[Co(NH3)2(C2O4)2]·H2O,

Violet-K[Co(NH3)2(C2O4)2]·H2O,

[Co(NH3)4C2O4]Cl,

K3[Co(C2O4)3]·3H2O

 iii) Blue-K [Co en(C2O4)2]·H2O,

Violet-K[Co en(C2O4)2]·H2O,

[Co en2(C2O4)]Cl·H2O.

Of these, the blue and the violet varieties are probably to be regarded as new complexes, stereoisomeric with each other.
Spectrochemical Study of Microscopic Crystals. XVII. The Structure of Cupric Salts with Monocarboxylic Fatty Acids
Authors: Yamada Shoichiro , Nakamura Hiroji , Tsuchida Ryutaro
Published: July 2006

In order to examine the structure of cupric alkanoates, the dichroism in the visible and the ultra violet region has been determined by the microscopic method with normal butyrate, valerianate, capronate and caprylate of copper (II). Visible and ultra-violet absorption spectra in organic solvents and infrared absorption spectra in Nujol mulls have been determined with the above compounds, along with cupric palmitate and stearate. Iso-alkanoates have also been examined in a similar way.

All these compounds in the crystalline state and in organic solvents are found to show similar absorption spectra having the dichroism with characteristics fundamentally similar to those of cupric acetate and propionate which had earlier been reported. From these results, it has been concluded that all the above compounds consist of the dimeric molecules.

The anhydrous forms of the compounds have been shown to consist of the dimeric molecules resembling those of the hydrated form. All the above compounds show absorption bands at about 43 and 80×1013/sec. The former is polarized along the Cu(O)4-plane and the latter along the direction binding the two copper atoms in a molecule.
Dielectric Properties of Starch. I. Audio Frequency Region
Authors: Ono Sôzaburo , Kuge Takashi , Koizumi Naokazu
Published: July 2006

The results of dielectric measurements for α- and β-modification of potato starch containing 0.0-13.9% sorbed water at audio frequency region are described. At different temperature regions, two different dielectric loss processes are found which we call low frequency loss process and high frequency loss process. Discussions on the low frequency loss process are made. Qualitatively, both modifications of starch have the similar dielectric properties. From the analysis of the polarization of the sorbed water, it may be concluded that sorbed waters change their properties gradually as sorption is increased, while they also loosen the micell structure of starch.
Polarographic Investigations of Vitamin C. I. On the Oxidation Waves of l-Ascorbic Acid and the Reduction Wave of Dehydro-l-ascorbic Acid
Authors: Ono Sôzaburo , Takagi Masanosuke , Wasa Tamotsu
Published: July 2006

l-Ascorbic acid (A. A.) shows an oxidation wave at pH less than 8 and two in a more alkaline range. After standing of A. A. in alkaline solution, the third oxidation wave has been observed.

Dehydro-l-ascorbic acid (D. A. A.) has been also tested in alkaline solution. The mechanism of the electrode oxidation of A. A. and its decomposition in alkaline solution are discussed. The reduction wave of D. A. A. has been obtained at pH 2 to 5, in which the half-wave potential is about −0.3 to −0.5 V. (vs. N.C.E.).

The wave height is about 1/1000 of its expected diffusion current at room temperature. The wave has all the typical characteristics of the kinetic current. The wave height is roughly proportional to the concentration and is not appreciably influenced by pH and the components of the buffer solution, but the shape of the wave is strongly deformed by adding small amounts of surface active substance such as gelatin.

The reduction product of D. A. A. at the dropping mercury electrode has been polarographically proved to be A. A.

Discussions are made on the configuration of the inactive form of D. A. A. and the reversibility of the A. A. and D. A. A. system.
Dielectric Constant of Liquid Consisting of Anisotropic Molecules
Authors: Yasumi Masasi , Okabayashi Hideo , Komooka Hitoshi
Published: July 2006

Our previous theory of dielectric constant of liquid consisting of spherical molecules having an isotropic polarizability is extended to the case when the molecule has an ellipsoidal shape and an anisotropic polarizability.

The theory is compared with experimental results for about thirty substances. The coincidence is quite satisfactory with few exceptions. For non-polar substance, better agreement between the experimental value and the theoretical value is achieved if we use our formula instead of the Lorentz-Lorenz formula.
Polarographic Studies of Metallic Complexes. II. Isothiocyanato-ammine and Related Complexes of Chromium (III)
Authors: Maki Nobufumi , Shimura Yoichi , Tsuchida Ryutaro
Published: July 2006

1. In neutral and unbuffered solution of 0.1 f potassium chloride, 0.1 f potassium thiocyanate, or 1 f potassium thiocyanate, the complex ion, [Cr(NH3)n(NCS)6−n]n−3 and [Cr en3]3+ were all reduced irreversibly in two steps at the dropping mercury electrode. The first diffusion current corresponds to the reduction, chromium(III)→chromium(II), and the second to the reduction, chromium(II)→chromium(0).

2. In the solution of 0.1 f potassium chloride, the polarograms of [Cr en2X2]+ type complexes show three waves. Each of the first two waves, corresponding to a gain of one electron, represents the reduction of chromium(III) to chromium(II) and the last wave, corresponding to a gain of two electrons, represents the reduction to the metallic state. As regards the first two waves, the former wave represents the reduction of the original chromium(III) complexes to chromium(II) state and the latter represents the reduction of the aquated chromium(III) complexes to chromium(II) state.

3. In agreement with the results obtained for cobalt(III) complexes by Holtzclaw et al., the trans isomer of [Cr en2(NCS)2]+ has a little more negative half-wave potential than the corresponding cis-form.

4. The polarographic stabilities of chromium(III) complexes increase in the following order of the ligands:

Cl^-<NCS^-<en<NH_3

5. The catalytic effects on the double wave of oxygen have been found for [Cr(NH3)2(NCS)4]−, [Cr(NCS)6]3−, or cis-[Cr en2(NCS)2]+. Such special polarographic behavior was not found in the other chromium(III) complexes.
Colloid Chemical Studies on Starching Materials. II. Intrinsic Viscosity of Polyvinyl Alcohol in Soap Solutions
Authors: Nakagaki Masayuki , Nishibayashi Hiroko
Published: July 2006

The concentration dependence of the viscosity of polyvinyl alcohol in solutions of constant soap concentration is studied. At the soap concentration lower than its critical micelle concentration, the effect of soap on the viscosity of polyvinyl alcohol is very little. At the soap concentration near the critical micelle concentration, soap molecules are combined with the polymer, the latter behaving like a polyelectrolyte. At high soap concentration, the polymer behaves like a non-ionic polymer in a very good solvent.
Resolution of Amino Acids. I. Resolution of Racemic Phenylalanine and γ-Phenyl-α-aminobutyric Acid by Leucine Aminopeptidase
Authors: Tanaka Atsushi , Izumiya Nobuo
Published: July 2006

Dl-Phenylalaninamide and Dl-phenyl-aminobutyric acid amide were resolved to l-amino acids and d-amino acid amides by the partially purified leucine aminopeptidase preparation.

The products in the digests were separated conveniently by the use of ion-exchange resin, Amberlite IRA-400, in the case of Dl-phenylalaninamide, while by the differential solubility in the case of Dl-phenylaminobutyric acid amide.

The parts of d-amino acid amide hydrochlorides obtained were changed to d-amino acids by acid hydrolysis.
The Study of the Adsorption of Detergents at a Solution-Air Interface by Radiotracer Method. I. Adsorption Isotherm for the Solution of Sodium Alkyl Sulfates
Authors: Matuura Ryohei , Kimizuka Hideo , Miyamoto Shigeru , Shimozawa Ryosuke
Published: July 2006

The adsorption of the three alkyl sulfates, SDS, STS and SHS, at the solution-air interface has been measured directly by means of the radiotracer method. It has been proved that the surface adsorption increases with increase in the concentration and has a tendency to be saturated at concentrations near cmc for each detergent solution. The results have shown that the adsorption increases with increasing chain length. The Gibbs adsorption equation has been cheked and discussed.
Irreversible Photobleaching of the Solution of Fluorescent Dyes. V. Photobleaching of Erythrosin
Authors: Imamura Masashi
Published: July 2006

Photobleaching of the aqueous alcoholic erythrosin solutions in air and in vacuo was investigated. In general, erythrosin showed behavior similar to eosin. An excited dye molecule which participates in the primary processes is the long-lived species, having a lifetime of the order of 10−7sec. It was concluded that the primary process in aerobic aqueous erythrosin solution proceeds via the process, D+O2→D······O2, as in the case of eosin. It was found that excited erythrosin is somewhat more reactive than excited eosin towards dissolved oxygen, while it is less reactive towards alcohols in vacuo. Some quantitative values on the reactivities were given.
Polymerization of Methyl Methacrylate Initiated by a Combined Action of Trichloroacetic Acid and Dimethylaniline
Authors: Uehara Ryoichi
Published: July 2006

The polymerization of methyl methacrylate is initiated even at room temperature by a combined action of trichloroacetic acid and dimethylaniline. In case of bulk polymerization, the initial rate of polymerization is proportional to each of the square roots of the concentrations of trichloroacetic acid and dimethylaniline. In case of polymerization in benzene, the initial rate depends upon the concentration of methyl methacrylate. These relationships can be reasonably explained by assuming a bimolecular reaction between trichloroacetic acid and dimethylaniline to form radicals as the initial reaction of the polymerization. Hydroquinone acts as an inhibitor for this reaction.
Synthetic Studies on the Benzofuran Derivatives. Part V. Synthesis of Furano (2′,3′: 7,8)-isoflavone
Authors: Fukui Kenji , Kawase Yoshiyuki
Published: July 2006

1) Furano(2′,3′: 7,8)-isoflavone (III) was prepared from benzyl 4-hydroxy-5-benzofuranyl ketone (II) and ethyl orthoformate.

2) 7-Hydroxy-8-formyl-isoflavone (V) was obtained from 7-hydroxy-isoflavone (IV) by the hexamine method. 5′-Car-bethoxy-furano(2′,3′: 7, 8)-isoflavone (VI) was prepared from 7-hydroxy-8-formyliso-flavone (V) and ethyl bromomalonate by Tanaka’s method for benzofuran synthesis. The ester VI was hydrolyzed to the free acid VII and then decarboxylated in quinoline with copper powder to the isoflavone III.
Behavior of Zirconium-95 and Niobium-95 in Dilute Hydrochloric Acid toward Cation Exchange Resin
Authors: Yajima Seishi
Published: July 2006

By passing 0.2 N hydrochloric acid solution of tracer amounts of 95Zr and 95Nb (about 10−11 mol./1., 10−13 mol., or 1 μC, with respect to each nuclide) through a cation exchange resin column (Dowex 50–X8, Amberlite IR-120, or Diaion SK) and eluting with 0.2 N hydrochloric acid, a fraction containing mainly 95Nb was obtained. A fraction containing mainly 95Zr was then obtained by eluting with 0.5% oxalic acid or 3 N hydrochloric acid. With higher concentrations of non-active zirconium and niobium (about 106 mol./1. each), similar results were also obtained.

As the 0.2 N hydrochloric acid solution of 95Zr–95Nb became aged, the adsorbability of 95Zr decreased. Effect of hydrochloric acid concentration on the adsorbability of 95Zr and 95Nb was studied and the concentration range 0.1 to 0.3 N was found to be suitable for separation.

The adsorbability of 95Nb increased with an increase in the concentration of strontium ion.
Spedrochemical Study of Microscopic Crystals. XVIII. The Color and the Structure of Compounds of a Magnus Green Salt Type
Authors: Yamada Shoichiro , Tsuchida Ryutaro
Published: July 2006

The color and the structure of the compounds of a Magnus green salt type, [Pt(amine)4] [PtCl4], have been studied. The dichroism with crystals of [Pt(methylamine)4] [PtCl4] and [Pt(ethylamine)4] [PtCl4] has been quantitatively determined at room temperature in the visible and ultraviolet region by the microscopic method. From the measurements, the unusually deep color of the former has been shown to be ascribed to a direct type of interaction between platinum atoms. No interaction of this sort is present in the crystal of the latter, which is pink in color. It is suggested that the compounds having a formula of [Pt(alkylamine)4] [PtCl4] may generally be classified into two kinds, one being colored green and the other pink. In the crystals of the former there is a direct type of interaction between platinum atoms at the center of the planar complexes, but no interaction of such a sort is operative in the crystals of the latter.
The Formation of Stable Semiquinone of Methylene Blue by the Irradiation of Visible Light and γ-Rays
Authors: Koizumi Masao , Obata Hiroshi
Published: July 2006

In connection with Swallow’s observation that methylene blue in 22.9 N sulfuric acid aqueous solution containing a small amount of alcohol is reduced to a stable semiquinone when irradiated with γ-rays in vacuo, some experiments were done to investigate the role of alcohol.

It was elucidated that alcohol acts most certainly as an OH scavenger. Benzoic acid was found to be an effective OH scavenger in this case just as in usual solutions.

In the absence of alcohol either the formation of semiquinone or the irreversible decomposition of dye scarcely ever takes place in vacuo while in the aerated solution, only the latter reaction slowly proceeds. A plausible interpretation of these results was given.

It was further found that the formation of stable semiquinone can easily occur on irradiation of Swallow’s system with the visible light.
Stress Relaxation of Non-electrolytic Thermo-reversible Gels Concentration Dependence of Distribution Function of Relaxation Times. Polyvinyl Alcohol-Glycerin-Water Gels
Authors: Arakawa Kiyoshi
Published: July 2006

From a stress relaxation experiment by means of a chainomatic balance relaxometer the stress relaxation curves were obtained for the gel of polyvinyl alcohol-glycerin-water system, which was taken as an example of non-electrolytic thermoreversible gel. Gels of 8.3%, 9.9% and 12.1% were used. The temperature of the samples was changed between about 2°C and 75°C. Master relaxation curves were obtained for each concentration over the range of time, 10−4∼105 hours, using the time temperature superposition principle. According to Alfrey’s approximation, relaxation spectra were calculated.

The following results were obtained.

1) The master relaxation curves exhibit a fairly complicated nature on concentration dependence.

2) The logar vs. T–Ts relation obeys approximately the formula by Williams, Landel and Ferry in the range of T–Ts, −40∼0°C, but outside the range deviates fairly from it.

3) The apparent activation energy is 60 kcal./mole, which is nearly kept constant over the temperature- and concentrationrange in the present work.

4) The shift of the relaxation spectrum due to the change of concentration is not uniform over the region of box type. The maximum point in that region shifts upwards and to the longer-time side with increase of concentration.
Ultraviolet Absorption Spectra of Nitro-, Dinitro- and Trinitro-substituted Benzenes
Authors: Abe Takehiro
Published: July 2006

1) In ethanol and in water the progressive blue shifts of the 260 mμ band of nitrobenzene for the nitro compounds are observed in the order of increasing number of nitro groups.

2) Only TNB shows visible weak absorption bands in acetone.

3) In an aqueous solution of sodium hydroxide these nitro compounds show intense absorption bands at longer wavelengths as the number of nitro group increases.
Formation and Aging of Precipitates. VIII. Formation of Monodisperse Particles (1) Gold Sol Particles by Sodium Citrate Method
Authors: Takiyama Kazuyoshi
Published: July 2006

Gold sol particles prepared by sodium citrate method were monodisperse. The size of gold particles decreased exponentially with increasing initial concentration of the auric ion, and increased exponentially with the reaction temperature. At the initial stage of the reaction of the gold sol formation, the gold nuclei were formed rapidly. After the nucleation the number of particles was kept constant over the whole period of reaction and the particles grew with the autocatalysis-like reaction at the surface of the particle.
Irreversible Photobleaching of the Solutions of Fluorescent Dyes. VI. Photobleaching of Uranin in Alkaline Solutions
Authors: Imamura Masashi
Published: July 2006

Investigation of the photobleaching of uranin solutions has led to the same conclusions as for eosin and erythrosin, concerning the primary processes both in aqueous and in alcoholic media. Strongly alkaline solutions of uranin in aqueous alcohol show an irreversible photobleaching in vacuo. On the reactivities of the excited uranin, and on the comparison of them with those of two other xanthene dyes previously investigated, some discussions have been given.
Studies on Organic Reagents for Inorganic Analysis. IV. Syntheses of New Phenylfluorone Derivatives and their Reactions with Metal Ions
Authors: Sano Hirotoshi
Published: July 2006

2,3,7-Trihydroxy-9-(3′-nitrophenyl) fluorone, 2,3,7-trihydroxy-9-(4′-nitrophenyl)fluorone, and 2,3,7-trihydroxy-(2′-sulfophenyl)fluorone were synthesized by a comparatively simple procedure, for the purpose of studying the reaction between the colorimetric reagent and metal ions and to search for a useful colorimetric reagent. The effects of the substituents introduced on the absorption maxima of the dyes and the metal chelates formed, and on the reactivities of the dyes with metal ions such as germanium(IV), zirconium(IV), and titanium(IV). 2′Sulfophenylfluorone metal chelates are soluble in an ethanolic or cyclohexanolethanolic solution. 3′-Nitrophenylfluorone is most excellent as the colorimetric reagent for the determination of metal ions because of the high stubility high sensitivity and low absorbance of the blank solution.
Optical Properties of Colored Colloidal Systems. I. Theoretical Studies on the Extinction of Light by the System of Small Spherical Particles
Authors: Nakagaki Masayuki
Published: July 2006

The extinction, scattering and absorption of light by the colored colloidal systems of small spherical particles have been discussed. Approximate equations for these quantities have been derived for a case where the size of particles and the absorption coefficient of the dispersed phase are relatively small. Using these equations, the numerical values of the quantities have been computed for the systematically varied values of the relative index,(m0−ik0), and of α.

It is shown by the results of the com putation that the values of the extinction and the absorption by the colloidal systems of small colored spheres (whose α-value is smaller than about 0.5) are the smaller, the greater the value of m0. On the other hand, the scattering increases with m0,ik0 and α.

The values of the scattering coefficient calculated by the approximate equations showed sufficient agreement with the values by the Mie theory as far as α is smaller than 0.6.
Studies on the Mannich Reaction. I. On the Formation of Piperidine Derivatives (1)
Authors: Uchino Norito
Published: July 2006

1) In the reaction of acetophenone with formaldehyde and ammonium chloride, tris-(β-benzoylethyl)-amine hydrochloride (III·HCl) and4-hydroxy-4-phenyl-5-benzoyl-1-(β-benzoylethyl)-piperidine hydrochloride (IV·HCl) were produced via bis-(β-benzoylethyl)-amine hydrochloride (II·HCl) after mono-(β-benzoylethyl)-amine hydrochloride (I·HCl).

2) Phenyl vinyl ketone readily reacted with compound I·HCl or II·HCl to give compounds III·HCl and IV·HCl.
On the Phase Transition of Hexamethyldisilane
Authors: Suga Hiroshi , Seki Syûzô
Published: July 2006

Measurements of the heat capacity (200∼300°K) and the vapor pressure (274∼310°K) were carried out covering the transition and melting points of hexamethyldisilane. The following results were obtained; Ttr 221.8°K, ΔH(transition) 2330 cal./mol., ΔS(transition) 10.5 e. u.; Tf 287.72°K, ΔH(fusion) 721 cal./mol, ΔS(fusion) 2.51 e. u.; vapor pressure equations,

& logP(mmHg)=-2105.4/T+8.5503

& (274.5∼286.6°K)

& logP(mmHg)=-1953.1/T+8.0105

& (287.6∼310.4°K);

ΔH sub 9640±25 cal./mol., ΔSsub 26.0±0.17 e.u., ΔG°298.16(sub.) 1900±76 cal./mol.; ΔHvap 8943±16 cal./mol., ΔSvap 23.5±0.05 e. u., ΔG°298.16(vap.) 1940±31 cal./mol.

These data showed that the present crystal belongs to the class of plastic crystal. We have discussed the qualitative nature of the phase transition in the present crystal from the point of view of entropy, referring to the X-ray and the nuclear magnetic resonance studies. The remarkable “vapor snake” phenomenon was also observed on this material.
Stereoregular Polymers. I. Polymerization of Styrene by Triethylaluminum-Titanium Tetrachloride Catalysts
Authors: Murahashi Shunsuke , Nozakura Shun’ichi , Sumi Masao , Hatada K\={o}ichi
Published: July 2006

Styrene was polymerized by the heterogeneous catalysts of Ziegler’s type which were prepared under various conditions. The important factor which have pronounced effects on the stereospecificity and the catalytic activity of the mixture are concluded to be the existence of the remaining titanium tetrachloride,ethylaluminium chlorides and some soluble aluminium-titanium complex compounds, and the crystalline nature of the solid catalytic mass.The first three are considered to be responsible for the atactic polymerization of styrene and can be removed by washing with n-heptane. The crystallinity of the solid catalysts seems to be necessary for its high tereospecificity and catalytic activity.

The solid catalyst was examined by X-ray. It was found that the crystalline component of the catalyst did not correspond to TiCl3 or TiCl2, and thus it was suggested that some crystalline complex compounds containing Al and Ti or some other modification of TiCl3 (or TiCl2) would be responsible for the effective catalytic component of Ziegler catalyst. The authors also suggested that the fact might be one of the important differences between the heterogeneous catalysts of Ziegler’s type and Natta’s type.
The Mannich Base of Troponoid and its Application. II. On 5-Bromomethyltropolone Derivative
Authors: Seto Shuichi , Ogura Kyozo
Published: July 2006

Reaction of 3,7-dibromo-5-hydroxymethyltropolone with hydrobromic acid affords 3,7-dibromo-5 -bromomethyltropolone, which has a high reactivity and reacts with various anionoid reagents to undergo substitution of bromine in the bromomethyl group. In this manner it is possible to extend the substituent by forming C–O, C–N, C–S and C–C bonding at the tip of the methyl group in position 5 of the tropolone ring.
Magnetochemical Investigation on Thermal Decomposition of Silver Oxide
Authors: Tobisawa Sh\={o}taro
Published: July 2006

(1) It was found, by means of the thermal and magnetic balance, that the decomposition temperatures of silver oxide and of silver oxide containing silver carbonate are 354 and 372°C, respectively.

(2) The magnetic susceptibilities of metallic silver obtained by the decomposition and of silver oxide are −0.21×10−6and −0.48×10−6 units per gram at room temperature, respectively. Metallic silver is normally diamagnetic from room temperature to 1100°C.

(3) Under the present experimental conditions, the rate of decomposition is represented by the equation dx⁄dt=aitbi for the whole course of the decomposition, where i is the subscript for each stage, and generally both ai and bi depend on the temperature. It is considered that nuclei are created at intervals as the reaction proceeds.
Absorption Spectra of Dyes. II. On Non-additivity of Absorption Spectra of Binary Mixtures of a Direct Dye and Some Acid Dyes in Aqueous Solution
Authors: Tanizaki Yoshié , Kobayashi Teruaki , Ando Noboru
Published: July 2006

1. Absorption spectra of mixtures of Direct Sky Blue 6B with p-X-aniline → γ acid, in which the substituent X means H, CH3, OCH3, Cl or NO2, and the components in aqueous solution were observed in the visible and near ultraviolet regions.

2. All the absorption bands showed non-additive property, excepting the bands in the region of 400∼460 mμ of the mixtures of Sky Blue and X-β shown in Figs. 2 and 3. And optical densities of observed bands of a mixture were generally smaller than sums of the values of each component, but when the acid dyes made by α coupling were used as other components, increases were seen at the positions corresponding to wave lengths of the first bands of them.

3. An explanation for these non-additive properties was given by means of the interaction between the corresponding bands of components.

4. At the same time, in this connection, it is pointed out that the apparent single band of the first of p-X-aniline → γ acid in α coupling consists of two bands and similarly the first band of Direct Sky Blue 6B may also consist of two bands.
Estimation of the Energy of Hydrogen Bonds Formed in Crystals. I. Sublimation Pressures of Some Organic Molecular Crystals and the Additivity of Lattice Energy
Authors: Aihara Ariyuki
Published: July 2006

Sublimation pressures of a number of organic molecular crystals were measured by a viscosity gauge. The heats of sublimation of these compounds were examined in relation to their molecular structures, and it was concluded that an additivity rule could be applied to the lattice energies of these crystals as a first approximation.
Stress Relaxation of Thermo-Reversible Gels. Polyvinyl Alcohol–Congo Red–Water System
Authors: Arakawa Kiyoshi
Published: July 2006

Stress relaxation curves were obtained for the gels of the polyvinyl alcohol-conga red-water system in the temperature range, 15∼60°C, by means of a chainomatic relaxometer. The molecular weight of polyvinyl alcohol was 8.5×104, and gels of 15.0 and 17.5% were used, where the concentration of congo red was adjusted to be 1/10 of that of polyvinyl alcohol. Master relaxation curves were obtained for each concentration over the range, 10−2∼109hr, and relaxation spectra were calculated by the second order approximation. The following results were obtained.

1) The logaT vs. T relation gives a single curve for two concentrations, and does not obey the equation of WLF form, Also it has characteristics similar to that of agar-agar gels.

2) The apparent activation energy is kept constant to be 42 kcal. below about 43°C, and above this temperature it sharply increases with temperature.

3) The reduction on concentration to a single composite relaxation curve seems to be possible in rough approximation.
Study on the Reductive Spinel—A New Spinel Formula AlN–Al2O3 instead of the Previous One Al3O4
Authors: Yamaguchi Goro , Yanagida Hiroaki
Published: July 2006

A compound between aluminum oxide and aluminum nitride can be produced in a reductive atmosphere above 1650°C.

A new spinel formula AlN–Al2O3 should be adopted instead of the previous one Al2O–5Al2O3 or Al3O4.

The physical constants of AlN-Al2O3 are as follows: crystal structure Fd3m, Z=8, a=7.940 Å; density 3.78g./cc.; dielectric constant 23.8; refractive index 1.80; magnetic susceptibility −0.34×10−6/g
Abnormal Reduction of 2-Methoxy-5-hydroxy-1-naphthylacetic Acid
Authors: Matsumoto Takeshi , Suzuki Akira
Published: July 2006

1,2,3,4-Tetrahydro-5-hydroxy-1-naphthylacetic acid has been obtained from 2-methoxy-5-hydroxy-1-naphthylacetic acid by reduction either with sodium and n-butanol, or with lithium and liquid ammonia-ethanol. In the former case, under moderate conditions, 1,2,3, 4-tetrahydro-2-oxo-4, 5-dihydroxy-1-naphthylacetic acid has been isolated as a by-product.
Studies on Dehydroalanine Derivatives. I. Synthesis of N-Carboxy-dehydroalanine Anhydride
Authors: Sakakibara Shumpei
Published: July 2006

N-Carboxy dehydroalanine anhydride was first synthesized from carbobenzoxy dehydroalanine. The structure of the N-carboxy anhydride was confirmed by the analysis of its infrared spectrum and by the investigation of its chemical behavior. The hydrolytic reaction of the N-carboxy anhydride was compared with that of N-carboxy Dl-alanine anhydride, and it was supposed that dehydroalanine carbamic acid might exist stably in dioxane at ordinary temperature.
A Note on the Proton Magnetic Resonance Spectra of Some Thiophene Derivatives
Authors: Takahashi Kensuke , Matsuki Yasuo , Mashiko Tatsuo , Hazato Genjiro
Published: July 2006

1) The chemical shifts of the ring protons for twenty-two kinds of thiophene derivative were measured, and the qualitative discussions on the substituent effects were also given.

2) The coupling constants between the ring protons for thiophene derivatives can be generally assumed to be J45\simeqJ23>J34>J25>J24\simeqJ35.