bluuebunny/crossref_metadata_2025 huggingface dataset:
The Infrared Spectra of Methylhydropolysiloxanes
Authors: Sakiyama Minoru
Published: July 2006

1) Infrared spectra of some methylhydropolysiloxanes involving the units, H(CH3)2SiO1⁄2 and H(CH3)SiO2⁄2, were studied. The assignments of Wright and Richards with methylpolysiloxanes were comfirmed in this study.

2) The stretching and the bending band involving an Si–H bond are found in the range 2120–2170 cm−1 and 760 cm−1, respectively.

3) Characteristic absorption bands of the unit H(CH3)2SiO1⁄2 are observed near 900 cm−1 and 830 cm−1, while the unit H(CH3)SiO2⁄2 does not give the characteristic band and the band related with this unit is different in each compound.
Mercury Photosensitized Reaction of Cyclo-octatetraene and the Comparison with the Direct Photochemical Reaction
Authors: Yamazaki Hideo
Published: July 2006

The reaction products of both the mercury photosensitized reaction and the direct photochemical reaction are the same, i.e. acetylene, benzene, orange-colored liquid (presumably bicyclo form of C8H8), polymer and a trace of styrene; the noncondensable products at liquid nitrogen temperature such as hydrogen and methane were not detected.

A quantitative experiment has been made on the decomposition reaction, in which cyclo-octatetraene shows a similar behavior to ethylene in the pressure dependence of the quantum yield. The quantum yields of the decomposition are of the same magnitude in both the mercury photosensitized and the direct photochemical reaction. The result shows that the two reactions proceed via the same excited state (probably triplet), directly or indirectly.

An investigation has also been made on the polymerization reaction, for which the total pressure change and the absorption spectrum of the reaction products have been examined in the course of the reaction. It is concluded that the polymerization takes the place via orange-colored liquid as an intermediate.

In the study of the reaction of hydrocarbons with Hg(63P1) atom a great deal of evidence has now been accumulated which shows the fact that the reaction always accompanies hydrogen production. The mercury photosensitized reaction of cyclooctatetraene is one of the rare exceptions in this generality.
Synthetic Studies on the Benzofuran Derivatives. Part III. Reaction of 7-Hydroxy-8-formyl-2-methylisoflavone with Ethyl Bromomalonate and Synthesis of Furano(2′,3′:7,8)-2-methylisoflavone
Authors: Matsumoto Takashi , Kawase Yoshiyuki , Nanbu Mutsumu , Fukui Kenji
Published: July 2006

5′-Carbethoxy-furano(2′,3′: 7,8)-2-methylisofiavone (IV) was obtained from 7-hydroxy-8-formyl-2-methylisoflavone (III) and ethyl bromomalonate by Tanaka’s method for benzofuran synthesis. The condensation product IV was hydrolyzed to give the free acid V, which was decarboxylated in quinoline with copper powder to yield furano(2′,3′: 7,8)-2-methylisoflavon (VIII). The structures of the condensation product and its derivatives were discussed.
Electronic States of p-Benzoquinone. IV. Infrared Spectrum and Assignment of Vibrational Frequencies in the Ground Electronic State
Authors: Anno Tosinobu , Sadô Akira
Published: July 2006

The infrared absorption spectra of p-benzoquinone in carbon disulfide and carbon tetrachloride solutions in rock salt region are measured and interpreted together with the Raman data reported by Stammreich and Forneris. A complete, although more or less tentative, assignment of the fundamental frequencies to modes of vibrations is proposed.
Thermal Decomposition of Chromic Anhydride Supported on Alumina
Authors: Matsunaga Yoshio
Published: July 2006

The thermal decomposition of chromic anhydride supported on gamma-alumina at 300°, 350° and 450°C was examined by chemical analysis and by magnetic susceptibility measurements. The stabilization of the plus-six oxidation state of chromium in a highly dispersed state was confirmed by the present experiments. In addition, by comparing the oxidation number and the magnetic susceptibility of chromium, it was found that the behavior of supported chromic anhydride in large aggregates is also anomalous. Contrary to the case of the thermal decomposition of massive chromic anhydride, the intermediate oxides CrO2.6 and CrO2.4∼5 were not found. The large aggregates of chromic anhydride on alumina lose the greater part of their active oxygen at relatively low temperatures and crystallize continuously into chromia with further loss of oxygen.
π-Electronic Structures of α-Naphthoquinone and Anthraquinone
Authors: Kuboyama Akira
Published: July 2006

Electronic structures of p-benzoquinone, α-naphthoquinone, and anthraquinone were studied with the simple MO method, using the same integral values as adopted in the SCF MO calculation for p-benzoquinone. As for charge distributions, the negative charges of oxygen atoms slightly increase in the order p-benzoquinone, α-naphthoquinone and anthraquinone. The calculated dipole moment (2.2 D) of α-naphthoquinone seems too large. As for bond orders, the reasonable results were obtained. Two problems concerning the near UV absorption bands (1. a similarity among the π–π transition bands of the three p-quinones, 2. a relative magnitude of the n–π transition energy in the order of p-benzoquinone, α-naphthoquinone and anthraquinone) can be clearly explained with the calculated results. Especially, the effect of the electrondonating group on the π–π transition bands of α-naphthoquinone and anthraquinone can also be favourably explained, according to the modified Herzfeld-Nagakura-Baba’s formula, with the calculated results. It seems sure that for the o-quinone type compounds the similar result can be obtained with the same method as used for the p-quinone type compounds.
Synthesis of 3,3-Disubstituted-2-Piperazinones
Authors: Kametani Tetsuji , Taub William , Ginsburg David
Published: July 2006

Several 3,3-disubstituted-2-piperazinones have been synthesized for pharmacological testing as potential hypnotics.
Studies on the Interaction of Surface Films with Solute in Solution. I. Potentiometric Titration of Aqueous Dye Solution and Calculation of Ionization Constant of Dye
Authors: Muramatsu Mitsuo
Published: July 2006

Change of pH of aqueous dye solution was traced by titrating with the solution of hydrochloric acid or sodium hydroxide. From these data, ionization constants for each ionizing group in chrysoidine, methyl orange, tropäolin OO and aluminon were calculated, making use of equations based on the law of mass action with a specially-selected parameter. The validity of the ionization constants thus determined were confirmed by reasonable coincidence of the titration curves obtained by calculation using these data with those observed, over the wide range of pH. In the case of Congo red, however, it seemed better to treat it as a high-molecular electrolyte. Ionization constants calculated by an equation based on such a treatment explain the experimental result better than those based on the treatment similar to the case of other simple dyes.
Studies on the Interaction of Surface Films with Solute in Solution. III. Effect of Dissolved Dyes upon the Monolayer of Octadecylamine
Authors: Muramatsu Mitsuo
Published: July 2006

The interaction between octadecylamine in monolayer and various dyes in aqueous substrate under varying pH was studied. Such a basic dye as chrysodine or crystal violet remarkably expanded the monolayer when pH of the solution was in a certain range on alkaline side. This has been attributed to the interactions between the molecules of dye themselves and that between dye and octadecylamine. Thus, it is mainly dipolar and van der Waals’ attraction, which was considered to be overshadowed by ionic repulsion when substrate pH was in the other region. Additional possibility of ion-dipole attraction due to the remaining charge of the monolayer was discussed in connection with the ionizations of octadecylamine and basic dyes.

In contrast with this, the monolayer expanded remarkably when it was spread on an acidic solution of acid dye. The behavior could be accounted for by the sum of ionic, dipolar and van der Waals’ attraction. The possibility of the formation of colloidal aggregate of dye with which octadecylamine interacts has been discussed, in connection with the effect of metal ion in the substrate upon the monolayer of stearic acid.
Studies on Serine Peptides. IV. Synthesis of l-Seryl-l-histidyl-l-leucyl-l-valyl-l-glutamic Acid with Strepogenin Activity.
Authors: Okawa Kenji
Published: July 2006

l-Seryl-l-histidyl-l-leucyl-l-valyl-l-glutamic acid having strepogenin activity has been synthesized from O-Bz-l-serine as a starting material in a good yield by Sheehan’s dicyclohexylcarbodiimide method.
Heats of mixing of Dichloroethan with Non-polar Liquids
Authors: Amaya Kazuo , Fujihsiro Ryoichi
Published: July 2006

For three solution of dichloroethane which is regarded as a typical molecule having internal rotation isomers, the excessive enthalpies arising from the internal reaction were calculated according to a simple theory derived from the Onsager model, and were compared with the result obtained from the measurements of heats of mixing for these solutions. The agreement was not very good and it seems to owe to the overestimation of the reaction field based on the simple molecular modern in the Onsager model. Especially for the dichloroethane-benzene system, special interactions may be expected to exist between dichloroethan and benzene.
Studies on Polymerization and Depolymerization of ε-Caprolactam Polymer. V. On the Reaction Mechanism of the Catalytic Polymerization of ε-Caprolactam by Alkali Metal
Authors: Yumoto Hirosuke , Ogata Naoya
Published: July 2006

When alkali metal reacts with ε-caprolactam, it was found experimentally that hydrogen and N-alkali metal ε-caprolactam are produced at first. The rate of polymerization of ε-caprolactam in the presence of N-alkali metal derivative was studied. The change in the electric conductivity during polymerization was also measured. In this case the polymerization is expected to proceed by an ionized molecule.
The Determination of Boron in Glass Using Radium-Beryllium Neutron Source (Neutron Absorption Technique)
Authors: Kusaka Yuzuru
Published: July 2006

The neutron absorption technique using radium-beryllium neutron source has been show to be useful for rapid assay of boron in the samples containing other low cross-section elements. This method may also be useful for the analyses of other high cross-section elements.

The writer wishes to express his hearty thanks to Professor Masayoshi Ishibashi of Kyoto University and President Bunsaku Arakatsu and other members of the Chemical and Physical Laboratory of K\={o}nan University for their kind guidance and valuable advice through this study, to Professor Shoji Tsuchihashi of K\={o}be University for furnishing glass samples, and to Mr. Haruo Tsuji for considerable help in repeating and checking the procedures in many of the experiments.
Rotatory Dispersion of Metallic Co-ordination Compounds. I. Rotatory Dispersion in the First and the Second Absorption Bands of Cobaltic Compounds
Authors: Hidaka Jinsai , Yamada Shoichiro , Tsuchida Ryutaro
Published: July 2006

Rotatory dispersions in the visible and the ultraviolet region have been determined with cis-[Co en2Cl2]Cl and cis-[Co en2ClNO2]Cl, and dispersion curves have been analyzed by the method of successive approximation.

Both the complexes show two inversive dispersions in the wave-length region of the “first absorption band”, and only one dispersion in the region of the “second absorption band”.

The magnitude of those dispersions was found to be of the same order.

An inversive dispersion was also observed in the region of the “specific absorption band”.

In the wave-length region of the “first absorption band”, there appear two inversive dispersions due to the component absorptions, in accordance with the dichroism measurement. As for the inversive dispersions in the region of the “first absorption band”, the sign of the Cotton effect for the one is reverse to that for the other in the violeo-salt, but in the cis-chloronitro-salt, the Cotton effect is the same for the two components.

A possibility of determining the absolute configuration was suggested from the rotatory dispersion curve in the wavelength region of the “first absorption band”.
Studies on the Synthesis of Metal Complexes. IV. The Cobalt (III) Complexes of Ammoniatriacetic Acid
Authors: Mori Motoshichi , Shibata Muraji , Kyuno Eishin , Okubo Yoshito
Published: July 2006

The cobalt(III) complexes containing ammoniatriacetato group (ata) as a quadridentate ligand are newly prepared:

i) α-K[Co ata(OH)(OH2)]·2H2O

ii) β-K[Co ata(OH)(OH2)]·3H2O

iii) K2[ataCo(OH)2Co ata]·6H2O

iv) K2[Co ata(CO3)]·H2O

v) K2[Co ata(C2O4)]·H2O

In order to determine the structural formulae of these complexes, their visible, ultraviolet and infrared spectra were measured, as well as their thermal decomposition and their potency to coagulate ferric oxide sol.
On the Absorption Spectra of Hexamminecobalt (III) and Related Complexes. II. Theoretical Study on Shifting and Spilitting of the First and the Second Band Due to Substitution of Ligands
Authors: Yamatera Hideo
Published: July 2006

A general theory has been presented to discussed spectra of transition metal complexes and to apply them to the problem of shifting and spliting of the absorption band of the cobalt (III) complex due to replacement of some of the ligends. The problem was discussed from the molecularorbital and the electrosttaic point of view.
Formation and Aging of Precipitates. IX. Formation of Monodisperse Particles (2) Barium Sulfate Precipitate by EDTA Method
Authors: Takiyama Kazuyoshi
Published: July 2006

Monodisperse spindle-shaped particles of barium sulfate were formed by means of the decomposion of barium-EDTA complex with hydrogen peroxide in the presence of sulfate. The logarithm of the size of the particle produced was linear with the logarithm of the concentration of reagents. The particles grew at the same rate of liberation of barium ion from the complex. The number of particles per unit volume of the reaction mixture was kept constant during the growth process of particles.
Kinetics of Hydrolytic Reaction Catalyzed by Crystalline Bacterial α-Amylase. I. The Influence of pH
Authors: Ono Sôzaburo , Hiromi Keitaro , Yoshikawa Yoshiko
Published: July 2006

The influence of pH on the rate of the hydrolytic reactions of amylose catalyzed by the crystalline bacterial α-amylase of Bac. amyloliquefaciens Fukumoto has been examined at various substrate concentrations and temperatures.

The apparent Michaelis constant \={K}m is constant over the pH range examined (3.6∼8.4), whereas the apparent rate constant k2 for the breakdown of the enzymesubstrate complex into the reaction products and free enzyme decreases on both the acid and the alkaline side of the optimum pH 5.85. The relative rate - pH curves are not affected by the substrate concentration. From these facts, it is concluded that at least two ionizable groups in the enzyme are involved in the breakdown of the complex, although these groups are not directly responsible for the formation of the enzyme-substrate complex.

The ionization constants and the heats of ionization of the two groups involved in the reaction have been determined. From these values, the ionizing groups are inferred to be the carboxyl and imidazole (or amino) groups. The ionized form of the former and the positively charged form of the latter are considered to be essential for the breakdown process.

Tentative mechanisms of the reaction are proposed.
Surface Chemistry of Synthetic Protein Analogues. VII. Polytyrosine and its Related Polypeptides
Authors: Isemura Toshizo , Yamashita Takuya
Published: July 2006

The monolayer properties of synthetic polypeptides which have phenolic OH groups in the side chains such as poly-l-tyrosile and poly-Dl-tyrosine were studied to investigate the effect of hydrogen bonding by tyrosyl OH groups. Poly-o-benzyl-Dl-tyrosine and poly-Dl-phenylalanine were also studied for comparison.

At air/water interface poly-l-tyrosine and poly-Dl-tyrosine occupy much smaller aerea per residue than any other poly peptide films, and have very small surface moment, if they were spread from the solution in pyridine and isopropyl alcohol mixture. These polypeptides might be spread in a strict sense not in an extended monolayer but in a coiled state, suggesting the hydrogen bond between phenolic OH and –CO– or –NH– groups in the main chain. On the alkaline substrate the film expands considerably because of the breaking of hydrogen bonds by the ionization of phenolic OH. At petroleum ether/water interface, the film is also expanded by releasing of van der Waals force. Interfacils moment changes its sign due to whether the aqueous phase is acid. or alkaline. It suggests that p-hydroxybenzyl groups are in the oil phase at oil/acid solution, whereas they are in the aqueous phase at oil/alkaline solution. Poly-l-tyrosine assumes the configuration very similar that of poly-l-tyrosine is spread from a solution in dichloroacetic acid which is a strong hydrogen bond braking agent.

Poly-o-benzyl-Dl-tyrosine gives a monolayer which is somewhat more condensed than poly-Dl-phenylalanine at air/water interface, whereas it occupies a larger area per residue than poly-l-tyrosine, poly-Dl-tyrosine and poly-Dl-phenylalanine at oil/water interface. All these findings are caused by the existence of very large side chains in poly-o-benzyl-Dl-tyrosine.
Synthesis of Aspartic and Glutamic Hydrazides and their Chromatographic and Ionophoretic Separation. C-Terminal Groups of Whale Insulin
Authors: Narita Kozo , Ohta Yumiko
Published: July 2006

Aspartic α- and β-monohydrazides and aspartic α, β- and glutamic α, γ-dihydrazides were prepared and their qualitative separation has been performed by means of paper ionophoresis and chromatography. During ionophoresis in acidic medium, the dihydrazide partially decomposed into the isomers of monohydrazides liberating hydrazine. The hydrazinolysis products of whale and beef insulins were analyzed by the aid of elution chromatography on a Dowex 50 column and it was observed that the C-terminal positions were occupied by each one mole of alanine and asparagine in both cases. Furthermore, the present experiments suggested that all of the non-terminal carboxyl groups of the hormone belonged to only glutamic acid residues. Complicated reaction of the acidic amino acids or their amides with hydrazine was discussed.
Thermodynamic Studies on Cobalt Complexes. IV. On the Thermal Dissociation and the Solubility of Aquopentamminecobalt(III) Chloride
Authors: Mori Motoshichi , Tsuchiya Ryokichi , Okano Yasuhiro
Published: July 2006

1. The standard free energy of formation of aquopentamminecobalt(III) chloride in the solid state was calculated by measuring its dissociation pressure.

2. From this value and the standard free energy of formation of aquopentamminecobalt(III) ion, the free energy change of the solution of aquopentamminecobalt(III) chloride was calculated. From this value and the solubility data the activity coefficient of aquopentamminecobalt(III) chloride in the saturated aqueous solution was calculated.

The free energy changes of the solutions of hexamminecobalt(III) chloride, bromide, nitrate and perchlorate as well as of aquopentamminecobalt(III) chloride were found to be a linear function of the logarithms of their solubilities.

3. The thermodynamic stability of hexamminecobalt(III), aquopentamminecobalt(III) and chloropentamminecobalt(III) chlorides in the solid state and in the aqueous solution was discussed.
Vinyl-polymerization with Alkylboron Derivatives
Authors: Ashikari Nobuyuki
Published: July 2006

Such alkylboron derivatives as dialkylboron chloride, dialkylborinic acid, dialkylboronous ester, and dialkylboron oxide as the catalysts for the polymerization of vinyl compounds were studied. Although dialkylborinic acid was a good catalyst, it was pretty difficult to isolate it purely, therefore, only a brief description was made in this paper. Of course, some dialkylborinic acids can be isolated purely under suitable conditions. In regard to this, further investigation will be performed.

The polymerization rates of styrene with these catalysts, the relation between the conversion and the intrinsic viscosity, and the influence of oxygen on the polymerization rate were studied. The polymerization rate of some monomers with dialkylboronous ester is maximum when O2/catalyst in mole ratio is 0.22.
Polymerization of Methyl Methacrylate Initiated by a Combined Action of p-Tolyl Methyl Sulfone, Dimethylaniline and Oxygen in Air
Authors: Uehara Ryoichi
Published: July 2006

The polymerization of methyl methacrylate is initiated by a combined action of p-tolyl methyl sulfone, dimethylaniline, and oxygen. The efficiency of the initiating system is increased by using dimethylanilines substituted with electron-donating groups in the para position. The fact that the 1:1 copolymer of styrene and methyl methacrylate is formed by means of this initiating system suggests the formation of radicals to initiate the polymerization from the initiating system.
Intramolecular Interaction between Hydroxyl Group and π-Electrons. VI. Electronic Effect on the Interaction in ω-Arylalkanols
Authors: Oki Michinori , Iwamura Hiizu
Published: July 2006

The electronic effect on the intramolecular interaction between the hydroxyl group and the π-electrons of the benzene nucleus was studied with various ω-aryl-alkanols. In 2-arylethanols, introduction of an electron-releasing group into the benzene nucleus gives rise to the shift of the νO–H absorption maxima to a lower wave number and to greater integrated intensities of the band due to the interacting form, and introduction of an electron-attracting group to a higher wave number and smaller integrated intensities. However, the wave number of the band due to the interacting form is not affected by the position of the substituent, as far as the substituent is the same. Thus, the structure represented by IX is favored. On the other hand, a compound with an electron-releasing group in the meta position always shows greater integrated intensities of the band due to the interacting form than the para-substituted isomer and this fact saves structure VIII from entire rejection. Hence, the authors tentatively assign structure IX as the most favorable with participation of structure VIII to some extent.

In 3-arylpropanols the interaction is observed only in the compounds with an electron-releasing group and 3-(p-chloro-phenyl)-propanol shows the normal νO–H absorption for primary alcohols. The phenomenon that 3-arylpropanols show smaller interaction in spite of the appearance of the band due to the interacting form at a lower wave number is attributed to the unfavorable change in both energy and entropy.

In 4-arylbutanol no interaction is observed, even though a strongly electron-donating group is introduced.

Thus, as the authors predicted, it has been proved that the intramolecular interaction occurring in 2-phenylethanol is different in nature from that in benzyl alcohol.
Studies on the Interaction of Surface Films with Solute in Solution. IV. Effect of Congo Red Dissolved in Aqueous Substrate upon the Monolayers of Octadecylamine, Cetyl Alcohol, Ethyl n-Hexadecyl Ether, Ethyl Stearate and Cholesterol
Authors: Muramatsu Mitsuo
Published: July 2006

Effect of dissolved Congo red upon the monolayers of octadecylamine, cetyl alcohol, ethyl n-hexadecyl ether, ethyl stearate and cholesterol spread on the substrate containing the dye has been studied, under varying pH of the solution. It has been observed generally that all monolayers expanded when they were spread on aqueous solution, the pH of which was in such a region that the molecules of dye were almost in zwitterion form. Dipolar and van der Waals’ attraction were tentatively postulated to explain the nature of the cohesive force by which the molecules of dye were bond together so that the colloidal aggregates were formed in the solution. The expansion of the monolayer can be accounted for by the binding of the aggregate to film materials. This explanation could successfully be applied to the films of such nonionic substance as cetyl alcohol, ethyl n-hexadecyl ether and ethyl stearate.

The largest expansion of the monolayer of octadecylamine was observed when the substrate containing dye showed acidity so that the molecules of dye were partly of negative charge while those of octadecylamine were of positive charge. In this case we had better take account of the possibility of ion-ion attraction between octadecylamine and dye, in addition to the forces which appeared in the cases of nonionic substances.
Crystallinity Studies of Polychlorotrifluoroethylene by the Infrared Method. II. Kinetics of the Crystallization
Authors: Matsuo Hiroshi
Published: July 2006

The isothermal rate of crystallization in polychlorotrifluoroethylene was measured at temperatures ranging from 172 to 190°C below the melting point by following the change of observed absorbance of crystalline band at 440 cm−1. The isothermal rate of crystallization and apparent induction time are dependent on temperature. The data on the kinetics of the crystallization are compared with the result of Avrami’s analysis. At temperatures between 190 and 185°C the nucleation process will be promoted by heterogeneities which exist in the melt. Between 184 and 178°C it will be mainly governed by homogeneous nucleation.
Ultraviolet Absorption Spectra of Substituted Phenylureas
Authors: Tsuzuki Yojiro , Motoki Shinichi , Migita Kazuko
Published: July 2006

Ultraviolet absorption spectra of several nuclear substituted phenylureas have been measured with the attempt to study the electronic effect of the carbamide group, and the resonance stabilization in three dulcin isomers.
The Preparation and Properties of N-Salicylideneglycinato-aquo-copper(II), Sodium N-Salicylideneglycylglycinato-cuprate(II) and Related Compounds
Authors: Nakahara Akitsugu
Published: July 2006

The two new compounds, N-salicylideneglycinato-aquo-copper(II) and sodium N-salicylideneglycylglycinato - cuprate(II) were prepared and investigated as to their structure.

Their infrared, visible and ultraviolet absorption spectra together with those of some related compounds were measured and discussed.
Thermal Effects of Some Kaolin Minerals. II. Halloysite
Authors: Takahashi Hiroshi
Published: July 2006

The structural change of halloysite with heat-treatment in the relatively low temperature region has been studied, and was compared with those of kaolinite and Kibushi-clay. There are three processes, same as in the case of kaolinite. The first process is accompanied by the loss of the inter-layer and adsorbed water, and tho second process by the loss of the lattice water. In the third process, which is an amorphous state corresponding to the metakaolin state, the rearrangement of ions takes place for the mullite nucleation. The rate of the structural change depends on the degree of crystalinity of the original kaolin mineral.
The Roles of Prolyl Residue in Polypeptide Monolayers. I. On the Chain Configurations Deduced from Surface Pressure and Potential Measurements
Authors: Isemura Toshizo , Ikeda Shoichi
Published: July 2006

To elucidate the roles of prolyl residue in polypeptide monolayers, the surface films of poly-Dl-alanine, poly-l-prolyl-l-leucylglycine, copoly-1 : 1 : 1-(l-proline, l-leucine, Dl-alanine), poly-l-proline and poly-l-hydroxyproline were studied by the surface pressure and potential measurements.

The area of minimum surface compressibility and the smallest area of constant surface moment were assigned to each of the first three polypeptides which were found to form monomolecular films. In the region of large area their surface moments were equal to one another and, therefore, the orientations of carbonyl groups might be the same. From these data their chain configurations at the interface were deduced. Poly-Dl-alanine exists in the β-configuration and the other two have the similar configuration except for the bonds attached to prolyl residues. Based on the departure in surface pressure behavior of copoly-1 : 1 : 1-(l-proline, l-leucine, Dl-alanine) from that of poly-l-prolyl-l-leucylglycine, the arrangement of prolyl residues in the sequence of the former polypeptides was discussed. In the poly-l-proline film it is likely that the parts of cis peptide bond form the film and the parts of trans bond dissolve into the aqueous subphase.

The polypeptide films were found to be more expanded as the prolyl content was higher, although the arrangement of prolyl residues also affected the expansion of film. From the comparison of poly-l-proline film with poly-l-hydroxyproline, the evidence was obtained that the expansion of film comes from the decrease in number of hydrogen bonds because of the presence of prolyl residues. The condensation or expansion and its related properties of the film were interpreted in terms of the chain rigidity or flexibility and the intrachain interaction.
Effects of Dry Grinding on Kaolin Minerals. III. Halloysite
Authors: Takahashi Hiroshi
Published: July 2006

The effects of several-hundred-hour mechanical-mortar dry grinding of halloysite were studied by X-ray diffraction, differential thermal, electron microscopic and other methods and they were compared with those of kaolinite and Kibushiclay. It has been found that there are two sorts of structural change caused by dry gringing in halloysite as in the case of kaolinite. One is the production of a non-crystalline material attended with disordering of crystallites, and the other is the process of reaggregation. In a certain stage of grinding, the reaggregates come to have a zeolitic structure. This stage of grinding corresponds to the maximum point on the base exchange capacity curve and the inflection point on the density curve. The particle which has a zeolitic structure is uniformly spherical. As the grinding progresses further, halloysite changes into an amorphous substance, and the particle size increases irregularly. In consequence, it was found that the effects of dry grinding on kaolin minerals depend strikingly on the structural perfectness of unit layers of the original kaolin minerals, that is, the internal degree of crystallinity.
Phenothiazine Derivatives. IV. Reactions of Thionyl Chloride with Some Substituted Diphenylamines and with NaphthylphenyIamines
Authors: Fujimoto Manabu
Published: July 2006

Reactions of thionyl chloride with some substituted diphenylamines and with naphthylphenylamines were studied. N-Acetyldiphenylamine gave the known 1,3,7,9-tetrachlorophenothiazine. Methyldiphenylamine gave a small yield of the known 3,7-dichloro-10-methylphenothiazine besides the same tetrachlorophenothiazine as the main product. The following new compounds were obtained from respective starting materials and their structures were deduced: 3,7-dichloro-10-(4′-chlorophenyl)-phenothiazine from triphenylamine, 1,3,7,9-tetrachloro-2-hydroxyphenothiazine from 3-hydroxydiphenylamine, 2,4,7,9-tetrachloro-3-phenothiazone from 4-hydroxydiphenylamine, 3-amino-2,4,7,9-tetrachlorophenazathionium chloride from 4-aminodiphenylamine, 3,7-diamino-2,4,6,8-tetrachlorophenazathionium chloride from 4,4′-diaminodiphenylamine, 3-amino2,4,6,8-tetrachloro-7-methoxyphenazathionium chloride from 4-amino-4′-methoxydiphenylamine, x, 5,9,11-tetrachlorobenzo[a]phenothiazine from α-naphthylphenylamine, and 1,3,x,x′,11-pentachlorobenzo-[b]phenothiazine and x,6,8,10-tetrachlorobenzo[c]phenothiazine from β-naphthylphenylamine.
Electrical Conductance of Concentrated Aqueous Solutions of Copper Sulfate
Authors: Suryanarayana C V , Alamelu S
Published: July 2006

The electrical conductance of aqueous solutions of copper sulfate has been measured over a wide range of concentrations up to saturation. The equation connecting conductance and concentration in the range of high concentrations recently formulated by Suryanarayana and Venkatesan has been tested with the data obtained for copper sulfate solutions. The equation is found to be valid over a wide range of concentration from 0.3862m to saturation at temperatures ranging from 30°C to 60°C. Slight deviations have been observed at lower concentrations.
Substituent Effects on the Ultraviolet Absorption Spectrum of 1,3,5-Trinitrobenzene in Some Solvents
Authors: Abe Takehiro
Published: July 2006

(1) In ethanol and in water the maximum absorption bands of the substituted trinitrobenzenes are observed at longer wavelengths and possess smaller molar absorbancies than 1,3,5-trinitrobenzene, a benzene nucleus of which possesses some greater positive charge than those of the derivatives.

(2) Picric acid shows similar absorption curves in solvents like ethanol, water and acetone. This similarity seems to show that picric acid dissociates in all solvents.

(3) On treating the trinitrobenzenes with aqueous sodium hydroxide solution, the red colors are produced. The colors given by the trinitrobenzenes having substituents like –N(CH3)NO2, –Cl and –OH, are labile, while those produced from trinitrobenzene and 2,4,6-trinitrotoluene are rather stable. The spectrum of the red color of trinitrobenzene closely resembles that of Tetryl.
Antioxygenie Activity of Lecithin and its Hydrolysis Products. II. α- and β-Glycerophosphoric Acids
Authors: Urakami Chieko , Kameyama Haru , Okada Mitsuko
Published: July 2006

It has been demonstrated that the method of purification of the substrate by low temperature crystallization is not suitable for the study of antioxidant activity of the glycerophosphoric acids and that further purification by crystallization as the urea complex gives consistent results. In such a highly purified substrate, both acids have been found to be active in a comparable strength.

The study of ultraviolet absorption of the phosphorus-containing substances isolated by the column chromatography has shown that the glycerophosphoric acid molecule acquires a highly conjugated system during autoxidation. Discussions have been presented as to possibilities incurred in the formation of such highly conjugated compounds.
Phenothiazine Derivatives. V. Synthesis of Hydroxyphenothiazines
Authors: Fujimoto Manabu
Published: July 2006

The phenolic compound resulting from the rearrangement of phenothiazine 5-oxide in acetic acid was found to be 4-hydroxyphenothiazine, and to be different from 2-and 3-hydroxyphenothiazines which were derived from 3- and 4-hydroxydiphenylamines, respectively, by fusion with sulfur and iodine.
Formation and Aging of Precipitates. XI. An Electron Micro-Diffraction Study on Nucleation of Barium Sulfate Precipitate from Homogeneous Solution
Authors: Takiyama Kazuyoshi
Published: July 2006

The nucleation process of the precipitation of barium sulfate from the homogeneous solution of persulfate-thiosulfate system was observed by the electron micro-diffraction method. The particles grew continuously, but the distinct crystal structure began to appear in the particles having the length of 100 to 200 Å in diameter, corresponding to the nucleus calculated thermodynamically.
Remarks on the Molecular Calculation of Naphthalene and Anthracene
Authors: Mataga Noboru , Nishimoto Kichisuke , Mataga Shizuyo
Published: July 2006

Electronic structures of naphthalene and anthracene have been studied by the selfconsistent field MO method employing our semiempirical parameters. The calculated electronic spectra, bond lengths, ionization potentials and electron affinities are in a good agreement with expriment. Some discussions have been given in connection with the method of “atoms in molecules” and others.
The Study of Adsorption of Detergents at a Solution-Air Interface by Radiotracer Method. II. The Kinetics of Adsorption of Sodium Alkyl Sulfates
Authors: Matuura Ryohei , Kimizuka Hideo , Miyamoto Shigeru , Shimozawa Ryosuke , Yatsunami Katsumasa
Published: July 2006

The rate of adsorption of sodium dodecyl sulfate, sodium tetradecyl sulfate and sodium hexadecyl sulfate at the solution-air interface has been measured by radiotracer method. It has been found that the surface excess of a detergent is proportional to the concentration of the solution and the square root of time of aging at the initial stage of adsorption. The simple diffusion theory has been checked and it has been found that the results of the present experiment can not be explained by the simple diffusion theory. The idea of energy barrier has tentatively been applied and the values of energy barrier have been calculated.
γ-Hydroxyarginine, a New Guanidino Compound from a Sea-cucumber. I. Isolation and Identification
Authors: Fujita Yoshimasa
Published: July 2006

A new guanidino compound was isolated from a sea-cucumber, Polycheira rufescens, and identified as γ-hydroxyarginine. γ-Hydroxyornithine and γ-guanidino-β-hydroxybutyric acid produced enzymically from the guanidino compound were also isolated and identified. It was, further, concluded that the new guanidino compound susceptible to arginase and l-amino acid oxidase should be γ-hydroxy-l-arginine, although the configuration of the γ-hydroxy group was not yet decided.
Electronic Structures of Naphthalenediols. I. α, α′-Naphthalenediols
Authors: Nishimoto Kichisuke , Fujishiro Ryoichi
Published: July 2006

The simple LCAO MO method was applied to the electronic structures of α, α′-naphthalenediols, using the same parameters as those of phenol based on the ASPMO calculation. The theory proved that

(a) the lowest π-orbital of the molecule would be the most sensitive to the influence of the external molecular field,

(b) the absorption spectra of diols were satisfactorily correlated with their energy level diagrams, and

(c) the extra delocalization energies produced by the charge migrations from the hydroxy groups into the naphthalene ring increased linearly with the increment of the magnitude of charge migrations.
The Mannich Base of Troponoid and its Application. I. Synthesis of 5-Hydroxymethyl and 5-Formyltropolone Derivatives
Authors: Seto Shuichi , Ogura Kyozo
Published: July 2006

Application of the Mannich reaction to 3,7-dibromotropolone gave 3,7-dibromo-5-morpholinomethyltropolone, from which 5-hydroxymethyl and 5-formyl derivatives were derived. It was found that the hydroxymethyl group of 3,7-dibromo-5-hydroxymethyltropolone can be easily displaced, and that 3,7-dibromo-5-formyltropolone has the characteristics of an ordinary aldehyde and reacts with ketones and malonic acid.
The Formation Constants of Metal Acetate Complexes. I. Polarographic Determination of the Formation Constants of Acetatonickel(II) Complexes
Authors: Tanaka Nobuyuki , Kato Kiyoko
Published: July 2006

A new method for the determination of the formation constants of metal acetate complexes has been developed. The method is based on the polarographic measurement of the sum of the equilibrium concentrations of hydrated metal ions and metal acetate complexes in the presence of an appropriate auxiliary complex-form-ing substance. One of the advantages of the method is that no estimation is required in the course of the calculation. The other is that no information of the dissociation and formation constants is required concerning the auxiliary complex-forming substance.

The method is applied to the study of acetatonickel(II) complexes using nitrilo-triacetate as an auxiliary ccmplex-forming substance. The results reveal that only monoacetatonickel (II) ions, NioAc+, exist in the solution containing acetate up to 0.2m in concentration. The formation constants KNiOAc at ionic strength 0.2 are caluclated to be 2.6 at 15°C and 2.4 at 35°C.
Effects of Protonation on the Electronic Structure and Spectra of Nitrogen Heterocycles
Authors: Mataga Shizuyo , Mataga Noboru
Published: July 2006

The self-consistent electronegativity method has been applied to calculate the electronic structure and spectra of some protonated nitrogen heterocycles. This method may be regarded as an improvement of our method ii which has led to poor agreement with experiment because of the neglect of the inductive displacement in σ-core caused by protonation. The calculated results with the present method, however, are in rather poor agreement with experiment, and it is only a small improvement of the method ii.

Comparing the present results with the previous ones obtained with method i and ii, some discussions about the nature of the protonation effect on the electronic structure of these molecules have been given. In addition, formulae which represent the magnitude of inductive effect on each atom as a function of the distance or number of bonds from the protonated atom have been given.
Dye-sensitized Photopolymerization of Vinyl Compounds. Polymerization of Styrene by Cyanine Dyes. III
Authors: Watanabe Ai
Published: July 2006

Extensive studies on the photopolymeri-zation of styrene by virtue of cyanine dyes were performed and it was reconfirmed that only the chain initiation is promoted by the direct interaction between the excited dye and the styrene molecule. Activation energies for the photochemical initiation process were experimentally determined for several dyes of iodide, bromide and chloride. In general the activation energy depends on the kind of halogen ion and from this result it was concluded that halogen ion plays an essential rôle in the reaction. A general tendency was observed that the activation energy diminishes as the wavelength of absorption maximum of dyes becomes shorter. A plausible scheme for the chain initiation process was given, in which an electron transfer from X− to D+ is involved in the process of activation.
Catalytic Hydrogenation in Vapor Phase with Urushibara Nickel Catalyst
Authors: Hata Kazuo , Watanabe Ken-ichi , Watanabe Hamao
Published: July 2006

Catalytic hydrogenation in vapor phase with new types of Urushibara nickel catalyst was carried out.

1) New types of U–Ni were prepared from nickel chloride and aluminum. U–Ni–BA and U–Ni–AA were respectively obtained by treating the precipitated nickel with alkali or acetic acid.

2) These catalysts are quite easy to prepare and were proved to be useful for hydrogenation. Above all, U–Ni–AA is, the most convenient for vapor phase hydrogenation, since it was found to be highly active and the aluminum served as carrier. It was also used in hydrogenation in liquid phase.
The Study of the Adsorption of Detergents at a Solution-Air Interface by Radiotracer Method. III. The Effect of Inorganic Electrolytes on the Adsorption of Sodium Dodecyl Sulfate
Authors: Matuura Ryohei , Kimizuka Hideo , Yatsunami Katsumasa
Published: July 2006

The direct measurement of the adsorption of 35S labelled dodecyl sulfate ion at the solution surface and the measurement of the surface tension were carried out on the aqueous solutions of sodium dodecyl sulfate containing a given concentration of an excess salt. The salt concentrations studied were 0.01, 0.1, 0.3, 0.5 and 1n for sodium chloride, and 0.1 n for potassium-magnesium, manganous and aluminum chlorides.

1. The adsorption of dodecyl sulfate ion reaches equilibrium within one minute for all the systems under investigation.

2. The presence of excess of salt gives rise to the remarkable increase in the adsorption of dodecyl sulfate ion, but at the concentrations of excessive salts of about 0.1 n or more, the effects of the concentration and nature of the salts on the adsorption of dodecyl sulfate ion are not so appreciable.

3. The adsorption of dodecyl sulfate ion was well expressed by the Gibbs adsorption equation of n=1 for the systems under investigation.
Syntheses of Chlorinated Copper Phthalocyanines from Chlorophthalic Anhydrides
Authors: Shigemitsu Masahiro
Published: July 2006

Syntheses of chlorinated copper phthalocyanines from various chlorophthalic anhydrides were conducted. Formation of phthalocyanine depends upon the contents and positions of chlorine atoms of chlorophthalic anhydrides.
Color Characteristics of Copper Phthalocyanine and its Chlorinated Derivatives
Authors: Shigemitsu Masahiro
Published: July 2006

The variation of color of copper phthalocyanine and its chlorinated derivatives in polymerized linseed oil was investigated.

The β-form of copper phthalocyanine is more conspicuous than the α-form in their variation of color.

Chlorine atoms at 3, 6- or 4, 5-positions of phthalocyanine nucleus give very different actions according to their variations of color, even if their chlorine contents are the same.
Theoretical Study on the Mechanism of the Aromatic Substitution
Authors: Nagakura Saburo , Tanaka Jiro
Published: July 2006

The mechanism of the aromatic substitution was studied on the basis of the energy level diagrams determined for both the aromatic molecule and the reagent. From the consideration of the relative heights of the highest occupied and lowest vacant orbitals of the former to those of the latter, it was deduced that a large electron transfer occurs at some stage of the reaction from the aromatic molecule towards the reagent for the electrophilic substitution and in the reverse direction for the nucleophilic substitution.

In connection with this electron transfer mechanism, it was expected that the orientation rule observed with the aromatic substitution can be explained by free valency values of the aromatic cation, neutral molecule and anion for the electrophilic, radical and nucleophilic substitutions respectively. It was shown that this expectation is fully satisfied for various aromatic substitutions.
Dichroism of Dyes in the Stretched PVA Sheet. II. The Relation between the Optical Density Ratio and the Stretch Ratio, and an Attempt to Analyse Relative Directions of Absorption Bands
Authors: Tanizaki Yoshié
Published: July 2006

1) An expression for the optical density ratio was derived as a function of the stretch ratio.

2) Dichroism of the crystal violet and auramine yellow ion in stretched PVA sheets was observed, and the relation of the optical density ratio to the stretch ratio was plotted. It was shown that the theoretical expression derived here could explain rather well the experimental relation between these two quantities.

3) The analytical results were as follows. The main absorption band and the shoulder of the crystal violet ion did not orginate from the two isomers but were perhaps due to one species. For the auramine yellow ion the angle between the transition directions corresponding to the first and the second band might be approximately a right angle provided that the absorption-planes were in a same plane.
Polarographic Studies of Metallic Complexes. V. Tetrammine Series of Cobalt(III) Complexes
Authors: Maki Nobufumi , Shimura Yoichi , Tsuchida Ryutaro
Published: July 2006

1. All the cobalt(III) complexes of tetrammine series, [Co(NH3)4X2] or [Co(NH3)4Y], were reduced irreversibly in two steps at the dropping mercury electrode. The first wave, corresponding to a gain of one electron, represents the reduction of Co(III)→Co(II) and the second, corresponding to two electrons, represents the reduction of Co(II)→Co(0).

2. The polarographic stability of the cobalt(III) complexes of tetrammine series are ranked in the following order of the ligand ; for the complexes of [Co(NH3)4X2] type,

IO3−, Cl−<NO2−<NH3<OH2 <SO32−

(supporting electrolyte; 0.5FK2SO4),

and for the complexs of [Co(NH3)4Y] type,

leuc−<ox2−<alan−< CO32−<gly−<en

(supporting electrolyte; 0.5FK2SO4).

3. The half-wave potentials of the reduction step of Co(III)→Co(II) for all the tetrammine cobalt(III) complexes exhibit always more positive values than those of the corresponding bisethylenediamine cobalt(III) complexes.