bluuebunny/crossref_metadata_2025 huggingface dataset:
Kolbe’s Reaction of Higher Fatty Acids. III. Anode Potential in the Electrolysis of Laurio Acid with Platinum Anode
Authors: Matsuda Ryoichi , Hisano Takeo , Terazawa Toshio , Shinohara Norio
Published: July 2006

An aqueous solution of lauric acid, containing potassium hydroxide and potassium carbonate, was electrolysed at 40±0.5°C with smooth platinum electrodes. Not only were two constant anodic potential stages, 1.5∼1.6 and 2.4∼2.6V. vs. S.C.E., clearly found, but also an abrupt shift from the lower stage to the higher one was distinctly observed. The main reaction at the lower stage is the evolution of oxygen. In addition, at the higher stage the discharge of laurate ions is accompanied by an oxygen evolution that is markedly retarded compared with that at the lower stage. It may therefore, be inferred that the transition of potential from the lower stage to the higher is caused by the formation of a film of adsorbed laurate ions.
Molecular Rotations of Glucides in Relation to their Structures. VIII On the Product of the ζ-Coefficients of the Hydroxyl and the Methyl Groups
Authors: Yamana Shukichi
Published: July 2006

By using a new molecular model and the new datum concerning the [M]D20(W) of α-d-isorhamnose, the ζOHζCH3 in the case of methyl pentose and the [M]D20(W) of β-d-isorhamnose, now unknown, were re-calculated. The obtained value of ζOHζCH3 was nearly equal to that in the case of substances which have a cyclohexane-ring. The new value of the [M]D20(W) of β-d-isorhamnose satisfies Hudson’s methyl glycoside rule.
Raman Spectrum of γ-Glycine
Authors: Balasubramanian K , Krishnan R S , Iitaka Yoichi
Published: July 2006

Using λ 2536.5 excitation the Raman spectrum of single crystal of γ-glycine has been recorded for the first time. Thirty-nine Raman frequencies have been reported. Comparing the spectrum of γ-glycine with its infrared absorption spectrum and also with the Raman spectrum of α-glycine, proper assignments have been given to the internal frequencies. The lattice lines observed in Raman effect and infrared absorption have been satisfactorily accounted for.
Adsorption of Cesium by Japanese Acid Clay
Authors: Oi Noboru , Ohashi Eijiro
Published: July 2006

Japanese acid clay, a montmorillonite-type one, exhibited a special affinity for cesium-137 from an aqueous solution. The phase epuilibrium of the adsorption was confirmed, and the Kd values were used to analyze the data.

The Kd value of cesium was highest in pure water, but it was decreased by increasing the aqueous acid, alkali and salt concentration.

When clay which had been treated at 400∼ 500°C was used, the Kd value increased two- or three-fold. This phenomenon corresponds to the formation of 10 Å c-axis spacing and the dispersion of the structural water of the clay. This peculiarity, however, appears only at a low cesium concenration, below 10−6 mol./l. At a higher cesium concentration, the adsorption of cesium depends simply on the cation exchange capacity of the clay; heat-treated clay showed a poorer adsorption.

The adsorption of cesium from a fission products mixture was also simply examined.
Dimer-Monomer Equilibrium Constants for Acetic Acid and the Three Chloroacetic Acids in Benzene
Authors: Nagai Yoichiro , Simamura Osamu
Published: July 2006

Acetic, monochloroacetic, dichloroacetic, and trichloroacetic acid in benzene show an infrared absorption band due to the OH stretching vibration of the monomeric form at 3472, 3438, 3410, and 3389 cm−1, respectively. The dimer-monomer equilibrium constants for these acids in benzene at 20°C have been evaluated, from the change in intensity of these bands with the acid concentration, to be 0.036, 0.041, 0.092, and 0.91 mol./1., respectively.

The observed shift in frequency indicates that there is an interaction, similar to hydrogen bond formation, between the hydroxyl of a carboxyl group and the π-electron system of a benzene nucleus and that the stronger acid interacts more strongly with benzene, resulting in a larger shift in frequency.
Determination of Aluminum, Cerium(III) and Lead with Fluoride by an Amperometric Indicator Method
Authors: Varma Asha
Published: July 2006

Determinations of aluminum, cerium(III) and lead by fluoride involving complex formation, KAlF6 and precipitations, CeF3 and PbClF or PbBrF have been carried out successfully using amperometric indicator method at 0.04V. with two identical polarized platinum electrodes. A small amount of ferric chloride is used as an indicator, the reduction of which beyond end point constitutes the indicating system. Upto the equivalence point, current remains constant, and then it falls due to the reduction of the trivalent iron complex which is formed on addition of excess fluoride. The method is simpler in technique, sensitive and rapid, and the results obtained are good and satisfactory with accuracy of the right order of magnitude even at lower concentrations, as low as 104m. At still higher dilutions the maximum error rises to about ±5.0%.
Electric Properties of the Single-crystal and Thin Film of α,α′-Diphenyl-β-picrylhydrazyl
Authors: Inokuchi Hiroo , Harada Yoshiya , Maruyama Yusei
Published: July 2006

The electronic conductivity of two forms of α,α′-diphenyl-β-picrylhydrazyl, the single crystal and the thin film, was observed. The resistivity (ρ15) at room temperature along c-axis (1×1010 Ω cm.) is 105 times lower than that perpendicular to the axis (1×1015 Ω cm.), but its activation energy (Δε) against temperature is in good agreement (1.5 and 1.6 eV.). These large anisotropy may be introduced from that of the arrangement of molecules in the crystal. In the case of thin film, the values of ρ15 and of Δε are ∼1010 Ω cm., 1.7 eV. for surface type cell and ∼1013 Ω cm., 2.7 eV. for sandwich-type cell respectively. A great difference on the characteristics of photoconduction and on the current-voltage relation in these two types of cell was found.
Influence of Substituent Groups on Nuclear Reactivity in the Formation of Substituted Biphenyls by Reaction of Aromatic Diazo and Related Compounds with Aromatic Liquids. V. Phenylation of Nitrobenzene and Anisole
Authors: Inukai Takashi , Kobayashi Katsumi , Simamura Osamu
Published: July 2006

N-Nitrosoacet(anilide-14C) has been decomposed at 20°C in a mixture of benzene with nitrobenzene or with anisole, and the reaction products have been analyzed for biphenyl and isomeric nitrobiphenyls or isomeric methoxybiphenyls by isotope dilution method. From these results the partial rate factors for the phenylation have been calculated to be for nitrobenzene: o, 9.38; m, 1.16; and p, 9.05; and for anisole: o, 3.56; m, 0.93; and p, 1.29.
Dehydration of Bile Acids and their Derivatives. IX. Oxidation of Methyl 3α-Acetoxy-Δ7-cholenate with Selenium Dioxide
Authors: Osawa Ryuzaburo
Published: July 2006

Carefully repeated experiments have shown that, contrary to Fieser’s report3), methyl 3α-acetoxy-Δ7-cholenate and some other un-saturated bile acids (5β) listed in Table I give positive results in the selenium dioxide test. This finding was substantiated by the fact that two oxidation products of methyl 3α-acetoxy-Δ7-cholenate were isolated, one of which was proved to be methyl 3α-acetoxy-7ξ, 15ξ-dihydroxy-Δ8(14)-cholenate.

It is very interesting to note that, unlike the Δ7-steroids of the 5α-series, not only C7-H, but C15-H of the unsaturated bile acid mentioned above was oxidized with selenium dioxide to give hydroxyl groups, both of which remained without being acetylated under the experimental conditions described.
Electronic Structures of Benzyl Cation and Related Compounds
Authors: Mori Yuji
Published: July 2006

The electronic structure of the benzyl cation has been calculated on the basis of an approximation of the composite systems in order to explain the electronic spectrum of the benzyl cation from the point of view of electron-transfer interaction between the fragments. The calculations show a satisfactory agreement with the experimental observations.

For the electronic spectra of some other cations, simple calculations have been carried out as an application of the treatment for the benzyl cation. The results for the diphenyl-and triphenyl-methyl cations show qualitative agreement with the experimental results.
Assignments of the 35Cl Nuclear Quadrupole Resonance Spectra in Multichlorobenzenes by the Measurement of the Zeeman Effect
Authors: Morino Yonezo , Toyama Masaharu , Itoh Koichi , Kyono Saburo
Published: July 2006

Assignments of the 35C1 nuclear quadrupole resonance spectra have been made for some multichlorobenzenes by the Zeeman studies of single crystals. Three resonance lines in 1, 3, 5-trichlorobenzene, have been assigned, in the order of increasing frequency, to Cl3, Cl1 and Cl5 designated by Milledge and Pant in their X-ray study ; two lower frequencies in 1, 2, 3, 4-tetrachlorobenzene to Cl1 and Cl4 and two higher ones to Cl2 and Cl3; and in pentachlorobenzene, the second highest frequency to the chlorine atom at the para position with respect to the single hydrogen atom. The shifts of the resonance frequencies have been accounted for in terms of the induction effect. It is likely that the ortho effect is produced by the direct field arising from the charges on the neighboring atoms rather than the indirect one propagated through the chemical bonds. The interpretation of the three frequencies in 1,3,5-trichlorobenzene has also been attempted from the viewpoint of the intermolecular effect. It has been suggested that an induction effect independent of the directions takes place in this crystal among the neighboring molecules.
Studies on Modified Hydrogenation Catalyst. I. Selective Hydrogenation Activity of Modified Raney Nickel Catalyst for Carbonyl Group and C=C Double Bond
Authors: Fukawa Hideaki , Izumi Yoshiharu , Komatsu Shinichiro , Akabori Shiro
Published: July 2006

Hydrogenation activity of the Raney nickel catalyst for carbonyl compounds was greatly diminished, when the catalyst was treated with a solution of amino acid. On the other hand, no appreciable change in its hydrogenation activity for C=C double bonds occurred upon this treatment. When mesityl oxide was used as a substrate, selective hydrogenation was most clearly demonstrated.

The effect of conditions of modification, such as concentration of the modifying solution, immersion time and kind of modifying reagent on the activity of the modified catalyst, were investigated.
Effects of Nonelectrolytes on the Temperature of the Maximum Density of Water. II. Organic Compounds with Polar Groups
Authors: Wada Goro , Umeda Saburo
Published: July 2006

The temperature of the maximum density (T. M. D.) of aqueous solutions of various organic polar substances at various concentrations were measured dilatometrically, and the degrees of elevating the T. M. D., ΔT, were estimated. The information derived from the experimental results includes:

1) At any concentration, the values of ΔT for all substances used in the present study are inevitably negative, in contrast with the cases of alkyl monovalent alcohols, reported on in the preceding paper.

2)ΔT′, defined as the difference between the actual elevation of T. M. D. and that when the solution is assumed to be an ideal mixture, is given by an empirical formula, ΔT′=ax+bx2, where a is a characteristic constant of the solute, indicating the degree of the interaction between the solute and water; it generally has a more negative value as the substance is more polar.

3) Benzene does not interact with water; therefore, ΔT′=0 and a=b=0 in so far as it is soluble in water.

4) An additivity correlation concerning a is realized from the composing radicals, and the a values assigned to respective radicals show a simple parallelism with their own polarities.

5) The b parameter is negative for all substances ; the absolute value of this is greater as the molar volume becomes larger.
Ultraviolet Absorption Spectra of Lead Aldose-cysteinate
Authors: Takahashi Fujio , Mizuguchi Jun
Published: July 2006

Lead Aldose-cysteinates in solution were found to show an ultraviolet absorption maximum at 270 mμ. Moreover, lead complexes of various thiol-containing compounds were found to show the same absorption spectra as aldose-cysteine. From these results, it has been suggested that the absorption maximum appears when lead is coordinated through the sulfur atom.
Polarographic and Chronopotentiometric Studies on the Dissociation Reaction of Nitrilotriacetatocadmate(II) Complexes
Authors: Tanaka Nobuyuki , Ebata Kazuko , Takahari Tomoo , Kumagai Tsutomi
Published: July 2006

The dissociation reaction of nitrilotriacetatocadmate(II) complexes has been investigated polarographically and chronopotentiometrically in the presence and the absence of acetate ions. The results indicate that the treatment reported by Koryta for the effect of acetate ion on the kinetic current is appropriate.

The rate constant of the dissociation reaction of nitrilotriacetatocadmate(II) complexes is a function of hydrogen ion concentration and expressed as

k=3.4+2.5×105[H+]+2×108[H+]2

at 25°C.
The Acid-Catalyzed Isomerization of Cyclohexyl Phenyl Ketoxime in Liquid Sulfur Dioxide
Authors: Tokura Niichiro , Shiina Katsuo , Terashima Tetsuo
Published: July 2006

1. The hydrochloric acid-catalyzed isomerization of β-cyclohexyl phenyl ketoxime has been carried out in liquid sulfur dioxide. The effects of temperature, light, deuterium chloride and the concentrations of hydrogen chloride have been examined.

2. The overall rate may be expressed as;

R=kso2[oxime]+kHCl[oxime]·[HCl]1.5

and the kSO2 and the kHCl have been estimated. The reason for the order of hydrogen chloride, 1.5 has also been discussed.
Syntheses of Dl-Hydroxylysine and Dl-Allohydroxylysine
Authors: Izumiya Nobuo , Fujita Yoshimasa , Ohno Motonori
Published: July 2006

A diastereomeric mixture of Dl-hydroxylysine hydrochlorides was obtained with a good yield through hydrogenation of diethyl (γ-hydroxy-δ-nitro-n-butyl)-acetamidomalonate with palladium catalyst in a solvent of acetic acid, which was followed by hydrolysis of the reduced product. Dicarbobenzoxy lactone was prepared with a yield of 91% from hydroxylysine hydrochloride obtained above. A solution of diastereomeric dicarbobenzoxy lactones in dioxane was treated with sodium hydroxide equivalent to the amount of normal form. The salt obtained after saponification converted into a pure normal dicarbobenzoxy lactone, a pure allo compound being isolated from the unsaponified portion. The two lactones were converted into chromatographically pure normal and allohydroxylysine monohydrobromides by the action of hydrogen bromide in acetic acid.
Spark lonization of Semi-metallic and Metallic Elements and of Ionic-crystals
Authors: Yuasa Toshiyoshi
Published: July 2006

Using a mass spectrometer, the nature of the mass spectrum produced by the spark ionization source of semi-metallic and metallic elements and of ionic-crystals was studied, and it was found that only semi-metallic elements are capable of producing their polyatomic ions in a significant concentration.

When the samples of alkali halide single crystals were taken out from the spark source after sparking, it was observed that the crystals held their shape and, moreover, that color centers had been formed finely.

In the light of the experimental results, the mechanism of the ion formation in the spark was discussed, and it was pointed out that some relation might exist between the crystal structure of the solid sample and the formation of the gaseous molecular ion.
Electronic Spectra of Polynitrophenols and their Anions
Authors: Abe Takehiro
Published: July 2006

The absorption spectra of p-nitrophenol, 2, 4-dinitrophenol, picric acid and their anions, all in water, were measured in the presence or absence of either hydrochloric acid or sodium hydroxide. The long wavelength absorption maxima of these polynitrophenols shift toward blue in the order of p-nitrophenol, 2, 4-dinitrophenol and picric acid, with increasing molar absorbancy indexes in the same order. The absorption maxima of the anions similarly shift toward blue. The absorption maxima of each anion lie at longer wavelengths than do those of the corresponding polynitrophenol. These red shifts are greater with the increasing number of the nitro group. The high-intensity bands of these nitro compounds containing two or three electron-attracting substituents are interpreted from the viewpoint of Nagakura and Tanaka’s theory of the intramolecular charge transfer spectra.
The Assignment of the Molecular Vibrations of Hexachlorobenzene
Authors: Saëki Shinnosuke
Published: July 2006

The infrared absorption spectra of hexachlo-robenzene were measured in a gaseous state from 4000 to 300 cm−1, and in solid state from 300 to 100 cm−1. The Raman spectra of the same substance were measured in solutions in benzene, carbon tetrachloride and carbon disulfide. The depolarization ratio of each Raman line was also observed qualitatively. The assignment of the observed absorption bands and Raman lines was determined, partly by referring to that of benzene.
The Infrared Absorption Spectra of p-Dichlorobenzene and p-Dichlorobenzene-d4
Authors: Saëki Shinnosuke
Published: July 2006

The infrared absorption spectra of p-dichloro-benzene and p-dichlorobenzene-d4 were measured from 300 to 700 cm−1 in a gaseous state with cesium bromide prism, from 300 to 100 cm−1 in a solid state with gratings, and, using a newly constructed long path (720 cm.) high temperature cell, from 1700 to 700 cm−1 in a gaseous state with a sodium chloride prism. The frequencies and band envelopes of observed absorption bands were reported.

On the basis of these results, the assignment of the infrared active normal vibrations of these molecules was determined. The assignment was checked by means of the application of the product rule, and the correctness was verified by the good agreement between the theoretical and experimental values.

The assignment was also determined for the observed combination bands, using the Raman fundamental frequencies presented in the previous paper as well as infrared frequencies.
Infrared Absorption Spectra of Hydrazides. II. Sodium Hydrazides
Authors: Mashima Mitsuo
Published: July 2006

The infrared absorption spectra of HCONH·NCOH· Na, CH3CONHNCOCH3· Na, CH3CON·HNCOC6H5· Na, and C6H5CONHNCOC6H5· Na and their N-deuterated derivatives have been examined in the rock salt region. The characteristic frequencies of the ions (RCON·HNCOR′)- have been obtained, and the influence of an electronic charge on the amide frequencies has been discussed.
The Reaction of Tropoids and Quinone Derivatives. II. Reaction of Several Tropolones and p-Benzoquinone
Authors: Seto Shuichi , Sato Humio
Published: July 2006

Reaction of tropolone and p-benzoquinone was carried out in methanol containing acetic acid and the structure of products so obtained was determined. Tropolone gave 5-(4′-hydroxyphenoxy)tropolone and 3-(p-benzoquinonyl)-tropolone, 3-bromotropolone gave 3-bromo-7-(p-benzoquinonyl) tropolone, and 3, 7-dibromotropolene gave 3,7-dibromo 5-4′-hydroxy-phenoxy)tropolone by this reaction. Benzofurotropones were derived from benzoquinonyltropolones.

In order to prove the structure of the product by admixture, benzocoumarin derivative was prepared by the reaction of the diazonium salt of anthranilate and p-benzoquinone.
A Kinetic Study of the Isotopic Exchange of Indium between the Indium Ion and its N-2-Hydroxyethylethylenediamine-N,N′,N′-triacetate Complex in an Acid Solution
Authors: Saito Kazuo , Tsuchimoto (nee Tamura) Michiko
Published: July 2006

1) The isotopic exchange of indium between the indium ion and its EDTA-OH complex was kinetically studied in an acid solution, indium-114 m being used as tracer.

2) Separation of the indium ion from its EDTA-OH complex was satisfactorily carried out with 8-quinolinol (oxin) at a pH about 3, and no appreciable heterogeneous exchange was observed between the precipitate and the solute.

3) The exchange constant R was proportional to the concentration of the complex, the hydrogen ion and the ions such as dihydrogen citrate, but was independent of the concentration of the indium ion. It was affected by the ionic strength to a less extent, and the Arrhenius activation energy was 11 kcal. per mole.

4) A plausible reaction mechanism was postulated on the basis of the kinetic data. The dissociation of the protonated indium EDTA-OH complex appears to be the ratedetermining step.
De-localization of Bond Eigenfunctions in π-Electronic Systems. IV. Non-Empirical Calculation of the π-Electronic States of the Cyclobutadiene Molecule
Authors: Takekiyo Shozaburo
Published: July 2006

Calculations of the π-electronic energy levels, the wave functions, and the probabilities of the resonance structures of cyclobutadiene molecule have been made by an approximate method, proposed in part I, using the nonorthogonal Slater orbitals. Results have agreed quantitatively with the values calculated by the usual HLSP method.

Calculations have also been made using the orthogonalized atomic orbitals. Agreement of the results with those obtained by the usual method has been recognized.
Studies on the Reduction of Phosphorus Trichloride with Copper Powder in Non or Less Polar Solvents
Authors: Nakagawa Masanao
Published: July 2006

A phosphorus trichloride solution in non or less plar solvents was subjected to reaction with copper powder in a flask equipped with a reflux condenser or in an autoclave with an inner tube of “Teflon” and the resulting solution was examined with respect to the phosphorus content and the ratio of Cl/P. By these treatments the phosphorus trichloride was partially reduced with copper powder, and the phosphorus content decreased by the formation of a certain compound of phosphorus trichloride or its lower chloride or phosphorus with copper or cuprous chloride. The degree of the reduction depends on the property of the solvent and on the temperature of the treatment, whereas the decrease in the phosphorus content slightly depends on the property of the solvent. Silicon tetrachloride inhibits the reaction even at 200°C. This action may be due either to the adsorption of silicon tetrachloride on the surface of copper powder or to the solvation of phosphorus trichloride with silicon tetrachloride, or it may be due to the effects of both the adsorption and the solvation.
Vinyl Copolymerization. I. Copolymerization of Acrylonitrile with Methyl Methacrylate
Authors: Suzuki Momotaro , Miyama Hajime , Fujimoto Shiro
Published: July 2006

Rates of copolymerization, of AN-MM for various mixing ratios of the two monomers were measured by the thermistor method. The heat of copolymerization, which was obtained by comparing the results of the thermistor method with those of the usual analytical method, agrees very well with Alfrey’s equation. Also, the non-constancy of φ can be explained by Arlman’s theory. It is concluded that the termination constants for mixed radicals are larger than those homogenous radicals and, furthermore, that the rate constant for a normal cross-termination reaction is about ten times as large as that of the cross-termination reaction having a penultimate unit.
Thermal Decomposition of Acetaldehyde in the Presence of Hydrogen Sulfide. I. Kinetics of the Reaction
Authors: Imai Naomi , Yoshida Yasuo , Toyama Osamu
Published: July 2006

The hydrogen sulfide-catalyzed thermal decomposition of acetaldehyde has been investigated over the temperature range 340 to 494°C. The initial rates of decomposition approximately fit the rate equation

−d[CH3CHO]⁄dt=k[H2S] [CH3CHO]

 +k′[H2S] [CH3CHO]1⁄2

where

k=1012.7±1.0exp(−31400±3100⁄RT) mol−1ml.sec−1

and

k′=1012±0.27exp(−41100±1200⁄RT) mol−1⁄2ml1⁄2sec−1

A comparison of the above results with those of the decomposition inhibited by propylene and isobutylene, which will be reported on in the following paper, suggests that the first term of the rate equation probably represents a molecular decomposition catalyzed by hydrogen sulfide, while the second represents a radical-chain decomposition. Combining the chain mechanism generally accepted for the pyrolysis of acetaldehyde alone with the reactions CH3+H2S=CH4+HS and HS+CH3CHO=H2S+CH3CO, both of which have been shown to be important in the photolysis of acetaldehyde with added hydrogen sulfide, a rate equation is derived by which the second term of the experimental rate equation and the temperature depedennce of its rate constant k′ can be explained.
Determination of Deuterium in Organic Compounds
Authors: Tamiya Nobuo
Published: July 2006

A device to simplify the deuterium analysis of organic compounds was described. The combustion of organic samples and the reduction of deuterium containing the water produced were both carried out in sealed glass tubes. By this procedure one could completely avoid the “memory effect” and get satisfactory results, as shown by the examples of amino acid analysis.
Using Iron Ores of Kalabagh. I. Production of Limonite-Alkali Method
Authors: Ali M I
Published: July 2006

An industrial process of limonite production has been developed in this laboratory using local iron oxide ore of Kalabagh by alkali method. Sodium hydroxide was allowed to react with pulverized ore at 200∼225°C to produce sodium ferrite. This product was then hydrolyzed to obtain hydrated ferric oxide (limonite) and alkali in aqueous solution. The method was further modified in the light of some operational difficulties.

Hydrolysis was carried out under varied conditions for maximum recovery of alkali and the recovery upto 80% found to be economical. A graphical representation of this recovery was also given.
Diphenylcarbazone as an Internal Indicator in Volumetric Analysis. VII. Determination of Mercury
Authors: Deshmukh G S , Rao A L J
Published: July 2006

A simple and direct method of estimating mercury by standard potassium iodide with diphenylcarbazone as an indicator has been described. The results are accurate and comparable favorably with the classical procedures.
Effects of Tyrosyl Residue on the Polypeptide Monolayers
Authors: Yamashita Takuya , Isemura Toshizo
Published: July 2006

The monolayers of poly-Dl-phenylalanine (I), poly-l-tyrosine (II), copoly-1:1-(l-tyrosine, l-phenylalanine) (III), copoly-1:1: 2-(l-tyrosine, o-benzyl-l-tyrosine, l-phenylalanine) (IV), and copoly-1: 1-(l-tyrosine, glycine) (V) have been investigated at the air/water and oil/water interfaces.

The surface moment of I decreased by 50∼60 mD more on alkaline than on the acid subphase, probably owing to the keto-enol transformation of the peptide bond. The decrease in the surface moment of II is about 100 mD; this decrease seems to be caused by the ionization of the side chains and by the enolation of the peptide bond.

At the air/water interface, the effects of the dissociation of the tyrosyl residue on the II-A relations of II, III, IV and V were not very remarkable, probably because of the peptenol effect and the van der Waals force between side chains. It was found that the monolayers of I, II, III and IV assume a β-configuration. On the other hand, the film of V occupies much less area per residue than those in the β-form, which might be attributed to the folded structure caused by the strong intrachain hydrogen bond due to the glycyl residue.

At the oil/water interface, the films of I, III and V expand more and the change in subphase pH seems to be more effective than at the air/water interface. These facts might be caused by the release of van der Waals force between the side chains.
Infrared Spectra of Troponoid Compounds. V. Absorption Bands in the Region of 1700∼1530 cm−1 of Tropone, 2-Chlorotropone and Tropolone
Authors: Ikegami Yusaku
Published: July 2006

Infrared absorption spectra of tropone, 2-chlorotropone, and tropolone in the region of 1700∼1500 cm−1 were measured in various states and in various solvents, and the variation of two strong Bands I and II in the region of 1700∼1530 cm−1 was investigated. The data are shown in tables and figures. These two bands are explained as the participation of both of the C=O and C=C stretching vibrations in a tropone skeleton. The variation of the spectrum of tropolone with the measuring condition is much smaller than that of tropone. This is because the carbonyl group in tropolone is fixed by the intramolecular hydrogen bond.
The Electronic Spectra and Structures of s-Triaminobenzenium and Some Related Ions
Authors: Mataga Noboru
Published: July 2006

The electronic spectra and electronic structure of TAB and TABH+ have been studied by the MO method. The calculated spectra agree satisfactorily with the observed values. The stabilities of the protonation products of various aminobenzenes have been studied by Hückel MO calculations. The results of these calculations give an interpretation of the observed facts that TAB in an aqueous solution is easily protonated on the ring carbon (pK∼5.5), although no such protonation occurs in the case of aniline or m-phenylenediamine, where the amino group is protonated. The stability of the protonation product of TOB has also been studied.

It has been pointed out that the spectum of TABH+ is rather similar to that of benzenium ion, although the basicity of the former is much larger than that of the latter. This fact has been explained theoretically.

Further, it has been observed that a relation between the calculated localization energy and the observed basicity constant for the protonation similar to those of many aromatic hydrocarbons approximately holds for TAB and TOB.
Distribution of Inorganic Impurities in Graphite Electrodes
Authors: Inagaki Michio , Noda Tokiti
Published: July 2006

The distribution of inorganic impurities in graphite electrodes was investigated by means of radiography, ash pattern technique and sulfur print technique. The pattern of the radiograph of an electrode corresponded closely with its ash pattern.

Radiography of graphite electrode was proved to be useful in showing not only the distribution of inorganic impurities in the electrode, but also the texture of the electrode, such as the shape and distribution of both coke grains and pores.
Synthetic Studies of the Derivatives of Nitroacetic Acid. II. The Synthesis of Isoxazolecarboxylic Acids from α,β-Unsaturated α-Nitroesters
Authors: Zen Shonosuke , Umezawa Sumio
Published: July 2006

1) α,β-Unsaturated α-nitroesters react with n-butylamine to give 4-substituted isoxazole-3,5-carboxylic butylamides. This is a new synthesis of isoxazole derivatives.

2) The mechanistic features of the above reaction have been explained.

3) The mild alkaline hydrolysis of the above butylamides gave 4-substituted isoxazole-3,5-dicarboxylic acids.
The Luminescence Spectra of Triply-ionized Rare Earths in the Calcination Products of Some Magnesium Compounds
Authors: Iwase Eiichi , Nishiyama Seijiro
Published: July 2006

(i) The luminescence spectra of samarium(III), europium(III), terbium(III) and dysprosium(III) ions embedded in the calcination products of Mg(NO3)2·6H2O, MgSO4·7H2O and MgCl2·6H2O have been studied under excitation by cathode-ray bombardment at room temperature. The calcination of these ions was carried out either at about 900°C for 30 min. or by further heating at about 1800°C for 5 min.

(ii) The luminescence spectrum of each of the rare earth ions in magnesium oxide matrix was obtained in its pure form in the case of the calcination products derived from Mg(NO3)2·6H2O. A number of distinguishing diffuse luminescence bands were observed arising from the sulfate component remaining in the calcination products derived from MgSO4·7H2O. Calcination products derived from MgCl2·6H2O had a composition very near that of magnesium oxide and contained only a small amount of chlorine. When the triplyionized rare earths here investigated were embedded in these calcination products, several intense and sharp luminescence bands were found which cannot be ascribed to those observed in pure magnesium oxide, but presumably result from their chlorine content.

(iii) The luminescence spectra of these triplyionized rare earths embedded in the matrices derived from the calcination of MgSO4·7H2O and MgCl2·6H2O were considered to be constituted of the bands observed in the matrix of pure magnesium oxide and those characteristic of a matrix containing either a sulfate- or chloride-component. The frequencies of some of the principal bands characteristic of the presence of sulfate- and chloride-components have been given for each of the triplyionized rare earths investigated here.

(iv) As to the intensity of the luminescence of samarium(III), europium(III), terbium(III) and dysprosium(III) ions embedded in the matrices of calcined magnesium compounds, the magnitude of variation arising from heat treatment at elevated temperatures may be arranged in the order of rare earth ions with increasing atomic numbers 62∼66, the most marked decrease being seen in the luminescence of samarium(III) ions with the smallest atomic number (62), and the most marked increase, in that of dysprosium(III) ions with the largest number (66).
Synthesis of Dl-Glutamic Acid from 1,1,1,5-Tetrachloropentane
Authors: Saotome Kazuo , Yamazaki Toshiaki
Published: July 2006

Dl-Glutamic acid has been synthesized from 1,1,1,5-tetrachloropentane. The process involves five steps through 1,1,1-trichloro-5-hydroxypentane (92%), 5,5,5-trichlorovaleric acid (94%), 5,5-dichloro-4-pentenoic acid (85%), α-chloroglutaric acid (82%), and Dl-glutamic acid (87%). The over-all field from 1,1,1,5-tetrachloropentane to Dl-glutamic acid was 52%.

In the dehydrochlorination of 5,5,5-trichlorovaleric acid to 5,5-dichloro-4-pentenoic acid, rather weak Lewis acid catalysts, such as bismuth chloride and zinc chloride were found to give the best results.
Studies on Amino-hexoses. VI. The Synthesis of Phenyl 2-Acetamido-3-O-(d-1′-carboxyethyl)-2-deoxy-α- and β-d-Glucopyranoside and Their Methyl Esters
Authors: Yamamoto Kazuhiko , Fujinaga Mamoru , Matsushima Yoshio
Published: July 2006

A convenient method for the synthesis of anomeric phenyl glycosides of N-acetyl muramic acid and their methyl esters has been described. The test of lysozyme action on these model substrates was negative.

The expenses of this research were covered by U.S. Public Health Service Grant No. AI-04586-02.
The Absorption Spectra of Cobalt(III) Complexes. III. The Spin-forbidden Bands
Authors: Fujita Junnosuke , Shimura Yoichi
Published: July 2006

The near infrared, visible and near ultraviolet absorption spectra of about fifty complexes of cobalt(III) have been measured and the data discussed mainly in order to find the relationships existing among the two weak spin-forbidden bands and the two well-known spin-allowed bands.
Studies of the Synthetic Inorganic Ion Exchanger. II. The Properties of Stannic Phosphate
Authors: Inoue Yasushi
Published: July 2006

A recommended procedure for the preparation of stannic phosphate and a discussion of its ion exchange properties have been presented.

Some of the results obtained are as follows.

1) The density of the stannic phosphate is 2.17 g./cm3.

2) Stannic phosphate is a weakly acidic cation exchanger and possesses several dissociable hydrogen atoms in the range of pKa. values. In a weakly acidic solution, in which the exchanger is useful, the exchange group having the pKa value of approximately three is most important.

3) The ion exchange equilibrium can be elucidated by the mass action law.

4) The affinity series for alkali metal coincides with the usual relationship observed in the ion exchange resin.

5) The rate-determining step is assumed to be the migration of ions through the water retained in the gel structure.

6) Stannic phosphate is unstable against heat treatment in air; that is, the separation of alkali metal does not go well with the exchanger dried at 110°C due to the slow rate of exchange.

7) It is fairly stable against heat treatment in water; that is, it undergoes only a slight decrease in ion exchange capacity even when it is treated in water at 250°C for 8 days.

8) It is stable against irradiation of about 109r.

9) The structure of stannic phosphate has been suggested on the basis of its thermal decomposition curve, its exchange capacity, its titration curves, and its X-ray diffraction patterns.
The Spectrophotometric Determination of Vanadium(IV) with Xylenol Orange
Authors: Otomo Makoto
Published: July 2006

The reddish-violet complex of vanadium with xylenol orange has been studied spectrophotometrically, and the conditions for using xylenol orange as a reagent for the determination of trace amounts of vanadium have been established. The complex shows a maximum absorption at 562 mμ, and the molar extinction coefficient of the complex is found to be 24000. It is a 1:1 complex and has a formation constant of 2.8×106 under the conditions studied. Such anions as oxalate, citrate and EDTA inhibit the color formation of the complex. Some of the interfering cations can, however, be completely or partially masked by adding a fluoride solution.
The Nuclear Magnetic Resonance Spectra of Olefinic Protons and the Substituent Effects. III. Trans-forms of Methyl β-Substituted Acrylates, β-Substituted Vinyl Methyl Ketones and β-Substituted Acryloyl Chlorides
Authors: Niwa Jun , Kasiwagi Hazime
Published: July 2006

In the NMR absorption of the trans-forms of β-substituted acrylates, β-substituted vinyl methyl ketones and β-substituted acryloyl chlorides, the chemical shifts of protons situated at the cis-position to the substituents have been roughly determined by Hammett’s σp and Taft’s parameter, 0.40σI+0.70σR. From a comparison of the HA-shifts of the six olefinic systems (RCHA=CHBX, R=CH3, C6H5, H, CO2CH3, COCH3, COCl), these systems have been classified into two types—one, systems resembling the benzene derivatives, and the other, resembling the ethylene derivatives. Nevertheless, it has also been observed that the slope of each correlation line, on the whole, decreased in the order of the σ-value of the invariable substituent. The methyl proton shifts of β-substituted trans-acrylates, too, depend upon Hammett’s σp. The shifts of the proton (HB) at the β-positon can not be discussed from the viewpoint of Hammett’s substituent effect. However, they relate qualitatively with the electronegativity of the first atom of the substituent group.
The Rheological Properties of Concentrated Suspensions. I. Some Theoretical Considerations Based on a Network Model
Authors: Takano Masaharu
Published: July 2006

The rheological properties of concentrated suspensions have been considered theoretically by the use of a network model in which the particles are linked at random by thermal and mechanical actions.

The effects of particle size, the viscosity of the medium and the mean free energy of the activation for breaking links between particles have been taken into account in the calculation of the number of interparticle links.

The links between particles have been conveniently distinguished into two kinds in stationary states: the primary links, which are elongated without the separation of neighboring particles in an instant, and the secondary links, which are broken and reformed reversibly in an instant. The primary links originate from circular structures in the flocculates.

The dynamic properties at very small deformations and the stationary flow properties have been derived theoretically as functions of the concentration and of the frequency or the rate of shear by assuming a generalized Maxwell model modified by Eyring’s non-linear viscous elements.

The correlation of the dynamic properties and the stationary flow properties and the dependence of the dynamic properties on amplitude have been considered theoretically by the use of the present network model.
Asymmetric Hydrogenation with Modified Raney Nickel. II. Studies on Modified Hydrogenation Catalyst. III
Authors: Izumi Yoshiharu , Imaida Masami , Fukawa Hideaki , Akabori Shiro
Published: July 2006

1) The asymmetric R-Ni catalysts were prepared by the treatment of R-Ni with various asymmetric compounds, and the asymmetric activity of a catalyst was measured by the hydrogenation of methyl acetoacetate

2) Optical rotatory direction and power of the reduced product was affected both by the configuration and molecular size of amino acid which was used as modifying reagent.

3) The asymmetric activity of catalysts treated with N-substituted amino acids, N-acyl, N-dimethyl and N-cyanoethyl derivatives of Glu and Asp, were much less than the activity of the catalyst treated with the corresponding amino acids.

4) The asymmetric activity of the catalyst treated with d-tartaric acid and l-malic acid was tested at various conditions. The asymmetric yield in the hydrogenation of methyl acetoacetate in the presence of the catalyst treated with d-tartaric acid solution of pH 5.1∼5.2 at 100°C was about 45 percent.
The Synthesis of Chelating Agents. II. The Synthesis of Aminoacetone-N, N-diacetic Acid and Its Chelating Behavior with Metal Ions
Authors: Ando Takeshi
Published: July 2006

1) Aminoacetone-N, N-diacetic acid or 1-amino-2-propanone-N, N-diacetic acid has been synthesized. This is the first iminodiacetic acid derivative to have a keto group as an additional coordinating site.

2) The acid dissociation constant and the chelate stability constants of this ligand have been determined by the pH titration method, at 25°C and 0.10 m ionic strength, for such metal ions as copper(II), lead(II), nickel(II), zinc(II), cadmium(II), cobalt(II), calcium(II), strontium(II) and magnesium(II).

3) It has been proved that the coordination of the carbonyl oxygen of this ligand to metal ions is appreciable, and the increase in the chelate stability has been explained by the contribution of the carbonyl coordination.
The Electron Spin Resonance and Electronic Spectra of the Anion Radicals of 4-Nitropyridine and 4-Nitropyridine 1-Oxide
Authors: Itoh Michiya , Okamoto Toshihiko , Nagakura Saburo
Published: July 2006

The ESR and electronic spectra of the 4-nitropyridine and 4-nitropyridine 1-oxide anions have been measured. The nitrogen and hydrogen hyperfine splitting constants of these two compounds have been determined. In order to analyze the ESR spectra exactly, the measurements have also been carried out with respective compounds containing 15N instead of 14N in the nitro group. The spin densities on the nitrogen and carbon atoms of these two anions have been estimated from the splitting constants. It has thus been found that the spin densities on the ring nitrogen and carbon atoms are undoubtedly larger in the 4-nitropyridine 1-oxide anion than in the 4-nitropyridine anion.

The electronic spectrum of the 4-nitropyridine anion has been measured and three peaks found at 313, 440 and 640 mμ. According to the molecular orbital calculations carried out with the π-electron system of the 4-nitropyridine anion, it has been concluded that the 440 mμ band may be regarded as the intramolecular charge transfer band, and that the 313 mμ band can be interpreted as the blue shifted band of the pyridine anion.
The Pectic Acid from the Pulp of Jackfruit (Artocarpus Integrifolia). I. Methylation Studies
Authors: Gupta U K Sen , Rao C V N
Published: July 2006

Water-soluble polysaccharide extracted from the pulp of jackfruit (Artocarpus Integerifolia) has been shown to be composed of l-rhamnose, d-xylose, l-arabinose, d-glucose, d-galactose and d-galacturonic acid. The jackfruit pectic acid has subsequently been extracted with ammonium oxalate and purified. The results of electrophoresis, mild hydrolysis and methylation studies indicate the presence of chains of 1 : 4 linked α-d-galacturonic acid residues in the pectic acid, which is physically associated with a neutral polysaccharide, a glucan. Periodate oxidation studies have also been reported.
The Polymer-like Property of a Non-ionic Detergent Having a Long Polyoxyethylene Chain
Authors: Tokiwa Fumikatsu
Published: July 2006

The solubilization and viscosity of polyoxyethylene dodecyl ether (PODE) solutions were studied as a function of the polyoxyethylene chain-length (p). The solubilization is in accordance with the isotherm S=Kcn, where S is the extent of solubilization, c, the concentration of detergent, and n and K, constants. The value of n increases with the p value and is slightly greater than unity for PODE of p>27. The K′-value calculated from Huggins’ equation, which is dependent on the p value, decreases at first with the p value and then somewhat increases in spite of the increasingly hydrophilic nature. The effective volume, Φ⁄c, of PODE, which is nearly independent of c except for the case of PODE in which p=7.6, increases regularly as the p value becomes larger. On the basis of these results, the polymer-like property of PODE of a considerably large p value and the interaction among aggregates of PODE were discussed in connection with ultracentrifugal data reported previously.
Sterically-hindered Organosilicon Compounds Containing Cyclohexyl Groups. I. Reactions of Organolithium Compounds with Tricyclohexylfluorosilane
Authors: Takakusa Michio
Published: July 2006

The reactions of tricyclohexylflurosilane with n-butyl-, phenyl-, isopropyl- and cyclohexyllithiums in boiling petroleum ether (90∼110°C) were studied, and tricyclohexylbutylsilane and tricyclohexylphenylsilane were prepared (41 and 72%, respectively) for the first time. A secondary alkyl group can not be bonded to the silicon of tricyclohexylsilyl group even under these drastic conditions.
Vinyl Polymerization. LXVII. The Polymerization of Vinyl Acetate in the Presence of Zinc Chloride
Authors: Imoto Minoru , Otsu Takayuki , Ito Toshio
Published: July 2006

A study of the effect of zinc chloride on the polymerization of vinyl acetate has been made. Zinc chloride can initiate the cationic polymerization of vinyl acetate at above room temperatures to yield the colored low-molecular weight polymer. However, in the low-temperature photopolymerization of vinyl acetate initiated by azobisisobutyronitrile, zinc chloride accelerates the radical polymerization and the colorless polymer which is insoluble in the monomer is obtained. Elementary analysis, infrared spectra and X-ray analyses show that the structure of this polymer after purification does not differ with that of ordinary poly-vinyl acetate and polyvinyl alcohol obtained through the hydrolysis of this polymer has no crystallinity superior to that of the ordinary sample.
The Selective Chelatometry of Calcium in the Presence of Magnesium with Ethylene Glycol-bis(β-aminoethyl ether)-N,N,N′,N′-tetraacetic Acid
Authors: Nakagawa Genkichi , Tanaka Motoharu , Wada Hiroko
Published: July 2006

The optimum conditions for the chelatometry of calcium with EGTA have been deduced from the theoretical consideration of the equilibria involved. Some experimental results have been given on the chelatometry of calcium in the presence of magnesium using the Zn-EGTA-PAN system as an indicator. This proposed method seems to be better than earlier ones.
Spectrophotometric Studies of the Complexes of Phenylazochromotropic Acid Formed with Thorium
Authors: Miyata Haruo
Published: July 2006

The dissociation constant of phenylazochromotropic acid, pKa, has been estimated spectrophotometrically to be 9.30 (25°C, μ=0.1).

The reagent reacts with thorium in the molar ratio 1:1, displacing one hydrogen atom, and the approximate value of the apparent stability constant of the complex, logK′, has been estimated to be 3.4∼4.9 in the 2∼3.5 pH value range.
Studies of the Absorption Spectra of Azo Dyes and their Metal-complexes. V. The Electronic Absorption Spectra of Metal-complexed Phenolazoacetoacetbenzylamides
Authors: Yagi Yoshiharu
Published: July 2006

The absorption spectra of metallized phenolazoacetoacetbenzylamides were investigated.

The isolation of the electronic effect of the amide phenyl ring by the insertion of the methylene bridge decreases the intensity of the D band, resulting in the hypso- and hypochromic displacement of the A, B and C bands.

The red-shifts of the A and C ligand-bands with the complex-formation indicate that the Co–O (O, phenolic oxygen) bonds increase their ionic character as compared with those of the metallized phenolazoacetoacetanilides.

The splitting of the A band in the spectra of metallized 2-hydroxy-5-nitrophenylazoacetoacetbenzylamide is possibly to be attributed to the polarization of the M–O (O, phenolic oxygen) bond by the electron-withdrawing nitro group.