bluuebunny/crossref_metadata_2025 huggingface dataset:
Absorption Spectra of Dyes. IV. Absorption Spectra of Mixtures of Chlorazol Sky Blue FF and Dyes Prepared from Sulfanilic Acid and Cresidine
Authors: Kobayashi Teruaki , Tanizaki Yoshié , Ando Noboru
Published: July 2006

1. The absorption spectra of the binary mixtures in aqueous solution of Chlorazol Sky Blue FF and sulfanilic acid → cresidine and sulfanilic acid → cresidine→ cresidine were measured at room temperature.

2. The mixture of Chlorazol Sky Blue FF and sulfanilic acid → cresidine shows the additive spectrum when the ratio of the two dyes is about 1:5 but the non-additive one when it is about 1:40. From this fact the authors pointed out that even if an equimolar or nearly equimolar mixture shows the additive spectrum, it often exhibits the additive one with a relative increase of one component, due to the interaction between the components. That the spectra of the mixture pass through an isosbestic point means that a Sky Blue molecule interacts with n molecules of sulfanilic acid → cresidine (n is unknown).

3. It was indicated that the mixture of Chlorazol Sky Blue FF and sulfanilic acid → cresidine→ cresidine showed the non-additive spectrum, and that this was well explained by assuming the formation of a 1:1 complex over the range of concentrations measured.

4. The authors discussed qualitatively the characters of the spectra and the stability of these complexes, comparing them with the complex of Sky Blue and Chrysophenine G, etc.
On the Mechanism of Oxidation by Cuprous Chloride, Pyridine and Air. III. On the Mechanism of Oxidative Cleavage of Benzil, α-Methyl Benzoin and Hydrobenzoin
Authors: Kinoshita Keiz\={o}
Published: July 2006

(1) Benzil is oxidized by aerial oxidation catalyzed by “oxidants A, B, C and D”.

(2) α-Methyl benzoin or hydrobenzoin is oxidized by aerial oxidation catalyzed by “oxidants A and B” only. This reaction is retarded by methyl alcohol.

(3) The mechanism of oxidative cleavage of benzil, α-methyl benzoin and hydrobenzoin, is described. It is also considered that the oxidative cleavage of benzil, α-methyl benzoin and hydrobenzoin, and the oxidative dimerisation of aniline are carried out through similar mechanism.
Recombination of Hydrogen Atoms on Various Transition Metal Surfaces
Authors: Nakada Kazuo
Published: July 2006

A study has been made of surface recombination of hydrogen atoms on various transition metals.

Hydrogen atoms were produced in the electric discharge tube by use of an alternating current. In order to prevent the reacting gas from reaching the undesired part of the sample, a method which may be called “an effusion method” was adopted here. The relative activity of two kinds of metal plates, stuck together by the solder or some such material, was determined, comparing the temperature rises of the sample by means of alternative exposure of each side surface to the reacting gas.

The following results were obtained:

a) Co>Fe>Ni>Ta>Mo>W>Ti>Cr>Mn>Cu

b) Zr>Ti>Th

c) Mo>U

These orders of activity were examined from several points of view through the comparison of recombination activity with the work function, the d-character, the experimental heat of chemisorption, etc.

The present results are still fragmentary but may suffice to show a qualitative trend.
The Kinetic Study of Surface-chemical Reactions at Extremely Low Pressures. II. The Thermal Reaction between Water Vapor and a Tungsten Filament. Part II
Authors: Hamamura Takuya
Published: July 2006

1) The end effect of filament upon the reaction probability was eliminated by means of the two-filament method. Its principle and procedure were described.

2) Reaction probabilities were determined at temperatures from 1430 to 1940°K and pressures of water vapor from 12×10−5 to 125×105 mmHg.

3) The reaction probability increased remarkably with the increase of temperature, but the rate of increase became smaller in the vicinity of 1700°K.

4) The order of reaction with respect to water vapor was found to lie between 0.60 and 0.86.
The Dissociation Constants of Carboxytropone and Carboxytropolones
Authors: Tanaka Nobuyuki , Oiwa I T , Kurosawa Toshiko , Nozoe Tetsuo
Published: July 2006

The thermodynamic dissociation constants of 2-carboxytropone, 3-carboxytropolone, 4-carboxytropolone, 5-carboxytropolone, 3-carboxy-4-methyltropolone, 3-carboxymethyltropolone, 3,4-dicarboxytropolone and 3-carboxy-4-carboxymethyltropolone have been determined by means of the pH titration with a glass electrode.

The relationships between the magnitudes of the dissociation constants and the structures of these compounds have been discussed.
The Reaction of the Aquopentamminechromium(III) Complex Ion in Aqueous Solution. I. Substitution Reaction of a Coordinated Water with a Chloride Ion
Authors: Hashimoto Shinpei
Published: July 2006

The substitution reaction of aquopentamminechromium(III) ion in which a coordinated water molecule is replaced by a chloride ion was investigated spectrophotometrically. The reaction proceeds according to the second order rate law, d[[Cr(NH3)5Cl]2+]/dt=\overrightarrowk2[[Cr(NH3)5OH2]3+]. [Cl−], and the rate constant varies regularly with the ionic strength of solution according to the Debye-Hückel type equation. The formation of outer sphere association complex in the solution was detected from the change in ultraviolet absorption. From these results the ratedetermining process of this reaction was inferred to be a unimolecular process through the outer sphere association complex. The experimental activation energy and the frequency factor of this reaction were determined to be 24.6 kcal.mol−1 and 1.2×1014l. mol−1min−1 (ω∼0.52), respectively.

The aquation of chloropentamminechromium(III) ion was also studied in the solutions of various ionic strengths and the reaction rate was found to vary to some extent with ionic environment.
Investigation on Mixed Complexes. II. Cyano Complexes of Copper and Nickel
Authors: Kida Sigeo
Published: July 2006

1. Mixed amino-cyano nickel(II) complexes, such as [Ni en2(CN)2], [Nien·(CN4)4]−2 and [Ni en(CN)2] in the solution containing the divalent nickel ion, ethylene-diamine and cyanide ion, are not formed.

2. In the solution containing the divalent or the monovalent copper ion, ethylene-diamine and the cyanide ion, no mixed amine-cyano copper(I) and copper(II) complexes are formed, except the copper-(II) complex of coordination number 5.

3. Among cyano copper(I) complexes, tricyano copper(I) ion is the most stable, and its coordination number may be 3.
Visible and Ultraviolet Absorption Spectra of Red Complexes of 1,3,5-Trinitrobenzene and its Derivatives with Ammonium Hydroxide
Authors: Abe Takehiro
Published: July 2006

The red complexes of trinitrobenzene, trinitrotoluene, tetryl and picryl chloride with ammonium hydroxide, regarded as intermediates in aromatic substitutions, were obtained. Each of these red complexes roughly shows a similar spectrum both in water and in ethanol. All their visible bands, however, shift to the red and have greater molar absorbancies in ethanol as compared with those in water. The red complex of trinitrobenzene shows an absorption curve analogous to that for the complex of tetryl, although they yield different products after further reactions. As the concentration of sodium hydroxide increases, the molar absorbancy for the spectrum of the red complex of trinitrtoluene decreases in water, probably owing to the action of OH−.
Application of the Theory of Regular Solutions to Binary Phase Equilibria. II. Dependency of the Interchange Energy upon Temperature
Authors: Ishida Kiyoharu
Published: July 2006

Theoretical expressions for estimating the interchange energy w were given in such form as to be obtained from the mutual solubility data. It has been found that the dependency of the interchange energy estimated from mutual solubility data in terms of \varphi-fractions upon temperature is satisfactorily expressed by the form of equations w⁄kT–(w⁄kT)c=K(|Tc⁄T–1|)n. The method of predicting the critical solution point was described as an example of the application of the theory of regular solutions.
The Assignment of Infrared Absorption Bands of p-Dichlorobenzene
Authors: Saëki Shinnosuke
Published: July 2006

The infrared absorption spectra of deuterated and non-deuterated p-dichlorobenzene were measured in the vapor state using a high temperature cell. The results obtained by the measurement permitted us the assignment of the observed fundamental bands with the aid of the product rule. For some frequencies which we could not measure under our experimental conditions, we used the frequencies observed by other workers in the solid state which enabled us to apply the product rule.
Studies on Antibiotics and Related Substances. X. Syntheses of Some Unsaturated Ketocarboxylic Acids, Anti-tumor Substances
Authors: Kinoshita Mitsuhiro , Umezawa Sumio
Published: July 2006

1) 2-(Dimethylaminomethyl)-3-ketobutane-1-carboxylic acid hydrochloride (VI) as well as 5-dimethylamino-3-ketopentane-1-carboxylic acid hydrochloride (I) has been obtained from levulinic acid, paraformaldehyde and dimethylamine hydrochloride by means of the Mannich reaction. Thermal degradation of I and VI afforded δ-methylenelevulinic acid (IV) and β-methylenelevulinic acid (VII), respectively.

2) 3-(Dimethylaminomethyl)-4-ketopentane-1-carboxylic acid hydrochloride (XII) as well as 6-dimethylamino-4-ketohexane-1-carboxylie acid hydrochloride (VIII) has been obtained from 5-ketocaproic acid, paraformaldehyde and dimethylamine hydrochloride by means of the Mannich reaction. Thermal degradation of XII and VIII afforded 4-keto-5-hexene-1-carboxylic acid (XI) and 4-keto-3-methylene-pentane-1-carboxylie acid (XIII), respectively.

3) The structures of IV, VII, XI and XIII have been proven.

4) Some derivatives of above-mentioned carboxylic acids have been described.

5) It has been found that IV, VII, XI and XIII possess significant antitumor and antibacterial activites; especially calcium salt of 4-keto-5-hexene-1-carboxylic acid (XI) gave an excellent result in animal experiments.
Effect of Compacting and Grinding on the Hydrogen Reduction of Nickel Oxide
Authors: Iida Yoshio , Shimada Kenzo
Published: July 2006

The rate of hydrogen reduction of nickel oxide increases with an increase in the compacting pressure although the bulk density of nickel oxide increases and the surface area does not vary with the pressure. The rate of reduction of nickel oxide which is prepared by the grinding of a single crystal and has a large particle size of 50 μ is higher than that of nickel oxide which is prepared by ignition of nickel sulfate and has small particle size of 0.5 μ. It seems reasonable to conclude that the accelerated reduction is attributed to the crystal distortion which may result from plastic deformation by grinding or compacting.
Polymerization of Methyl Methacrylate Initiated by N-Nitrosophenylurea
Authors: Uehara Ryoichi
Published: July 2006

N-Nitrosophenylurea is an efficient initiator of the polymerization of methyl methacrylate. The initial rate of polymerization of methyl methacrylate was linearly dependent upon the concentration of methyl methacrylate and the square root of the concentration of N-nitrosophenylurea. These facts suggest that the polymerization is initiated by radicals which are produced through a unimolecular first order decomposition of N-nitrosophenylurea.
Spectrochemical Study of Microscopic Crystals. XXII. The Structure of Cupric Mono-, Di- and Trichloroacetate
Authors: Yamada Shoichiro , Nishikawa Hiroaki , Tsuchida Ryutaro
Published: July 2006

In order to examine the structure of cupric chloroacetates, the dichroism in the visible and the ultraviolet region has been determined at room temperature by the microscopic method with mono-, di- and trichloroacetate. Visible and ultraviolet absorption spectra have also been determined with the above compounds in organic solvents.

The monochloroacetate consists of the binuclear molecules of the acetate-type in the crystalline state and in solution. It has been found that there is another form of the anhydrous monochloroacetate, which is colored blue and contains no binuclear molecule.

The dichloroacetate exists as binuclear molecules in ethyl ether and dioxane, but as mononuclear complexes in ethanol. The anhydrous dichloroacetate in the crystalline state consists of binuclear molecules of the acetate-type.

The trichloroacetate exists as mononuclear complexes in ethanol and in dioxane, and in the crystalline state. The compound exists as binuclear molecules in ethyl ether. Crystals of another form have also been obtained. These possibly consist of binuclear molecules.
Investigation on Mixed Complexes. V. A Conductometric Study of Cyano-ethylenediamine Complexes
Authors: Kida Sigeo
Published: July 2006

The conductometric method was applied to the determination of the formation of mixed complexes in solution, using the method of continuous variation. It was shown that

1) [Ni en3]2+ reacts with CN− and forms [Ni(CN)4]2− only, leading to the same conclusion as in the spectrophotometric investigation carried out previously.

2) [Pt en2]2+ forms only a tetracyano complex, but no mixed dicyano complex.

3) [Pd en2]2+, [Zn en3]2+ and [Cd en3]2+ form dicyano-ethylenediamine complexes in solution.
The Formation Constants of Metal Acetate Complexes. III. Polarographic Determination of the Formation Constants of Acetatocadmium(II) and Acetatocobalt(II) Complexes
Authors: Tanaka Nobuyuki , Kamada Minoru , Osawa Hisao , Satô Gen
Published: July 2006

The formation constants of acetatocadmium-(II) and acetatocobalt(II) complexes were determined at ionic strength of 0.2 at 15, 25 and 35°C with the procedure that is based on the polarographic measurement of the sum of the equilibrium concentrations of the hydrated metal ions and the metal acetate complexes in the substitution reaction involving EDTA complexes. The resulting formation constants KCdOAc and KCoOAc are 27 and 2.1 at 15°C, 16 and 0.6 at 25°C and 20 and 0.6 at 35°C, respectively.
Infrared Spectrum of Some Deuterated Crystalline Polystyrenes. I. Isotactic Poly-αd1-styrene
Authors: Kobayashi Masamichi
Published: July 2006

In Table I are given the results of discussions described above on the assignments of the absorption bands.

The bands characteristic to the isotactic polymers, i.e. the bands appearing in the region of 1400∼1180cm−1 or in the vicinity of 1070 and 900cm−1, are proved as associated with the CH2 and CH groups.

To make assignments of the bands more precisely, the studies are in progress on the infrared spectra of the other several deuterated derivatives, such as poly-βd1-, poly-α,βd2 and poly-β,β d2 styrenes.
Neutron Activation Analysis of Halogens in High-Purity Silicon
Authors: Nozaki Tadashi , Kawashima Toshi , Baba Hideo , Araki Hidemaro
Published: July 2006

A trace quantity of chlorine, bromine and iodine was determined simultaneously by neutron activation analysis. By careful distillation of a solution containing the alkali-fused silicon, chromium(VI) oxide and sulfuric acid, bromine and chlorine were distilled out separately, leaving iodine in the residual solution, which was then distilled out after adding oxalic acid.

Most kinds of high-purity silicon contained more than 0.1 ppm of a halogen, which was used in the course of its purification process, and also two other halogens, though of a smaller quantity.
Distribution of Unpaired π-Electron in Some Semiquinone Ions
Authors: Matsunaga Yoshio
Published: July 2006

The distribution of unpaired π-electron was calculated by the simple MO method using the proposed parameters αo=α+(1/2)β and α+(2/3)β for six semiquinone ions. The calculated splitting constants for the ring protons in p-benzo- and naphtho-semiquinone ions were found in good agreement with the experimental ones and the MO treatment with the proposed parameters seemed to be very helpful to the analysis of the hfs of ESR spectra of anthra-and bipheno-semiquinone ions. In the case of o-semiquinone ion, a much higher value of αo was required to obtain quantitative agreement. The assignment of splitting constants was attempted for the semiquinone ion from nin-hydrin. It was found that the simple MO method fails to predict the symmetry of the singly occupied MO in the semiquinone ion formed on reduction of dihydroxy-p-benzo-quinone. In addition the ESR spectra of the semiquinone ions from methyl- and hydroxy-naphthoquinones etc. were described.
Hydrogen Peroxide Oxidation. IV. A New Rearrangement Reaction of Phenyl Alkyl Ketones by Selenium Dioxide Catalyst
Authors: Sonoda Noboru , Tsutsumi Shigeru
Published: July 2006

1) Selenium dioxide catalyzed oxidation of phenyl alkyl ketone with hydrogen peroxide in tert-butyl alcohol gave α-phenyl carboxylic acid which was produced by the rearrangement of the phenyl group to the α-carbon atom as shown by Eqs. 2, 4 and 6. Therefore, the reaction mode is quite different from the Willgerodt reaction. The fact described above suggests that similar treatment may be generally applicable to the other aryl alkyl ketones.

2) The reactivity of phenyl alkyl ketone was lower than that of dialkyl ketone, and cleavage reaction was also observed. It is assumed that the cleavage products may be produced partly from the Baeyer-Villiger oxidation product because an active species in this reaction system is considered to be peroxy-selenious acid, a kind of peracid.
Studies on the Mucilage of the Root of “ Tororo-aoi” (Abelmoschus manihot, MEDIC). I. On the Characteristic Colloidal Nature of the Mucilage
Authors: Inokawa Saburo
Published: July 2006

1) The crude mucilage could be filtered after homogenizing by a mixer. By the addition of alcohol-ether mixture to the filtrate, the precipitates were obtained, which gave purified mucilage on redissolving in water.

2) The purified mucilage had noticeable elasticity and could be used for the research work instead of crude mucilage.

3) Some colloidal behavior of the purified mucilage was observed.
Graft Polymerization by Pre-heating Method Applied to Polyethylene Containing Benzoyl Peroxide
Authors: Okamura Seizo , Manabe Tomonobu
Published: July 2006

Some solid polymers containing initiator of radical polymerization of vinyl monomers can initiate graft polymerization by heating in air or in vacuo prior to polymerization. In the experiment on polyethylene film containing benzoyl peroxide (monomer: methyl methacrylate), the increase of time (from 0 to 60 min.) and the rise of temperature (from 20 to 120°C) in pre-heating procedure increase the graft polymerization rate. And also, the increase of time interval after pre-heating until polymerization results in the decrease of the graft polymerization rate.
Variation of Radiocarbon Concentration in Modern Wood
Authors: Kigoshi Kunihiko , Tomikura Yoshio
Published: July 2006

1) Using the tree ring samples, the variation of C-14 concentration in the atmosphere since 1782 has been measured by the use of trees growing in Japan. The results show a constant concentration of C-14 in the atmosphere during 1782 and 1950 within the error of 2%.

2) The depletion of C-14 concentration in the atmospheric carbon dioxide between 1782 and 1950 seems to be less than 2%.

3) The observed annual variations on the samples from Tokyo, Akita and Mie Prefectures show almost the same amount of increase after 1953. There is a good agreement between our data and those on the tree ring samples taken in California by Bien and Suess. The concentration of C-14 in the atmosphere averaged over a year seems to have little difference in the temperate zone of the northern hemisphere.

4) The variation of C-14 concentration in the atmosphere of the southern hemisphere seems to follow that of the northern hemisphere with a time lag of several months.
Studies on Anti-cancer Agents. V. Desulfurization by Hydrazine Hydrate. II. The Reaction of Benzyl and Piperonyl Disulfide with Hydrazine
Authors: Kametani Tetsuji , Fukumoto Keiichiro , Satoh Yumiko , Teshigawara Takashi , Umezawa Osamu
Published: July 2006

The desulfurization reaction which was reported in the previous paper in case of the reaction of p-nitrobenzyl disulfide and hydrazine hydrate was also observed in the similar reaction of benzyl and piperonyl disulfide. The reaction product was found to be benzaldazine derivative instead of the derivative of benzal hydrazine.
On the Thermal Dissociation of Organic Compounds. XV. Thermal Dissociation of Urethans in the Presence of Aromatic Amines
Authors: Mukaiyama Teruaki , Akiba Toyohiko
Published: July 2006

N-Phenyl phenylurethans dissociate readily into their component compounds in the presence of aliphatic amines and the plot for the second order reaction shows a straight line throughout a large portion of the dissociation. However, the rate of the dissociation of urethans in aromatic amines is much slower than in aliphatic ones and shows a tendency of increasing rate as the dissociation proceeds. The anomalous acceleration of the dissociation is due to the reaction products, urea and phenol.

In order to clarify the behavior of urea which accelerates the dissociation effectively, the rates of the dissociation of urethans in the presence of ureas and analogous compounds, such as urethans and amides, were determined.

The mechanism of the dissociation of urethans in aromatic amines which involve the product catalyzed reaction was discussed.
Hot-Atom Chemistry of Halogens in Cobaltammine Complex Salts. I. Hot-Atom Chemistry of Bromine in Bromopentammine Cobalt Complex Salts
Authors: Saito Nobufusa , Sano Hirotoshi , Tominaga Takeshi
Published: July 2006

The hot-atom effect was investigated on 80mBr and 82Br resulting from (n, γ) processes in ligand bromine of bromopentammine cobalt complex salts. The fraction of radiobromine retained in ligand (ligand yield) was compared for samples irradiated in different phases, and it increased in the following order: solution, resin, solid. It is interesting to note that in the irradiation of solids of bromopentammines [Co(NH3)5Br]Br2 showed almost the same ligand yield as other salts. The hot-atoms resulting from the anions may behave in the same way as those from ligands of the complex salts. The exchange of ligand bromine in these complex salts with bromide in water was regarded as being very slow at room temperature.

In the irradiation of the complex ion adsorbed on a cation exchange resin, a considerable fraction of radiobromine was trapped in the resin matrix. Treatments with either inorganic acids or a reducing agent did not remove the activity appreciably. Most of the radiobromine remaining in resin was presumed to be organically combined with the matrix.
Studies on Antibiotics and Related Substances. IX. Synthesis of Methyl 5-Methylenecyclopentanone-2-acetate, an Antitumor Substance and Related Compounds
Authors: Umezawa Sumio , Kinoshita Mitsuhiro
Published: July 2006

1) 5-(Dimethylaminomethyl)cyclopenta-none-2-acetic acid hydrochloride (I) and 2-dimethylaminomethyl isomer (X) have been synthesized from cyclopentanone-2-acetic acid by means of the Mannich reaction.

2) Methyl 5-(dimethylaminomethyl) cyclopentanone-2-acetate (II′) has been degraded to give methyl 5-methylenecyclo-pentanone-2-acetate (III), which has been hydrolyzed into 5-methylenecyclopenta-none-2-acetic acid (IV), a homologue of isosarkomycin.

3) Destructive distillation of the hydro-chloride (I) afforded methyl 5-methyl-4-cyclopenten-l-one-2-acetate(VI), an isomer of III.

4) It has been found that III and IV possess antitumor and antimicrobial activities.
Fluorine-19 Nuclear Magnetic Shielding in Some Monofluorinated Compounds
Authors: Ito Kazuo , Inukai Kan , Isobe Taro
Published: July 2006

The 19F NMR spectra of 2- and 3-fluoropyridines, 1-fluoropyrene, cyclohexylfluoride, 9-fluoroanthracene and 12-fluorochrysene were studied. No signal was obtained for the latter two compounds. The magnetic shielding constants obtained were attempted, together with those for fluorobenzene, 1- and 2-fluoronaphthalenes, to be correlated with some molecular indexes. It was found that the π-electron density in McWeeny’s sense (π-electron “atom charge” density) on the ring carbon atom, to which the fluorine in question is bound, is must probably correlated with the magnetic shielding of the fluorine nucleus. This result suggests that the variation in 19F magnetic shielding constants in these compounds may be attributed mainly to the variation in polarity in C–F σ-bonds. It was noted that such an idea is supported by nuclear quadrupole resonance experiments.
The Effect of Metallic Ions on Surface Chemical Phenomena. III. Solubility of Various Metal Dodecyl Sulfates in Water
Authors: Miyamoto Shigeru
Published: July 2006

Calcium, strontium-, barium-, lead-, manganese-, magnesium-, cobalt- and copper dodecyl sulfates were synthesized and their compositions were determined from the results of their elementary analysis and metal content analysis. Further, the solubility of these metal dodecyl sulfates was measured at various temperatures. From these data, these metal dodecyl sulfates except barium salt were found to have the Krafft points, values of which were shown also.
Relations between Electronic Absorption Spectra and Spatial Configurations of Conjugated Systems. VII. α-Substituted and α, α′-Disubstituted Stilbenes
Authors: Suzuki Hiroshi
Published: July 2006

The ultraviolet absorption spectra of some α- and α, α′-substituted stilbenes have been analyzed, and the most probable spatial configurations of these compounds have been inferred from the spectra by application of the calculation method described in the earlier part of this series. It is especially noteworthy that with α, α′-dimethylstilbene as well as its diethyl analogue the trans isomer shows the conjugation band at a shorter wavelength than the cis isomer, contrary to the generally accepted view that trans isomers of conjugated compounds should exhibit the conjugation bands at a longer wavelength than the corresponding cis isomers. This fact is considered to indicate that with these compounds the trans isomers are less conjugated than the corresponding cis isomers, and that the angle of twist of the “single” bond (interplanar angle) is larger in the trans isomers than in the corresponding cis isomers. This has been confirmed by the results of the calculations. Further, this is supported also by some pieces of information on the properties of these compounds, such as the reactivities, the exaltation of molecular refraction, and the nuclear magnetic resonance. With special emphasis on this respect, the correlation of some physical and chemical properties of these compounds with the spatial configurations of the molecules has been discussed in detail.
Oxidation of Ferrous Ions in the Aqueous Ferrous-Cupric System. I. Effect of Cobalt-60 Gamma-Rays
Authors: Hotta Hiroshi , Terakawa Akira , Ono Shinichi
Published: July 2006

The oxidation of ferrous ion in ferrous-cupric acidic aqueous solution by Co-60 gamma-rays was studied in order to find a good chemical dosimeter for high doses. Consequently, it is found that the non-treated solution containing the 10−3m cupric ion is useful for this purpose, for this amount of cupric ions is sufficient to suppress the effect of oxygen, and that the G-value of the ferrous-cupric system is dependent on the composition of the solution. The suppression can be explained by the scavenging of the HO2− ion by cupric ions. Furthermore, some discussions regarding the system are given in the present paper.
Separation of Uranium and Protactinium from Thorium by Amine Extraction
Authors: Ichikawa Fujio , Uruno Shinobu
Published: July 2006

Uranium, protactinium and thorium are satisfactorily separated from each other by secondary amine extraction. Amberlite LA–1 in kerosene diluent is used as the extractant. Separation from hydrochloric acid solution is superior to that from systems using other acids. The acid dependency of the extraction coefficient by anion exchange resin, but the former has selectivity for uranium. Under the total dose of 5×107r., the radiation damage of Amberlite LA–1 is negligibly small. From these results, it is evident that there is a possibility of applying the amine extraction to the recovery of uranium-233 from reactor blanket fuel.
Investigation on Mixed Complexes. Spectrophotometric Studies on Platinum(II) Complexes
Authors: Kida Shigeo
Published: July 2006

The spectrophotometric investigation has shown that in the substitution reactions of cyanide ion for halogens(X−) of the complexes, [Pt X4]2−, (X=Cl and Br) in solution, no mixed complex is formed.
Alkylalkoxypolysiloxanes. VIII. Lower Members of Cyclic Methyl- and Ethyl-isopropoxypolysiloxanes
Authors: Okawara Rokuro , Katayama Masuo
Published: July 2006

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

2) Methyl- and ethyl-isopropoxycyclotrisiloxane have been prepared and characterized. Those compounds were found to be stable.

3) Methyl- and ethyl-isopropoxycyclotetrasiloxane have been prepared and characterized.
Resolution of Amino Acids. II. Resolution of Racemic ε-Acyllysine and δ-Acylornithine Amides by Leucine Aminopeptidase
Authors: Izumiya Nobuo , Uchio Hakaru , Kamata Tetsuo
Published: July 2006

ε-Benzoyl-Dl-lysine amide, δ-benzoyl-Dl-ornithine amide and δ-carbobenzoxy-Dl-orithine amide were resolved to ω-acyl-l-amino acids and ω-acyl-d-amino acid amides by the partially purified leucine aminopeptidase preparation. ω-Acyl-l-amino acids and ω-acyl-d-amino acid amides were hydrolyzed to l- and d-amino acid hydrochlorides, respectively. The parts of ω-benzoyl-d-amino acid amides were changed to ω-benzoyl-d-amino acids by acid hydrolysis.
Near Ultraviolet Absorption Spectra of Acrolein and Crotonaldehyde
Authors: Inuzuka K\={o}z\={o}
Published: July 2006

The positions vibrational structures and blueshifts of absorption spectra of acrolein and crotonaldehyde in 33300∼25000 cm−1 region suggest that the transition is of the n-π* type. They are similar in vibrational structure except that the crotonaldehyde absorption is shifted towards higher frequencies with respect to that of acrolein. The vapor frequency of the 0–0 band is 25873 cm−1 for acrolein, smaller by 654 cm−1 than that of crotonaldehyde. The acrolein absorption has 1427, 1271 and 498 cm−1 progressions, which are assigned to the C=C stretching frequency, the C=O stretching frequency and skeletal bending frequency in the excited state, respectively. , For the crotonaldehyde there are 1360, 1237 and 450 cm−1 progressions, which are assigned to the C=C stretching frequency, the C=O stretching and the skeletal bending vibration in the excited state, respectively According to our calculation, the elongation q in the carbonyl bond length during the n-π* transition, is estimated to be approximately 0.1 Å.
Monolayers of Some Cyclic Peptides. Fungisporin and Gramicidin J1
Authors: Ikeda Shoichi , Isemura Toshizo
Published: July 2006

Monolayers of two naturally occurring cyclic peptides, fungisporin and gramicidin J1, were investigated by the measurements of surface pressure, potential, and viscosity. Fungisporin, an octapeptide composed of phenylalanyl and valyl residues, gave a monolayer of a condensed type. Gramicidin J1, an electrolytic heptapeptide containing a prolyl and two ornithyl residues, gave an unionized monolayer of an expanded type on an alkaline subphase. It behaved in a somewhat specific manner when neutral salt such as potassium chloride was present.

The configurations of these cyclic peptides in monolayer were suggested in such a way as intramolecular hydrogen bonding could cause a maximum number of seven-membered rings. Then fungisporin can take four possible square-like configurations, which are equally probable, and gramicidin J1 can take two possible configurations. When these configurations of both peptides are put on surfaces, side chains of all the d-residues always orientate oppositely to those of all the l-residues with respect to the surfaces.

In taking account of the condensation and expansion of these monolayers, together with those of tyrocidine A and B and gramicidin SA, it was concluded that cyclic peptides give more condensed monolayers as the contents of prolyl residue are higher. Thus a prolyl residue plays the same role in cyclic peptides as in linear polypeptides.

Gramicidin J1 gave a monolayer of more expanded type on a neutral subphase, and exhibited a characteristic behavior common with ionized monolayers when neutral salt such as potassium chloride was added. At very large areas the the behavior was adequately explained by the theory of the electric double layer, when only one ionized residue was assumed to concern the double layer.
Systematic Separation of Fission Products by Solvent Extraction Method
Authors: Kiba Toshiyasu , Ohashi Shigeru , Maeda Toyoo
Published: July 2006

A new scheme for separating fission products, zirconium-niobium-95, cerium-144, promethium-147, yttrium-90, strontium-90, ruthenium-106 and cesium-137, by the four-step liquid-liquid extractions was presented. First, zirconium-95 and niobium-95 were extracted from a 5 m hydrochloric acid solution into chloroform with cupferron. Second, rare-earth nuclides, cerium-144, promethium-147 and yttrium-90 were extracted from an acetate buffered solution of pH 4 to 5 into chloroform with cupferron. Third, strontium-90 was extracted from an acetate buffered solution of pH 8 into hexone (methyl isobutyl ketone) with TTA (2-thenoyltrifluoroacetone). Fourth, ruthenium-106 was extracted from 5 m hydrochloric acid solution with TBP (tri-n-butyl phosphate)-kerosene in the presence of stannous chloride or extracted with TBP in the presence of hydroxylamine. then cesium-137 was left in the last aqueous solution. Strippings of nuclides extracted in the organic phases could be attained by shaking each organic phase with nitric acid.
Ultraviolet Absorption Spectra of Aqueous Solutions and Single Crystals of Thioacetamide and Thiourea
Authors: Hosoya Haruo , Tanaka Jiro , Nagakura Saburo
Published: July 2006

Ultraviolet absorption spectra of thioacetamide and thiourea are measured under various conditions. In aqueous solution, three bands (210, 261 and 318 mμ) for thioacetamide and two bands (195 and 236 mμ) for thiourea are observed. Further, polarized ultraviolet absorption spectra are measured with their crystals. On the basis of the results regarding the polarized ultraviolet absorption spectra, the directions of transition moments can be determined as follows : 1) the directions of transition moments of the 261 and 210 mμ bands of thioacetamide are approximately parallel to the axis connecting the nitrogen and sulfur atoms and connecting the nitrogen and methyl carbon atoms, respectively, 2) the directions of transition moments of the 236 and 195 mμ bands of thiourea are parallel and perpendicular to the C=S axis, respectively. From the combination of the experimental results concerning the directions of transition moments with theoretical consideration based on semi-empirical LCAO treatment including configuration interaction, the assignment of the four absorption bands under consideration are finally determined. One of the noticeable conclusions is that the 195 mμ band of thiourea can be regarded as a typical intramolecular charge-transfer absorption.

It is shown that in the hydrochloric acid solution of thioacetamide the 261 mμ band decreases its intensity and a new band appears at 237 mμ. By measuring the dependence of intensities of these two bands upon the acid strength of the solution, it is concluded that the 237 mμ band is due to the conjugate acid of thioacetamide. The pKB value of thioacetamide is determined spectrophotometrically to be 1.2 at 24.5°C. From the comparison of the wavelength of the peak absorption of thioacetamide with that of its conjugate acid, it is seen that the proton is conceivably attached to the amino group.
On the Mechanism of the Extraction of Uranyl Nitrate by Tributyl Phosphate II. Infrared Study
Authors: Nukada Kenkichi , Naito Keiji , Maeda Utako
Published: July 2006

The complex formation of TBP in the systems-TBP-water, TBP-nitric acid, and TBP-uranyl nitrate was confirmed by means of infrared spectroscopy. The infrared spectra of uranyl nitrate in the system TBP-nitric acid-uranyl nitrate lead to the conclusion that the competition extraction of both uranyl nitrate and nitric acid takes place during the extraction process.
Effect of Temperature on the Viscosity and the Optical Rotation of Poly-ε-aminocaproyl-α-alanine
Authors: Ebata Mituo
Published: July 2006

Viscosity and optical rotation of a synthetic polymer, poly-ε-aminocaproyl-α-alanine, were studied connecting with the reversible heat coagulation. A minimum viscosity of the poly-ε-aminocaproyl-D,L-alanine solution was found at 55°C. Heating of the poly-ε-amino-caproyl-l-alanine solution produces an increase in its levo-rotation and a shift of its dispersion constant (λc value) to shorter wavelength. The mechanism of the reversible heat coagulation of the polymer was discussed to be based on the obtained result.
Quantitative Spectrochemical Analysis of Minor Elements in Silicates with Double Internal Standards
Authors: Hamaguchi Hiroshi , Kuroda Rokuro , Negishi Ryokichi
Published: July 2006

Two internal standards have been used in the spectrographic analysis of silicates, antimony(III) oxide for volatile elements and palladium black for the involatile group. The former was used as the standard for the determination of gallium, lead and tin, and the latter for the determination of nickel, cobalt, chromium, vanadium and scandium. A medium spectrograph is not suitable for the determination of chromium or tin, and scandium did not volatilize in a manner parallel to the palladium but it was possible to obtain reasonable results for the other elements.
Absorption Spectra of Dyes. VI. Steric Effects in Conjugated Systems of Benzidine Disazo Dyes and their Copper Derivatives
Authors: Kobayashi Teruaki , Tanizaki Yoshié , Ando Noboru
Published: July 2006

1. Absorption spectra of benzidine disazo dyes and their copper derivatives in aqueous solution were measured at room temperature, and they are compared with one another.

2. It was shown by a simple calculation that the dyes, each of which has sulfonic groups adjacent to the azo groups, have strained conformations caused by the repulsion between the sulfonic groups and the unshared electrons of nitrogen. It was also shown that the relationship between the relative positions of sulfonic groups to the azo groups and the relative absorption intensities could well be explained.

3. The absorption intensities of the copper derivatives were nearly equal, having no relation to the positions of the sulfonic groups, and in addition they were near to those of the non-copper dyes which have the sulfonic groups adjacent to the azo groups. Hence, it was pointed out that the introduction of copper caused the same extent of strain in conjugated systems as sulfonic groups did.
Paramagnetic Resonance of Radicals of Some Aromatic Vinyl Compounds. I
Authors: Morigagi Kazuo , Kuwata Keiji , Hirota Kozo
Published: July 2006

Paramagnetic resonance of radicals of the aromatic vinyl compounds in the tetrahydrofuran and dioxane solutions was observed: styrene, α-methyl styrene and p-methyl styrene. By analyzing the observed spectra the structure of the radicals is discussed. From these results it may be concluded that the reaction of the aromtic vinyl compounds with alkali metal proceeds through two steps ; formation of their radical anions, and successive addition of the monomers to this radical anion turning into “living polymers”.
Paramagnetic Resonance of Radicals of Some Aromatic Vinyl Compounds. II
Authors: Morigaki Kazuo , Kuwata Keiji , Hirota Kozo
Published: July 2006

Paramagnetic resonance absorption of the radicals of 1,1-diphenylethylene, stilbene and 1,4-diphenylbutadiene in tetrahydrofuran solution was investigated at room temperature. In diphenylethylene (DPF) radicals two kinds of spectra were observed corresponding to two states of the radicals; one is the DPE monomer anion and the other DPE polymer anion. In connection with the experimental results in the case of styrene, α-methylstyrene and p-methylstyrene described in the preceding paper, the process of polymerization of some aromatic vinyl compounds was discussed.
Hydrogen Peroxide Oxidation. V. Selenium Dioxide Catalyzed Oxidative Rearrangement Reaction of Desoxybenzoin
Authors: Sonoda Noboru , Tsutsumi Shigeru
Published: July 2006

1) Selenium dioxide catalyzed oxidation of desoxybenzoin with hydrogen peroxide in tertiary butyl alcohol gave diphenyl acetic acid which was produced by the rearrangement of phenyl group to the methylene carbon atom.

2) Baeyer-Villiger reaction was also occurred competitively in this reaction system, and benzyl benzoate was isolated as ester from the neutral products. Such an observation shows that the active oxidizing species may be some kind of peroxyacid. This fact is consistent with our previous assumption that peroxy-selenious acid is the most probable catalytic form.

3) It is assumed in the reaction path of the formation of the rearranged carboxylic acid that the initial state of the attack of the peroxyselenious acid to the ketone may be analogous to that of selenious acid. From this point of view, a possible reaction path was proposed.
Kerr Effect in Liquid State
Authors: Okabayashi Hideo
Published: July 2006

A formula for the Kerr constant in liquid state has been derived, in which the form of the local field is assumed to be the same as that derived previously. The formnla is able to explain experimental data to some extent, although there are some exceptions.
Organic Semiconductors with High Conductivity. III. Perylene-Iodine Complex
Authors: Uchida Tokiko , Akamatu Hideo
Published: July 2006

Concerning the solid complex of perylene-iodine system, it has been clarified that two sorts of molecular addition compounds are formed. One has the composition of Perylene· 1.5 I2 (or 2 Perylene· 3 I2) and the other is Perylene· 3 I2. Both complexes are semiconductive with low resistivity; the resistivity at the room temperature is 9∼10 ohm.cm. and the energy gap is 0.06 eV. Concerning those values, both complexes possess almost the same values. Not only the elecrical properties and the magnetic properties, but also, both complexes possess similar crystal structures. To explain those facts, the structural units for those complexes have been proposed. These consist of the conjugation between perylene molecules and iodine molecules with the charge tranfer type of interaction.
Polarographic Determination of the Formation Constant of Sulfatonickel(II) Complex
Authors: Tanaka Nobuyuki , Ogino Hiroshi
Published: July 2006

A method for the determination of the formation constants of less stable metal complexes has been developed. The method is based on the polarographic measurement of the sum of the equilibrium concentrations of hydrated metal ions and the complexes coordinating with acetate and/or co-existing ions in the presence of an appropriate auxiliary complex-forming substance. Essential advantages of the method are those of the method that was previously reported and applied to the formation constants of acetatonickel(II) complex.

The procedure developed is applied to the study of the nickel (II) complexes present in the acetate buffer solution containing nitrilo-triacetate as an auxiliary complex-forming substance and sulfate as co-existing ions. The results obtained reveal that, under the experimental condition, the monoacetatonickel(II) ions NiOAc+ and the monosulfatonickel(II) NiSO4 are present in the solution but not the acetatosulfatoniccolate(II) Ni(OAc)(SO4)−. The formation constants of monosulfato complex, KNiSO4, at ionic strength 0.2 are calculated to be 14.3±0.4 at 15°C, 11.6±0.9 at 25°C and 14.6±0.7 at 35°C.
Photoreduction of Methylene Blue by Visible Light in the Aqueous Solution Containing Certain Kinds of Inorganic Salts. II. Photobleached Product
Authors: Obata Hiroshi
Published: July 2006

In order to identify the photobleached substances which are produced when the aqueous solution of methylene blue is irradiated with visible light, the following three kinds of experiments were carried out.

1) Comparison of the absorption spectra of the photobleached product with those of leucomethylene blue, benzoylleucomethylene blue and acetylleucomethylene blue.

2) Comparison of the oxidative and reductive behavior of the photobleached product with that of leucomethylene blue.

3) Comparison of the pH dependence of the absorption spectrum of the photobleached product and that of leucomethylene blue.

It was concluded that the photobleached product is the leuco form dye and its oxidized form is most certainly a partially demethylated methylene blue, perhaps methylene azur A.
Infrared Spectra of Cyclohexanoxime and Cyclohexanoxime-d
Authors: Kimura Masao , Kuroda Yoko , Yamamoto Osamu , Kubo Masaji
Published: July 2006

The infrared absorption bands due to the functional group of cyclohexanoxime and cyclohexanoxime-d were reasonably assigned by taking into account the concentration dependence of these bands in solutions. Cyclohexanoxime having no conjugate system showed a spectral feature different in many respects from that of diacetyl monoxime or isonitrosoacetone already studied. The type of hydrogen bonding is −OH…N=C< both in solutions and in the solid state. Consequently, the stretching frequency of bonded OH groups of cyclohexanoxime is different from those of diacetyl monoxime and isonitosoacetone. The doubling of absorption bands was observed for both the OH in-plane bending vibration and the NO stretching vibration of free molecules. This suggests the presence of rotational isomers. The wave numbers of the C=N stretching vibration is higher, while that of the NO stretching vibration is lower than those of the corresponding vibrations of diacetyl monoxime and isonitrosoacetone. This indicates that the double bond character of the C=N bond in cyclohexanoxime is greater than that in oximes having a conjugate system.
Dye-sensitized Photopolymerization of Vinyl Compounds. Polymerization of Acrylonitrile by Stannous Chloride and Acriflavine. I
Authors: Watanabe Ai , Koizumi Masao
Published: July 2006

When the aerated solution of acrylonitrile, acriflavine and stannous chloride in the mixture of water and dimethylformamide is irradiated by the visible light, the polymerization of acrylonitrile immediately takes place. The presence of water and oxygen was found to be unnecessary for the reaction to occur. The dependence of rate on the concentration of each species and on the light intensity (I0) can be summarized as follows.

Acriflavine <ca. 1×10−5m, 1st order;

>ca. 3.5×10−5m, const.

Stannous chloride <ca. 3.5×10−3m, 1st order;

>ca. 1.2×10−2m, const.

Acrylonitrile, 2nd order

I 0, 1/2th order

It was further found that the average degree of polymerization is proportional to the monomer concentration. The scheme involving the photoreduction of dye by stannous chloride and its recovery by the existent oxygen cannot explain the present result. It was proposed as a new mechanism that a transient metallic ion of tin with an odd valency is formed and this, interacting with acrylonitrile, initiates the polymerization.