bluuebunny/crossref_metadata_2025_split huggingface dataset:
Flash Photolysis of Methylene Blue. I. Reversible Photolysis in the Absence of a Reducing Agent and in the Presence of Certain Kinds of Reducing Agents
Authors: Matsumoto Shiro 
Published: July 2006

Abstract
Transient spectra which appear in the flash photolysis of methylene blue in aqueous solvents of various pH values have been surveyed both in the absence and in the presence of a reductant. In the absence of a reductant, the triplet state of the dye has been observed to appear in two forms, with different degrees of protonation. The form found in neutral water seems to be formed directly from the excited singlet state of the dye. The pKA value of the acid-base equilibrium has been found to be approximately 6.8. A second transient has been found to be produced in water and in buffer solutions of a moderate pH value at a later stage of the photolysis. Its formation is more marked in buffer solutions, and it may be supposed to be a sort of charge-transfer complex between an excited dye ion and another dye component. The photolysis in the presence of ferrous ions, p-phenylenediamine or benzohydroquinone is nearly reversible, and the absorption of the original dye is restored after the illumination except in an extremely alkaline solution. The transitory formation of leuco methylene blue has been observed when ferrous sulfate or hydroquinone was used as the reductant below a pH value of 8.4, while that was not the case with p-phenylenediamine. The formation of leuco methylene blue from semiquinone has been found to be a bimolecular dismutation process in an acid medium when ferrous ions are the reductant, but when hydroquinone is used as the reductant at moderate pH values, it also reduces the methylene blue semiquinone. When hydroquinone is used as the reductant in a neutral or alkaline solvent, an increase in absorption is often observed at some longer wavelengths; this has tentatively been attributed to a complex between excited dye ions and reductant molecules. A comparison of the transient spectra obtained in various conditions has shown that the semiquinone of methylene blue exists in variously protonated forms in the following ranges: pH&gt;9, pH=3∼8, in 0.1∼1 n sulfuric acid, and in very concentrated sulfuric acid. The pH dependence of the quantum yield of the photoreduction obtained earlier has been tentatively related to the change in the degree of protonation of the triplet state and the semiquinone.
Flash Photolysis of Methylene Blue. II. Photolysis in an Aqueous Solvent in the Presence of N-Phenylglycines and Photolysis in Organic Solvents
Authors: Matsumoto Shiro 
Published: July 2006

Abstract
The flash photolysis of methylene blue in an aqueous medium with added N-phenylglycines or photolysis in organic solvents results in a more or less apparent bleaching of the dye. In the former case, the general features of the transient spectra are similar to those in the reversible photolysis treated in Part I. An absorption peak at 400 mμ in a solvent with a pH of 8.0 shifts to 430 mμ in a solvent with a pH of 8.8 ; it is to be attributed to the semiquinone of methylene blue. The absorption around 255 mμ increases at a later stage of the reaction, indicating the formation of leuco methylene blue. The photolysis seems to proceed in a way similar to that of the reversible cases. The results of flash photolysis with several derivatives of N-phenylglycine support the general idea of their reactivity obtained in a study with continuous illumination. There is a difference between the ways in which N-p-bromophenylglycine and N-p-methoxyphenylglycine retard the photoreduction, although this may be superficial. In the former case, some early intermediate (probably the triplet state of the dye) is deactivated almost catalyticaly, while in the latter case the deactivation takes place at the stage of a long-lived semiquinone-like intermediate. Peculiar features of photolysis with α-methyl-N-phenylalanine and N-phenyl-β-alanine have also been noted.
The degree of irreversible bleaching in an organic solvent has no regular relation to the ease with which the solvent molecule is dehydrogenated by an ordinary oxidant. The main part of the transient absorption in organic solvents is attributed to the semiquinone of the dye. The peak has somewhat red-shifted compared with that in water. Triplet absorption seems also to appear at an early stage of photolysis. The photolysis in 1- or 2-propanol reveals the reversible feature observed when ferrous ions were used as reductants.
A Convenient Method for the Monobromination of Active Methylene Compounds
Authors: Hata Tsujiaki 
Published: July 2006

Abstract
The monobromination of the active methylene compounds by means of the proportionation procedure between the active methylene compound and its dibromo-derivative has been investigated.
Next, the monobromination of various active methylene compounds by the use of dibromomalonitrile has been tried. The method proved remarkably effective for the synthesis of α-mono-bromoderivatives of active methylene compounds containing a phenyl group.
The Absorption Spectra of Chromium(II) Acetate and Copper(II) Acetate
Authors: Kida Sigeo , Nakashima Yoshiaki , Morimoto Yukiyoshi , Niimi Kiyoshi , Yamada Shoichiro 
Published: July 2006

Abstract
The electronic absorption spectra of chromium(II) acetate have been determined in ethanol and Nujol mull in the region between 10 and 40 kK. Dichroism in that region has also been determined with a single crystal of the compound. A new absorption band, which has not previously been observed, has been found at about 30.77 kK. (logε 2.22), in addition to a band at about 20.58 kK.
The origins of these bands have been discussed in relation to the absorption bands of copper (II) acetate.
The Ultrasonic Velocity and Absorption of Aqueous Solutions of Polyvinyl Alcohol
Authors: Arakawa Kiyoshi , Takenaka Nobuo , Watase Mineo , Kubota Kazunari 
Published: July 2006

Abstract
An ultrasonic pulse technique has been applied to measure the velocity and absorption of the longitudinal sound wave in aqueous solutions of polyvinyl alcohol at ultrasonic frequencies. Two samples of polyvinyl alcohol have been used: sample A, completely saponified polyvinyl alcohol, and, sample B, partially saponified Polyvinyl alcohol (including residual acetate groups by 12.2 mol.%). The following results have been obtained.
1) Ultrasonic velocity and absorption have been measured over the temperature range of 3∼70°C in the concentration range of 5∼15% by weight.
2) For sample A the temperature dependence of velocity is similar to that for pure water, but for sample B the velocity vs. temperature curves have been found to have a broader peak.
3) Concerning the concentration dependence of the velocity, in sample A the sound velocity increases with the increase in the concentration, but in sample B a reverse dependence of velocity on concentration has been found at higher temperatures.
4) The value of M2/ω amounts to about 2∼3 poises on the average for both samples.
5) The compressibility of polymer molecules in solutions has been calculated to be 26.5×10−12 c.g.s.u. on the average for completely saponified polyvinyl alcohol.
The Polarography of Terephthalaldehydic Acid
Authors: Nishiyama Masataka , Maruyama Masao , Hamaguchi Hiroshi 
Published: July 2006

Abstract
The d. c. and a. c. polarography of terephthalaldehydic acid has been investigated in buffered solutions containing no ethanol over the pH range from 1 to 13.
D.C. Polarography.–Terephthalaldehydic acid gives a pre-wave and three reduction waves. The pre-wave, which is due to the adsorption of the reduced form of undissociated molecules, is followed by wave I below pH 4.4. Our results above pH 4.4 accord approximately with Holleck and Marsen’s. The half-wave potential for the wave I is pH-dependent, and the E01⁄2 is −0.69 V. vs. SCE. The half-wave potentials of waves II and III, both pH-independent, are −1.30 and −1.60 V. vs. SCE under the conditions studied. The sum of the wave heights has been kept constant in the pH range from 4.4 to 13.2, and it corresponds to the two-electron reduction of the carbonyl group. The two-step waves, in which wave I is due to the reduction of the undissociated molecule and wave II, to that of its anion, in the pH range from 5.5 to 7.5 form a system of kinetic recombination currents. The recombination and dissociation rate constants have been calculated as kr=1.5×1081. (mol. sec.)−1 and kd=5.2×103 sec−1. The double waves above pH 8.2 have been explained by the carbinolate-free radical dissociation theory.
A.C. Polarography.–A. c. waves have been obtained to corresponding to the d. c. waves. The heights of the a. c. pre-wave and wave I are depressed below pH 5. This depression has been attributed to the strong adsorption of undissociated molecules at the dropping mercury electrode. The relationship between the a. c. wave height and concentration below pH 5 is non-linear. It has been noted that the a. c. kinetic current should be taken into account for the a. c. wave formation.
The electrode process for wave III is irreversible, and a. c. wave III is ill-defined.
A reduction mechanism over the pH range studied has been proposed.
Studies of Isocyanide. II. The Reaction of Isocyanide with Some Radical Sources
Authors: Shono Tatsuya , Kimura Masatoshi , Ito Yoshihiko , Nishida Kiyoto , Oda Ryohei 
Published: July 2006

Abstract
The reactions of cyclohexyl isocyanide with some radical sources, such as perbenzoic acid, benzoyl peroxide, t-butyl perbenzoate, N-nitrosoacetanilide, potassium phenylazoformate and di-t-butyl peroxide, have been studied. The isocyanide does not contribute kinetically to the mechanism of the decomposition of benzoyl peroxide, but the lone pair electrons existing on the carbon atom of isocyanide react very easily with free radicals, especially with acyloxy radicals.
In the reaction with benzoyl peroxide, t-butyl perbenzoate or the N-nitrosoacetanilide acyloxy radical chiefly contributes to the reaction. With potassium phenylazoformate, the phenyl radical is the main reacting species. However, in the case of perbenzoic acid, the reaction is heterolytic, and the main product is cyclohexyl isocyanate.
Synthetic Studies Starting from β-Cyanopropionaldehyde. I. The Synthesis of Adipic Dialdehyde
Authors: Motoki Shinichi , Satsumabayashi Sadayoshi , Tajima Isao 
Published: July 2006

Abstract
A detailed study has been made of the synthesis of adipic dialdehyde starting from β-cyanopropionaldehyde. The hydrolysis of the acetal of this cyanoaldehyde gave β-formylpropionic acid acetal, to which Kolbe’s electrolytic reaction was applied. The intermediate acetal acid has been successfully isolated in the case of ethylene acetal, whereas ethyl or butyl acetal decomposed by distillation into ethoxy or butoxy-γ-butyrolactone, the structure of which has been established by analysis, infrared spectra and conversion to β-formylpropionic acid. Methyl acetal was also readily hydrolyzed to free aldehydic acid during the course of the isolation. Electrolysis of the ethylene acetal of β-formylpropionic acid in methanol gave adipic dialdehyde as its diethylene acetal.
Synthetic Ammonia Iron Catalysts Containing Magnesia as Its Principal Promoter. I. The Catalysts’ Performances
Authors: Uchida Hiroshi , Terao Iwao , Ogawa Kiyoshi 
Published: July 2006

Abstract
A catalyst promoted singly by magnesia can be as active as one promoted singly by alumina. The activity of the former catalyst is increased by a succeeding reduction at 650°C to a higher level; the increased level is preserved even after the prolonged heating at this temperature. Potash, lime, and silica added as second promoters behave in their respective peculiar manners. Among the catalysts under investigation, a triply-promoted catalyst performs in nearly the same way as one of the catalysts of the alumina-promoted type in current use in industrial ammonia synthesis, provided the amounts of such kinds of promoters as magnesia, potash, and silica are appropriate.
The activity or the rate constant is expressed as a function of the temperature-independent parameters, which are the bed density, the specific surface area, activation energy, the frequency factor per unit of the catalyst surface area, and the reaction temperature. The effects of individual promoters have been discussed in view of the changes in magnitude of each parameter which result from their additions.
The catalysts of the magnesia-promoted type can be reduced much more easily than the catalysts of the alumina-promoted, type, but the reduction rate is only a little below that of the unpromoted catalyst.
The Direct Spectrophotometric Determination of Iron with Dibenzoylmethane in the Organic Phase
Authors: Umezaki Yoshimi 
Published: July 2006

Abstract
A method has been described for the direct spectrophotometric determination of up to 40 μg. of iron (III) with DBM in the organic phase.
An orange complex, which is formed with the addition of DBM and pyridine to the MIBK extract of iron, has a maximum absorbance at 410 mμ. The effect of the diluent on the color reaction has been studied; methanol has been selected as the best diluent of those tried. The color reaction conforms to Beer’s law and has a sensitivity of 0.0046 μg. Fe/cm2 for −logT=0.001. The effects of diverse ions on the determination of iron have been studied; it has been found that this method is simple and is sensitive and selective to iron.
The Condensation of Acetonitrile with Formaldehyde
Authors: Ogata Yoshiro , Izawa Yasuji , Osumi Yasuo 
Published: July 2006

Abstract
The condensation of acetonitrile with formaldehyde using sodium naphthalene as a base catalyst has been studied. The results showed that formaldehyde reacted with acetonitrile through the aldol-type condensation to form ethylene cyanohydrin (1.0∼7.7%). 2,4,6-Trimethyltriazine was detected as one of the by-products.
The Rheological Properties of Concentrated Suspensions. III. Dynamic Properties and Their Correlations with Stationary Flow Properties
Authors: Takano Masaharu 
Published: July 2006

Abstract
The dynamic properties and stationary flow properties of suspensions of barium sulfate in polyisobutylene and in linseed oil have been measured by the use of an electrically-recording rotational rheometer.
The concentration dependence, the influence of mixing conditions, the effects of the addition of water and of sodium stearate on the dynamic viscosity and the dynamic modulus, and the correlation of the dynamic properties with stationary flow properties have been examined experimentally.
In suspensions of barium sulfate in linseed oil, the dynamic viscosity and dynamic modulus increase monotonously with an increasing concentration, and no critical concentration is observed up to the highest concentration. The apparent relaxation time shows a slight increase with an increase in the concentration of particles.
In suspensions of barium sulfate in polyisobutylene, the dynamic viscosity and dynamic modulus increase abruptly above a critical concentration. The apparent relaxation time also increases remarkably above the critical concentration. The mean free energy of the activation for breaking links between particles and the mean number of links to be broken for the separation of two neighboring particles have been evaluated as 33∼34 kT and 1.49 respectively.
The influence of additives on dynamic properties resembles that on stationary flow properties and can be explained qualitatively by assuming a van der Waals-London attraction between particles. However, in a viscoelastic medium, contractive forces arising from the elastic property of the medium seems to be altered by the addition of additives.
For pseudo-plastic systems, the dynamic viscosity coincides with the apparent viscosity at lower frequencies. However, for plastic systems, the apparent viscosity may be higher or lower than the dynamic viscosity at lower frequencies, depending on the sensitivity of the network structures formed by particles and on the time necessary for the restoration of broken structures. The dynamic modulus at lower frequencies increases with an increase in the yield value, while the former increases proportionally to the latter at higher concentrations also.
The non-linearity of dynamic properties has been observed as a feature of their amplitude dependence. The change in the dynamic modulus is more remarkable than that in the dynamic viscosity.
The experimental results described above at least qualitatively agree with the theoretical predictions based on a network model.
The Photometric Determination of Titanium with Acetylacetone
Authors: Fujiwara Shizuo , Nagashima Kozo , Codell Maurice 
Published: July 2006

Abstract
A new method has been proposed for the determination of small amounts of titanium in various substances. Acetylacetone forms an intensely-colored red complex in an acid solution with titanium(III), but this complex had not previously been used for the photometric estimation of titanium, probably because of the great instability of its color. A process has now been proposed for stabilizing the color. Up to 30 mg. of niobium and 30 mg. of iron do not interfere. Interference is encountered from chromium and vanadium, and in their presence, or in the presence of more than 30 g. of iron, a mercury cathode separation must be made. The method has been applied to quantities of titanium as small as 0.2 mg. in 50 ml. of solution.
The Synthesis and 1,4-Addition Type Ring-opening Polymerization of N-Substituted Cyclic Iminocarbonates
Authors: Fujisawa Tamotsu , Tamura Yorikazu , Mukaiyama Teruaki 
Published: July 2006

Abstract
As one of a series of studies of 1,4-addition type ring-opening polymerizations, the synthesis and ring-opening polymerization of N-substituted cyclic iminocarbonates have been studied.
N-Alkyl and N-aryl cyclic iminocarbonates have been prepared by the reaction of sodium ethylene glycorate with the corresponding imidophosgenes. N-Halogeno cyclic iminocarbonates have been prepared from glycols, potassium cyanide and halogenes.
The ring-opening polymerization of the N-substituted cyclic iminocarbonates, which are considered to be cyclic enol derivatives of urethanes, in the presence of cationic catalysts gives the corresponding poly(ethylene N-substituted carbamates).
The Preparation of Poly(ethylene N,N′-Disubstituted Ureas) by the 1,4-Addition Type Ring-opening Polymerization of 2-Imino-1,3-oxazolidines
Authors: Nohira Hiroyuki , Nishikawa Yoshihiro , Mukaiyama Teruaki 
Published: July 2006

Abstract
Various 2-imino-1,3-oxazolidines have been prepared from β-chloroethylureas or from ethanolamines and cyanogen bromide.
N,N′-Disubstituted 2-imino-1,3-oxazolidines give poly(ethylene N,N′-disubstituted ureas) by 1,4-addition type ring-opening polymerization in the presence of a cationic catalyst such as boron trifluoride etherate. On the other hand, 2-unsubstituted imino-1,3-oxazolidines polymerize with difficulty and give polymers with low melting temperatures.
Radiolysis of Solid Glycine
Authors: Meshitsuka Gisuke , Shindo Kotaro , Minegishi Atsuko , Suguro Hiroshi , Shinozaki Yoshiharu 
Published: July 2006

Abstract
Solid glycine has been radiolyzed by 60Co γ-rays in vacuo at room temperature, and all the products except H2 have been measured after dissolving the irradiated samples in water. The hydrogen has been collected and measured directly from the irradiated solid samples. All products except H2 increase linearly with the dose, while H2 shows a plateau from a relatively low dose. The yields of products are as follows: G(H2)∼0.2, G(NH3)=4.8, G(CH3NH2)=0.2, G(CHOCO2H)=2.5, G(CH3CO2H)=2.3, G(CO2)∼0.2, and G(HCHO)∼0.03. The mechanisms of the primary process and the reactions to give final products have been proposed with reference to the results of the ESR studies.
The Bromination of Aromatic Compounds with a Mixture of Peroxyacetic Acid and Bromine in Acetic Acid
Authors: Ogata Yoshiro , Furuya Yoshiaki , Okano Kenji 
Published: July 2006

Abstract
Bromobenzene is obtained in a 56% yield when an acetic acid solution of peroxyacetic acid is slowly added to an acetic acid solution of bromine, benzene and a catalytic amount of sulfuric acid. The rate of the consumption of peroxyacetic acid has been expressed as v=k2 [CH3CO3H] [Br2], where k2 is independent of the concentration of benzene and of the acidity of solution. However, the rate of the formation of bromobenzene is accelerated by sulfuric acid and a more effective use of the attacking species is possible. A mechanism has been suggested which involves the ratedetermining formation of bromine monoxide or acetyl hypobromite, followed by its rapid attack on benzene. The rate is slower with benzene substituted with electron-attracting groups. Some evidence for the formation of acetyl hypobromite has been obtained by ultraviolet spectrophotometry.
Syntheses and Ultraviolet Spectra of Aromatic Azo Compounds. III. Methoxyazobenzene Derivatives
Authors: Nomura Yujiro , Anzai Hiroyuki , Tarao Ryokichi , Shiomi Kengo 
Published: July 2006

Abstract
1) Nine tolylazoanisoles, six dimethoxyazobenzenes, and six bromophenylazoanisoles have been synthesized by the reactions of Grignard reagents with zinc chloride double salts of diazonium compounds; thirteen of them are new compounds.
2) The ultraviolet and visible absorption spectra of the methoxyazobenzene derivatives have been measured, and some regularities of the absorption maxima have been observed in them.
Syntheses and Ultraviolet Spectra of Aromatic Azo Compounds. IV. Naphthylazobenzene Derivatives
Authors: Nomura Yujiro , Anzai Hiroyuki 
Published: July 2006

Abstract
1) α- and β-Naphthylazobenzene and their twenty-four derivatives with a substituent on a benzene ring have been synthesized by the reactions of Grignard reagents with zinc chloride double salts of diazonium salts. Twenty-one of them are new compounds.
2) Six naphthylazobenzoic acids have been prepared by the hydrolysis of the corresponding ethyl esters; five of them are new compounds.
3) The ultraviolet and visible absorption spectra of these naphthylazobenzene derivatives have been measured.
The Inhibitive Behavior of the Fluoride Ion and the Destruction of Its Protective Film in the Corrosion of Magnesium in Neutral Solutions
Authors: Wada Goro , Maekawa Seihei 
Published: July 2006

Abstract
Fluoride ions exhibit an anomalous inhibitive ability against the corrosion of magnesium ; this may be attributed to the formation of a fine film of insoluble magnesium fluoride. This film conducts the cathodic current fairly well, but it conducts the anodic current not at all, as far as it is not destroyed. The cathode reaction through the magnesium fluoride film has a low apparent activation energy because of its electronic conduction, while, when magnesium is anodically polarized, the film is no longer electron-conductive and still permits to a lesser extent the diffusion of any other charged particles; consequently, this is a kind of rectifier in a solution containing potassium fluoride alone.
If a solution contains chloride ions in addition to fluoride ions, the matter is quite different and fluoride ions rather promote the corrosion, like other halide ions. When magnesium, the surface of which has previously been covered with magnesium fluoride is anodically polarized in a solution containing only chloride ions or containing fluoride ions as well as chloride ions, the film soon begins to be destroyed at the initial stage, the bare area of high conductivity appears, and then the surface is gradually again covered with the bulky products, magnesium hydroxide, at the later stage. The destruction of the magnesium fluoride film may occur through a mechanical process regardless of the presence of fluoride ions.