bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Superstructure in Fine Aragonite Particles
Authors: Hiragi Yuzuru , Kachi Sukeji , Takada Toshio , Nakanishi Norihiko 
Published: July 2006

Abstract
An electron diffraction study was done with fine aragonite particles about 0.5 to 1.0 μ in size. The specimens were obtained by mixing a boiled calcium chloride solution (0.1 n) with 0.1 n of an ammonium carbonate solution. Extra spots were observed with half-integer indices {1⁄2,1⁄2,l}. This suggests the existence of a structure that differs from that of normal aragonite. From an X-ray diffraction study of the specimen, a {1/2, 3/2, 0} diffraction was also observed. The structure for explaining these half-integer diffractions is presented as a superstructure of aragonite; it belongs to the space group of D2h15−Pbca, with cell dimensions of A=8.420 Å, B=9.385 Å, and C=5.741 Å, and it containes 8 formula units in a unit cell. A dark-image photograph shows this anomalous area to be comparatively wide and suggests that the anomalous area is dominant in a crystal. The authors conclude that rapidly-precipitated aragonite powders contain a small quantity of the repeatedly-twinned crystals mentioned above.
Non-Debye Reorientation Processes of Molecules. Correlation Functions and Spectral Densities for Spherical Molecules
Authors: Shimizu Hiroshi 
Published: July 2006

Abstract
The non-Debye reorientation processes in which the Debye equation is inapplicable are studied for spherical molecules by using an equation proposed by the author. The physical meaning of the angular correlation in the non-Debye processes is discussed in detail. It is shown that in the non-Debye processes the non-dissipative decay of the mutual-phase correlation of rotating molecules must be taken into account, in addition to the dissipative decay due to molecular collisions, and that the use of the “microscopic viscosity” in the Debye equation is not plausible. It is also shown that, in contrast to the Debye processes, there is no one-to-one correspondence between the correlation time for molecular reorienation and the mean life time of the rotation, since the contribution from the nondissipative decay should be considered also. The vector and the tensor correlation functions,
〈cosθ(0)cosθ(t)〉 and 〈(1⁄2){3cos2θ(0)−1}{(1⁄2)3cos2θ(t)−1}〉,
and the corresponding spectral densities, the band shapes of infrared and Raman spectra respectively, are obtained theoretically for various conditions and are shown graphically. As illustravtie examples of the treatment, methane and deutero methane molecules are studied. Vector correlation functions are obtained from the observed band shapes of the infrared spectra of these molecules. Comparing the theoretical correlation functions with experimental ones, it is shown that a reasonable agreement between theory and experiment is obtained and that methane molecules have a typical non-Debye reorientation process even below the freezing point. Some characteristic features of the non-Debye process are also discussed.
A Study of the Hydration of Calcium Orthoplumbate. VII. The Mechanism of the Formation of Hydrate
Authors: Koishi Masumi 
Published: July 2006

Abstract
The hydration processes of calcium orthoplumbate are studied by means of a twin-type conduction calorimeter. The curves of the differential electromotive force vs. the hydration time have two characteristic maxima, corresponding to two exothermic processes: the first one is due to the immersion and dissolution of calcium orthoplumbate, while the second one is caused by the formation of crystalline hydrates. The heat liberated by the first process is about 1.14 cal./g. Ca2PbO4, while that liberated by the second process is about 52.22 cal./g. Ca2PbO4. The reaction in the second process proceeds by the 2/3 order; this may be explained by assuming that the rate of the reaction is determined by the surface area of the calcium orthoplumbate being hydrated.
Metal Complexes of Amino Acids. III. The Circular Dichroism of Cobalt(III) Ammine and Ethylenediamine Complexes with l-Amino Acids
Authors: Yasui Takaji , Hidaka Jinsai , Shimura Yoichi 
Published: July 2006

Abstract
In order to study the vicinal effect of the l-amino acid coordinated in a complex on the central metal ion, a number of cobalt(III) l-amino acid complexes of three types were prepared, i. e., [Co(NH3)5(l-amH)]X3, [Co(l-am)(NH3)4]SO4, and trans-[Co en2(l-amH)2]X3, where l-amH denotes an l-amino acid, and where X is Cl, Br, or I. The circular dichroism (CD) and the rotatory dispersion (RD) spectra of their aqueous solutions were measured in the wavelength range from 650 to 300 mμ. In the region of the first absorption band, both the [Co(NH3)5(l-amH)]3+ and the trans-[Co en2(l-amH)2]3+ ions show one or two CD bands to be expected in complexes of the C4v symmetry with a structure of the [Co N5O]-type and of the D4h symmetry with a structure of the trans-[Co N4O2]-type respectively. The positions of the CD bands observed in the trans complexes coincide well with the maxima of the split components, Ia and Ib, of the first absorption band. The CD spectra of different [Co(l-am)(NH3)4]2+ ions, in which l-am is a bidentate ligand, show a variety of behavior; they are discussed from a stereochemical point of view. An intense CD band of the [Co(l-prol)(NH3)4]2+ ion at about 510 mμ can be attributed to the vicinal effect of an asymmetric nitrogen atom of the coordinated l-prolinate ion. For the trans-[Co en2(l-amH)2]X3 complexes, the rotatory parameters and rotatory strengths were calculated by means of analyses of the experimental CD and RD curves.
Studies of the Organic Reaction of Metal Carbonyl. X. The Oxo Reaction of Ethyl Acrylate—The Effects of the Reaction Conditions on the Distribution of the Products
Authors: Takegami Yoshinobu , Yokokawa Chikao , Watanabe Yoshihisa 
Published: July 2006

Abstract
The ratio between the α- and β-carbethoxypropionaldehyde formed in the oxo reaction of ethyl acrylate is affected by various reaction conditions; the proportion of β-carbethoxypropionaldehyde increases with an increase in the reaction temperature, but decreases with an increase in the partial pressure of carbon monoxide or hydrogen. These effects can be explained on the basis of the reaction mechanism between cobalt hydrocarbonyl and ethyl acrylate (Y. Takegami et al., This Bulletin, 37, 1190 (1964)): in the first step of the reaction, ethyl acrylate reacts with cobalt hydrocarbonyl to give, selectively, α-carbethoxypropionylcobalt carbonyl (I), and then I isomerizes to β-carbethoxypropionylcobalt carbonyl (II). Accordingly, the rates of two competitive reactions, the isomerization of I to II and the reduction of I to the corresponding aldehyde, may be the factors determining the distribution of the oxo reaction products. Under the oxo reaction conditions, the isomerization of I to II seems to occur more easily at a relatively high temperature and to be prohibited by a high pressure of carbon monoxide. On the other hand, a relatively high pressure of hydrogen seems to be favorable to the reduction of I to the aldehyde.
Studies of Acenaphthene Derivatives. XII. On the Red Substance Obtained from Acenaphthenequinone and Ammonia
Authors: Tsuge Otohiko , Tashiro Masashi 
Published: July 2006

Abstract
In order to elucidate the chemical structure of red crystals (A) obtained from the reaction of acenaphthenequinone (I) with ammonia, the reaction of I with ammonia, formamide or benzylamine was reinvestigated. It has been made clear again that the compound A is not acenaphthazine (II) but acenaphtho[l, 2-b]isoimidazole-2-spiro-2′-acenaphthenone (III), and that Schonberg’s assumption of the structure of the compound A is incorrect. That reaction of I with benzylamine afforded II as yellow needles in a good yield. Also, it has been found that the reaction product (B) of I with formamide is a mixture of almost equal amounts of II and III.
The Crystal Structure of m-Hydroxybenzamide
Authors: Katsube Yukiteru , Sasada Yoshio , Kakudo Masao 
Published: July 2006

Abstract
Crystals of m-hydroxybenzamide are monoclinic with four molecules in a unit cell of dimensions a=11.59, b=5.03, c=15.53 Å, β=136.1°, space group P21⁄c. An approximate angular orientation of the molecule in the cell was quickly obtained by an application of the vector-set seeking method. The location of the molecule was then determined with the help of the orientation. The positional and anisotropic thermal parameters of the carbon, nitrogen and oxygen atoms were refined by means of the least-squares method with three-dimensional intensity data. The final R factor was 0.138. The carboxyamide group and benzene ring twist to each other about the C-C bond by an angle of 24.4°. The interatomic distances and bond angles are close to those expected. The molecules are linked by three types of hydrogen bonds to form the infinite double-layered sheets perpendicular to the c axis, and the crystal structure shows somewhat different features from those of the related compounds.
The Quenching Action of Benzoic Acid and Methylbenzoate on the Fluorescence of Naphthalene Derivatives. III. The Solvent Effect on the Quenching of the Fluorescence of Dimethylnaphthylamine by Methylbenzoate
Authors: Miwa Takuji , Koizumi Masao 
Published: July 2006

Abstract
The fluorescence and absorption spectra and the quenching of the fluorescence of N, N-dimethyl-2-naphthylamine by methylbenzoate have been measured in cyclohexane, benzene, p-dioxane, isopropyl ether, ethyl ether, ethyl acetate, tetrahydrofuran, acetone and N, N-di-methylformamide (in the order of DK values). The fluorescence and the absorption spectra show a red-shift with the polarity of the solvent. By the method of Lippert and Mataga, the dipole moment of the excited fluorescer molecule has been estimated to be 4. ID. In nonpolar and weakly polar solvents, the methyl benzoate-added systems give fluorescence spectra with a swell or a shoulder on the long wavelength side, but this does not occur in N, N-dimethylformamide. When methyl benzoate is used as the solvent, two peaks of fluorescence are observed. The new emission has been interpreted as a charge-transfer emission, and the temperature-dependence of the fluorescence spectra has led to the conclusion that an encounter of fluorescent and quencher molecules is prerequisite for the appearance of CT emission. The quenching efficiencies in different solvents have been dealt with in reference to that in N, N-dimethylformamide, since the quenching in this solvent has been found to be almost encounter-controlled. A general correlation has been found between the quenching efficiency and the polarity of the solvent. The quenching mechanism and also the appearance of the CT emission have been discussed.
Studies of the Chemiluminescence of Several Xanthene Dyes. III. The Effect of Added Foreign Dyes on Light Production
Authors: Kamiya Isao , Iwaki Ryojirô 
Published: July 2006

Abstract
The intensity of uranine chemiluminescence decreased when trypaflavine was added to the system. The enfeebling action seemed to be due to external quenching. On the contrary, the intensity of eosine chemiluminescence was enhanced by the presense of uranine. The values of Δ and σ are defined by the following equations:
(Remark: Graphics omitted.)
where IUE, IU and IE are the intensities measured in uranine-eosine, uranine and eosine systems respectively, and where T is the duration of eosine chemiluminescence. Δ increased with the increase in either the concentration of uranine or that of eosine, while σ increased only when the ratio of the uranine concentration to the eosine concentration increased. Δ increased with the increase in the temperature, while σ was little affected by the temperature. Δ increased upon the addition of organic solvents, while σ was little affected by the addition of the organic solvents. The enhancing action is due neither to the production of a stable compound which emits strongly nor to the increase in the rate of the decomposition of the dye. One possible mechanism of the enhancing action is that energy is transferred from an energy-rich intermediate produced by the reaction to an unoxidized uranine or eosine.
Studies of Poly-β-benzyl-l-aspartate Helix. II. The Circular Dichroism and Optical Rotatory Dispersion of Copolymers of β-p-Methyl, Chloro, or Cyanobenzyl-l-aspartate with β-Benzyl-l-aspartate
Authors: Hashimoto Masahisa 
Published: July 2006

Abstract
The observation of the circular dichroism (240–290 mμ) due to the aromatic side chain indicates that, in a chloroform solution, even the side-chain aromatic rings of the copolyaspartate chain in the right-handed helix are in a regular arrangement to form an outer helix. On the contrary, for the copolyaspartate chain in the left-handed helix, the aromatic rings are much less regular. The ORD measurements indicate that, in a dimethylformamide solution, the poly-β-benzyl-l-aspartate chain is essentially in a random coil form, whereas the para-substituted derivatives are essentially in a right-handed helix. Accordingly, for each series of copolymers, the transition from a random coil form to a right-handed helix is observed as the molar content of the para-substituent is increased. The copolypeptide chain of β-benzyl-l-aspartate and β(p-methylbenzyl)-l-aspartate (molar ratio, 1:1) takes either the left-handed helix in a chloroform solution or the right-handed helix in a dimethylformamide solution. Accordingly, for this copolypeptide, the transition from the left to right-handed conformation is observed at the mixing volume ratio, 90 : 10, of the chloroform-dimethylformamide solution.
Syntheses of l-Sorbosylthymines and Related Compounds
Authors: Tokuyama Kanji , Katsuhara Mitsuru 
Published: July 2006

Abstract
1, 3, 4, 5-Tetra-O-acetylsorbopyranosylureas were prepared from sorbopyranosyl chloride via 1, 3, 4, 5-tetra-O-acetylsorbopyranosylisocyanates. 1-Ureido- and 6-ureidosorbofuranoses were obtained from the corresponding aminosorboses. The transformations of the ureas thus obtained into N-(sorbose)thymines were achieved, although with difficulty, by the direct condensation of halogeno- or tosylsorboses with metal salts of thymine.
Kinetic Studies of the Solution Polymerization of Trioxane Catalyzed by BF3·O(C2H5)2. III. The Effect of the Monomer Concentration
Authors: Higashimura Toshinobu , Miki Tetsuro , Okamura Seizo 
Published: July 2006

Abstract
In the solution polymerization of trioxane catalyzed by BF3·O(C2H5)2, the dependence of the monomer concentration on the polymerization reaction has been studied. The kinetic order of the monomer concentration as determined from the course of polymerization is close to 2 (except in a non-polar solvent). The kinetic order of the initial monomer concentration is extraordinarily large in the polar solvent. On the other hand, the molecular weight of the polymers formed increases with an increase in the initial monomer concentration. In the polymerization of trioxane in a polar solvent such as nitrobenzene at a low monomer concentration, the molecular weight of the polymers does not increase in the course of polymerization, even at the initial stage of polymerization. The reason for this has been discussed in terms of the nature of the chain carrier.
The Hydroxide-Blacks of Ruthenium and Rhodium as Catalysts for the Hydrogenation of Organic Compounds. II. The Effects of Solvents and Added Alkalis in the Hydrogenation of Aniline
Authors: Nishimura Shigeo , Shu Tetsuo , Hara Tomoyoshi , Takagi Yuzuru 
Published: July 2006

Abstract
The hydrogenation of aniline with the hydroxide-black catalysts of ruthenium and rhodium was investigated, using various alcohols as solvents. The formation of dicyclohexylamine increased in the following order with respect to the solvents: t-butyl alcohol≅isopropyl alcohol &lt;&lt; ethyl alcohol &lt; methyl alcohol. It was shown that the addition of a small amount of alkali greatly hinders the formation of dicyclohexylamine. The effects of added ammonia and dicyclohexylamine were also investigated. The addition of ammonia retarded the rhodium-catalyzed hydrogenation much more seriously than the hydrogenation with ruthenium, but it was found that in the presence of alkali the hydrogenation with rhodium was not inhibited by the addition of ammonia.
An Analysis of the Proton Magnetic Resonance Spectra of Acrylic Acid in Solution: A Comparative Discussion of the Methods of the Analysis of ABC Spin Systems
Authors: Yamamoto Takeo , Fujiwara Shizuo 
Published: July 2006

Abstract
In an attempt to examine various existing methods for the analysis of high-resolution NMR spectra, the statistical theory has been applied to the least-squares iteration method presented by Arata, Shimizu and Fujiwara. The standard errors of chemical shifts and spin-spin coupling constants, and the singularity in the normal equation, have been discussed. Two sets of parameters which are placed close together have a possibility of producing a singularity in the normal equation. A way of eliminating the singularity has been presented. The method thus presented has then been applied to an analysis of the vinyl proton spectra of acrylic acid in carbon tetrachloride and in aqueous solutions of various pH values. It has been found that the spin-spin coupling constants do not change beyond the range of experimental errors under the conditions of the present study. The change in chemical shifts has been discussed in terms of the possible conformations of the molecules.
The Determination of Micro Amounts of Polythionates. III. A Photometric Method for the Determination of Tetrathionate by Means of Its Cyanolysis
Authors: Koh Tomozo , Iwasaki Iwaji 
Published: July 2006

Abstract
A photometric method capable of determining tetrathionate by exactly the same procedure as that used for pentathionate and hexathionate has been established. The optimum pH ranges for the reactions of tetrathionate, pentathionate and hexathionate with cyanide are 8.3–12.1, 8.0–8.8, and 7.8–8.9 respectively for the recommended procedure. From a consideration of the above experimental facts, it has been concluded that tetrathionate can be determined accurately by exactly the same procedure as that used for pentathionate and hexathionate when the pH value is within the range from 8.3 to 8.8. To the standard tetrathionate solution first the buffer solution and then a solution of sodium cyanide are added in order that the pH value of the mixture solution after the addition of the cyanide solution may be within the 8.3–8.8 range. The mixed solution is kept in the thermostat at 40°C for 30 min.; the tetrathionate is thereby converted into thiocyanate quantitatively. After the addition of a ferric nitrate - perchloric acid solution, the absorbancy of the solution of ferric-thiocyanate complex formed is measured at the wavelength of 460 mμ.
Ion-pair Formation of Some Substitution-inert Complexes and Sulfate Ions. Determination of Association Constants Using Polarographic Diffusion Current
Authors: Tanaka Nobuyuki , Ogino (née Ebata) Kazuko , Sato Gen 
Published: July 2006

Abstract
The polarographic diffusion current of some tervalent substitution-inert complex cations decreases by the addition of sulfate. From the change in diffusion current the association constants of substitution-inert complex and sulfate ions are obtained at ionic strength 0.1 (NaClO4) and 25°C. The values are 69±8, 58±8 and 4×10 for [Co(NH3)6]3+–SO42−, [Cr(NH3)6]3+–SO42− and [Cr(H2O)6]3+–SO42 respectively. The formation of [Co(NH3)6]3+–HSO4− is negligibly small compared with that of [Co(NH3)6]3+–SO42−.
The Reaction of Thiols with Propylene Oxide in the Presence of Free Radical Sources
Authors: Takebayashi Matsuji , Shingaki Tadao , Mihara Takakimi 
Published: July 2006

Abstract
The effect of free radical sources on the reaction of thiols with propylene oxide has been studied. In the presence of free radical sources, such as benzoyl peroxide, tetraphenylhydrazine and tetra-methylthiuram disulfide, the reaction gives a single addition product, 1-aryl(or aralkyl)thio-2-propanol, in the same manner as when alkaline catalysts are employed. When l(+)-propylene oxide is used, an optically-active 1-thio-2-propanol is obtained. However, azobisisobutyronitrile manifests no catalytic influence on the reaction. Mercury-vapor light also has no effect on the interaction of thiols and propylene oxide, while the light leads to the decomposition of thiols. The mechanism of the reaction has been discussed in terms of a thiyl anion intermediate.
Color Reactions of Dinitrobenzyl Pyridine and Related Compounds
Authors: Hiraoka Hiroyuki , Hardwick Russell E 
Published: July 2006

Abstract
Upon treatment with certain reagents, the photochromes, α- and γ-(2,4-dinitrobenzyl)pyridine and 2, 4, 2′, 4′-tetranitrodiphenylmethane form stable, blue-colored compounds which probably have chromophoric structures similar to those of the photochromic modifications of the original compounds (two examples of the permanently colored compounds are the n-methyl bases and the products from reactions with epoxy compounds). Kinetic and spectrophotometric studies of these colored compounds and of the anions of the original photochromes are reported. These results are compared with data on the photochromic tautomers.
Electrical Conduction of Organic Semiconductors under High Pressure
Authors: Shirotani Ichimin , Inokuchi Hiroo , Minomura Shigeru 
Published: July 2006

Abstract
The electrical conductivity and the temperature dependency of the organic semiconductors, five simple polycyclic aromatic compounds, two charge transfer complexes and a free radical, have been observed up to 1.6×105 kg./cm2. The conductivity thus increases to 105–107 times that at atmospheric pressure, while the band gaps decrease to about one fifth of the ordinary values. These abrupt changes may be caused by the overlapping of π-electron clouds of adjacent aromatic molecules.
Thermal and Radiation Oxidations of Benzene to Phenol in Aqueous Solutions Containing Metal Ions at Elevated Temperatures. VII. The Mechanisms of Phenol Formation as Studied by Stable Isotopes
Authors: Hotta Hiroshi , Suzuki Nobutake , Abe Toshihiko 
Published: July 2006

Abstract
When benzene was oxidized to phenol in an oxygen-18 enriched aqueous solution of iron and copper sulfates, the oxygen-18 was much concentrated to phenol. The oxygen-18 content depended on the kind of metal ion and on the temperature. This suggests that the oxygen in the phenol produced is donated not only by the molecular oxygen, but also by the water. Therefore, it is assumed for the termination process that phenol is formed by the ionic reactions. Furthermore, when an equimolar mixture of benzene and benzene-d6 was oxidized, the isotope effect of hydrogen, kH/kD, as estimated from the isotopic composition of the phenol produced, was about 1.2. This value seems to be small for the hydrogen abstraction reaction of radicals. Therefore, when we compare these results with the other facts reported previously, the main reaction of the propagation process may be supposed to be the abstraction reaction of hydrogen by phenyl peroxide. In this experiment, it was also found that phenol exchanges hydrogen with water. The rate constant of the exchange reaction was estimated by Bateman’s equation. The rate constant is the highest in the ferric sulfate solution.
The Heterogeneous Adsorption of Carbon Dioxide on the Nickel Surface as Studied by the Isotopic Desorption Method
Authors: Kobayashi Yasushi , Hirota Kozo 
Published: July 2006

Abstract
Further evidence on the adsorptive heterogeneity of the nickel surface has been presented by the use of the technique described in our previous paper. The results support the conclusion already proposed that more than 20–30% of the surface can adsorb carbon dioxide strongly over the temperature range between −78° and 300°C.