bluuebunny/crossref_metadata_2025 huggingface dataset:
Studies of Crystal Hydrates. VII. The Dielectric Properties of Capillary Water in Single Crystals of Dl-[Co(en)3]Cl·nH2O
Authors: Chihara Hideaki , Okawa Setsuo , Seki Syûzo
Published: July 2006

The dielectric constant and loss of single crystals of Dl-[Co(en)3]Cl3·nH2O have been measured between −150°C and room temperature in the frequency range 40 c./s. and 3 Mc./s. The water content, n, was varied from 0.27 to 3.6. The anomalous dispersion and relaxation absorption due to the hindered rotation of water have been observed and they are strongly dependent on n. The activation energies for the relaxation absorption have been determined for different n values and for different orientations of the crystals. A molecular mechanism for the absorption has been presented on the basis of the zeolitic nature of the water molecules in the crystal as determined previously from structural and thermodynamics investigation
The Kinetics of the Reaction of Aromatic Ketones with Nitrous Acid in Sulfuric Acid
Authors: Ogata Yoshiro , Furuya Yoshiaki , Ito Masahiro
Published: July 2006

The rates of the reaction of acetophenone, ring-substituted acetophenones, propiophenone and isobutyrophenone with nitrous acid in 98.6% sulfuric acid have been measured by means of spectrophotometry. The rates have been expressed as ν=k [ketone] [NO+] with acetophenones and propiophenone, while they are ν=k [ketone] with isobutyrophenone. The electron-attracting groups in acetophenone accelerate the reaction with Hammett’s ρ value of +2.6. A probable mechanism has been suggested which involves a rate-determining nitrosation of enolized ketone for acetophenone and propiophenone, and a rate-determining enolization of ketone for isbutyrophenone.
Structural Studies of the Gum Jeol Polysaccharide.
Authors: Bhattacharyya A K , Mukherjee A K
Published: July 2006

The polysaccharide obtained from gum jeol has been shown to be composed of d-galactose, l-arabinose, and d-galacturonic acid. The hydrolysis of the fully-methylated gum yielded 2,3,5-tri-O-methyl-l-arabinose (2.03 mol.), 2,3,4,5-tetra-O-methyl-d-galactose (3.1 mol.), 2, 3, 4-tri-O-methyl-d-galactose (1 mol.), 2,4-di-O-methyl-d-galactose (1.94 mol.), 2-O-methyl-l-arabinoses (1.05 mol.) and 2-O-methyl-d-galac-tose (1.1 mol.) in the neutral fraction of the hydrolysate. The reduced acidic fraction gave 2,3,4-tri-O-methyl-d-galactose (2 mol.) and 2,4-di-O-methyl-d-galactose (2 mol.). The structural significance has been discussed from the above results and from the results of periodate oxidation studies of the gum. The molecular weight of the methylated gum has also been determined by the light-scattering method.
Preferential Ion Transport in Electrodialysis through Ion-exchange Resin Membranes
Authors: Mandersloot W G B
Published: July 2006

Because of the great difficulties encountered when describing preferential ion transport in electrodialytic demineralisation from first principles, an empirical approach is more attractive. Preferential ion transport can be described as a simple separation process with a separation factor which is constant for a certain membrane pair under certain conditions, namely, a constant voltage drop per compartment pair at a constant flow velocity in the compartments, high enough to avoid any serious polarisation. Exceptions occur when one counterion is immobilised to a great extent in the resin, when specific strong binding forces are operative (e. g., ionpair formation), and also when the preferential absorption of a counterion is based on the preferential exclusion of the other counterion. The latter appears to be the case in the separation of Cl− and SO42− at high total electrolyte concentrations.

The order and magnitude of preference are, in the first instance, governed by the same factors which govern ion-exchange equilibrium. The separation of ions has been shown to decrease with an increase in the applied electric potential (current density). It has been demonstrated that heterogeneous membranes cause a concentration polarisation at lower current densities than homogeneous membranes and that this early polarisation can be detected from the preferential ion transport data before it can be measured in terms of the resistance of the membrane pack.
The Solvent Extraction of Ruthenium with 8-Hydroxyquinoline
Authors: Kato Toyoaki
Published: July 2006

The solvent extraction behavior of ruthenium(IV) with 8-hydroxyquinoline has been investigated in detail using ruthenium-106 as a tracer.

The complex formation in the aqueous phase is fairly slow and is the limiting step in the procedure, but it can be enhanced by heating. Complete extraction is attainable with n-butanol, benzene and other organic solvents after 8-hydroxyquinolate has been formed by one hour’s heating at 60°C with the excess reagent in an aqueous acetate medium of pH 4∼6. n-Propanol, especially when combined with n-butanol, is an efficient extraction solvent. The presence of ammonium salts, organic acids or their salts causes interference. 8-Hydroxyquinolate, once formed, remains extractable even at very low pH values. The stripping of ruthenium from the benzene extract is accomplished by contact with concentrated hydrochloric acid.

This solvent extraction is applicable to the colorimetric determination of minute amounts of ruthenium and to the isolation of ruthenium activities in mixed fission products.
Syntheses of Peptides Related to the N-Terminal Structure of Corticotropin. III. The Synthesis of l-Histidyl-l-phenylalanyl-l-arginyl-l-tryptophan, the Smallest Peptide Exhibiting the Melanocyte-stimulating and the Lipolytic Activities
Authors: Otsuka Hideo , Inouye Ken
Published: July 2006

1) A tetrapeptide, l-histidyl-l-phenylalanyl-l-arginyl-l-tryptophan, corresponding to the amino-acid sequence of positions 6 to 9 in the corticotropin and α-MSH molecules has been synthesized.

2) This synthetic tetrapeptide has been found to exhibit an MSH potency of 3.6×104 units per gram in the in vitro frog skin assay, and it is also active on lipolysis in rabbit perirenal adipose tissue. These results may confirm that the glycine at position 10 in the molecules of corticotropin and α-MSH is not essential for these biological activities.

3) It has been shown that the azide-couling procedure can be employed successfully for the synthesis of arginyl peptides provided it is used in combination with the NG-tosyl-arginine.

4) The preparation of NG-tosyl-l-arginine and some of the relevant compounds has been described.
Syntheses of Peptides Related to the N-Terminal Structure of Corticotropin. IV. The Synthesis of the Amino Acid Sequences, Lys-Pro-Val-Gly and Lys-Pro-Val-Gly-Lys
Authors: Otsuka Hideo , Inouye Ken , Jono Yoshiko
Published: July 2006

The amino acid sequence Lys-Pro-Val-Gly-Lys, which corresponds to positions 11 to 15 of the corticotropin molecule, has been synthesized in the form of a crystalline derivative, Nα-carbobenzoxy-Nε-t-butyloxycarbonyl-l- lysyi-l-prolyl-l-valyl-glycyl-Nε-t-butyloxycarbonyl-l-lysine methyl ester, from which the crystalline hydrazide has then been obtained. The syn-thesis of the Lys-Pro-Val-Gly sequence corresponding to positions 11 to 14 of corticotropin has also been described.
The Potential Constants of Phosphorus Trihalide and Phosphoryl Halides
Authors: Nakai Yasuo , Mori Kumiko
Published: July 2006

It is important to calculate the potential constants of phosphorus compounds systematically in order to determine physically meaningful potential constants.

First the normal vibrations of such pyramidal-type molecules as PC13 and PBr3 have been calculated by the use of a Urey-Bradley force field as supplemented by the interaction terms between two bond-stretching coordinates and between two angle-deformation coordinates, and then such phosphoryl halogenides as OPCI3 and OPBr3 have been calculated by the use of a Urey-Bradley-Shimanouchi force field.

The repulsion terms between nonbonded halogen atoms have been estimated from the interaction forces between inert atoms based on the Lennard-Jones formula.

The force fields used for the PX3-type and OPX3-type molecules in the present paper are different. However, it has been found that a relationship exists between the potential constants of such compounds as PC13, PBr3, OPCI3 and OPBr3, and those for mixed halogen phosphorus compounds, such as PCl2Br, PClBr2, OPCl2Br and OPClBr2.

The additional potential terms used for the PX3 type may arise from the resonance energy because of the interaction between the unpaired electrons of the P atom and the electrons existing in the PX bond and on the XPX plane.

In our present investigation, a linear correlation has been found to exist between the phosphoryl potential constants in phosphoryl halides and the sum of the Pauling electro-negativity constants of the halogens.
Radiation-Induced Selective Main-chain Scission in Polyvinyl Alcohol
Authors: Hirano Yutaka
Published: July 2006

Polyvinyl alcohols which are different in the mole fraction of the head-to-head structure, in which two of –OH substituents are situated on consecutive carbon atoms, have been irradiated with Co-60 gamma rays in a vacuum at room temperature in order to investigate the effect of this anomalous structure on the radiation-induced main-chain scission of the polymer. The selective main-chain scission in polyvinyl alcohol has been observed at such positions as the head-to-head structure. The average absorbed energy necessary to produce a main-chain scission, i. e., Ed, is about 1700 eV. for polyvinyl alcohol containing no head-to-head structure, while Ed is 100 eV. for polyvinyl alcohol containing a 1.54 mol.% head-to-head structure. A rapid increase up to a certain value in Gd, the number of chain scissions produced per 100 eV. of energy absorbed by the polymer, has been observed with the increase in the head-to-head structure content in the polymer chain. Thus, it has been postulated that there is a transfer of radiation energy from the head-to-tail structure to the head-to-head structure. An estimation has been made on the range of energy transfer from the Gd dependency on the concentration of the head-to-head structure.
The Stability of Calcium Complexes of Purely-separated Polyphosphate
Authors: Miura Masaji , Moriguchi Yoshiki
Published: July 2006

The formation of calcium complexes of purely-separated linear chain polyphosphates with chain lengths of 2∼8 phosphorus atoms has been studied by means of nephelometric titration at 25°C, pH values of 10∼12, and ionic strengths of 0.1 and 1.0. The following results have been obtained: 1) The number of phosphorus atoms bound to a calcium ion is about 2, regardless of the chain length at an ionic strength of 0.1, while it varies from 2 to 4 according to the chain length at an ionic strength of 1.0; 2) The stability of calcium polyphosphates increases with the chain length at both ionic strengths and levels off at a chain length of 6∼7 when the ionic strength is 0.1, though not yet when it is 1.0; and 3) The stability constant of a calcium complex of any long-chain polyphosphate is almost equal to that of a mixture of polyphosphates with the same average chain length.
Studies of the Synthetic Inorganic Ion Exchanger. IV. The Separation of the Fission Product and Uranium by Means of a Stannic Phosphate Cation Exchanger
Authors: Inoue Yasushi , Suzuki Shin , Goto Hidehiro
Published: July 2006

The separation of fission products and uranium has been carried out by means of a stannic phosphate cation exchanger. By using various concentrations of nitric acid and ammonium chloride solutions as eluants, the separation of uranium-strontium and uraniumcesium has been easily performed, but that of uranium-rare earths is very difficult. Among the various reagents investigated, a 1 m phosphoric acid solution is most suitable for the separation of uranium from rare earths. In view of the above results, the separation of uranium and gross fission products has been carried out; the resultant yield of uranium is more than 90%, and the decontamination factor is (2∼3)×103.

Part of the expenses for this investigation have been defrayed by a grant-in-aid by the ministry of education.
Nuclear Magnetic Resonance Spectra of Polymethyl Methacrylate in Solution. I. An Attempt to make Stereoregularity Measurements
Authors: Kato Yoshinori , Nishioka Atsuo
Published: July 2006

The NMR spectra of polymethyl methacrylates prepared with various initiators have been examined. Three resonance peaks of α-methyl protons observed with an increasing magnetic field correspond to three species of the monomer units, i. e., I-, D- and S-units respectively. The proportion of each peak area may be used to characterize the stereoregularity of the polymer chain. A ternary diagram has been proposed to represent the stereochemical configuration of the polymers. Together with the average sequence lengths of the units, the possible polymerization mechanisms are considered. Free radical polymers of methyl methacrylate seem to be describable with a single parameter which depends only on the polymerization temperature. Some polymers prepared with anionic initiators show a stereoblock character. The polymerization mechanism has also been discussed in some idealized cases.
On the Mechanism of Dehydrogenation of the 2,4,5-Triphenyl-4,5-dihydroimidazole over Solid Catalysts
Authors: Hayashi Taro , Kuyama Mineko , Takizawa Emiko , Hata Masako
Published: July 2006

1) Amarine has been completely dehydrogenated, without the presence of oxygen, by refluxing solutions in xylene, toluene, benzene or acetone with Raney nickel, whereas no dehydrogenation of isoamarine occurred at all under the same conditions. Amarine was also dehydrogenated without the presence of oxygen by refluxing solutions with platinum black, palladium black or active carbon. The dehydrogenation of amarine, carried out by refluxing a solution in benzene with sulfur powder, was accompanied by the evolution of hydrogen sulfide.

2) Amarine was adsorbed with active carbon from a solution in benzene at room temperature, whereas hardly any isoamarine was adsorbed under the same conditions, the difference in the dehydrogenation behavior of these cis- and trans-isomers being very marked.

3) Considering the results obtained, the dehydrogenation of amarine by refluxing solutions with solid catalysts may reasonably be considered cis-dehydrogenation, the mechanism being, as follows; an amarine molecule is adsorbed on solid catalysts with the side of the plane of an imidazole ring, to which cis 4- and 5-hydrogen atoms are attached, and these hydrogen atoms, which tend to move from the imidazole ring, are eliminated under the effect of solid catalysts. Isoamarine, which has a trans-conformation unfavorable to adsorption, is not subjected to dehydrogenation with solid catalysts.
The Thermal Decomposition of Ammonium Polymolybdates. I
Authors: Ma Eikoh
Published: July 2006

The thermal decomposition of ammonium di-, hepta-, tri- and octa-molybdate has been investigated by means of thermogravimetric analysis, ammonia determination and the use of an omegatron mass-spectrometer. Both weight-decrease curves and ammonia evolution curves exhibit stepwise decomposition, indicating that there should be a difference in bonding strengths of water and of ammonia, presumably as ammonium ions in the crystal, with molybdate ions. Hepta-, di- and trimolybdate decompose in three stages, and octamolybdate in two stages. A certain crystal structure should correspond to each stage. Dehydration precedes deammoniation. Dehydration is complete at about 130, 150 and 280°C with hepta-, tri- and octa-molybdate respectively. Deammoniation is complete in all at the same temperature of 360∼375°C. The existence of nitrogen above 250°C in vacuo has been established. Nitrogen is yielded in the process of the thermal decomposition through oxidation as well as through the catalytic decomposition of ammonia. Nitrogen reached a maximum around 320°C. As evidence for the formation of nitrogen through decomposition, hydrogen was also detected above 250°C, and was found to reach a maximum at about 320°C, although in a much smaller quantity.
The Polarographic Determination of Divalent Tin in Sodium Formate
Authors: Deshmukh G S , Murty S V S S
Published: July 2006

Well-defined cathodic and anodic polarograms of stannous tin in sodium formate have been reported. The diffusion current is directly proportional to the concentration of stannous tin between 10−5 to 10−4m. The anodic half-wave potential of tin is shifted to positive values with the increase in the concentration of Sn2+, whereas the cathodic half-wave potential is constant. The anodic polarogram is highly irreversible. The cathodic polarogram is also irreversible. The irreversibility of the anodic polarogram is increased with the concentration of stannous formate. This is evidenced by a corresponding increase in the difference between E3⁄4 and E1⁄4. Above pH 5.0 the anodic polarogram merges with the cathodic polarogram,. thereby limiting the polarographic determination of Sn2+ to the pH value 3∼5. The E1⁄2 of the anodic polarogram shifts to negative potentials when the pH was increased, whereas that of the cathodic wave is constant. The polarogram with equal wave heights obtained in 1 molar sodium formate at pH 3.0 with 0.005% gelatin has been taken for the determination of tin.
Infrared Spectra and Rotational Isomerism of Some Long-chain n-Alkoxy Ethanols
Authors: Srinivasan T K K , Jose C I , Biswas A B
Published: July 2006

The infrared spectra of n-alkoxy ethanols CH3(CH2)nO-CH2-CH2-OH with n=13,15,17,19 and 21 have been obtained in the solid and liquid states as well as in solution. From a study of the CH2 rocking modes of the (O–CH2-CH2-O) group at 893 cm−1 and 864 cm−1 during liquid-solid transformation and from the solution spectra in the hydroxyl-stretching region, it has been shown that this group exists predominantly in a gauche configuration in liquids or in solution, while both gauche and trans configurations are present in the solid state.
Studies of Methionine Sulfoxide. III. A New Colorimetric Method for the Determination of Methionine Sulfoxide and Its Derivatives
Authors: Morihara Kensaku
Published: July 2006

1) A new colorimetric method for the determination of methionine sulfoxide and its derivatives on the basis of the rearrangement of sulfoxide by the action of acetic anhydride has been established.

2) From about 10 μ to 80 μ mol. of methionine sulfoxide can be determined with an experimental error of 3 per cent.

3) The interference with the reaction by various amino acids and related substances has been investigated.

4) Several compounds related to methionine sulfoxide have been prepared and analyzed by the present method.
Studies of Peptide Antibiotics. I. Dipeptide Anhydrides as Models of Cyclic Peptide Antibiotics
Authors: Izumiya Nobuo , Kato Tetsuo , Fujita Yoshimasa , Ohno Motonori , Kondo Michio
Published: July 2006

The d-d, l-l, d-l and l-d stereomers of both valyllysine anhydride and phenylalanyllysine anhydride, and the d-l and l-l stereomers of both valylornithine anhydride and phenylalanylornithine anhydride, have been synthesized in order to compare them with the cyclic peptide antibiotics, with which they possess several structural features in common.

Synthesis has been achiveved by the dicyclohexylcarbodiimide-induced condensation of formyl, (or t-butyloxycarbonyl) valine (or phenylalanine) with the ω-carbobenzoxylysine (or ornithine) ester, followed by the treatment of the resulting acyl dipeptide ester with hydrogen chloride in methanol or ethyl acetate to remove the formyl- or t-butyloxycarbonylblocking group. The dipeptide ester hydrochlorides so derived have been converted by the action of ammonia to the corresponding carbobenzoxy-substituted dipeptide anhydrides and these, in turn, transformed to the desired unacylated dipeptide anhydride hydrochlorides by palladium-catalyzed hydrogenolysis.

Enzymic experiments have been carried out to determine whether the dipeptide anhydride hydrochlorides are attacked by trypsin or chymotrypsin. The results indicate that no hydrolysis of any of the anhydrides occurs. In this connection, valyllysines, phenylalanyllysines and lysylphenylalanine have been synthesized for the purposes of chromatographic comparison.

The effects of the dipeptide anhydride hydrochlorides on bacterial growth have been examined. The results indicate that no antibacterial activities are observed against microorganisms in a bouillon agar medium.
The Radiolysis of Liquid cis-2-Butene
Authors: Hatano Yoshihiko , Shida Shoji , Sato Shin
Published: July 2006

The radiolysis of cis-2-butene has been studied in the liquid phase at room temperature.

(1) The major products (and their G-values) were hydrogen (1.02), n-butane (0.83), 1-butene (0.40), trans-2-butene (2.29), C8 hydrocarbons (2.30), and higher polymers, the G-values being independent of the total dose. Small amounts of C1∼C3 and C5∼C7 hydrocarbons were also formed. The hydrogen and the lower hydrocarbons except for n-butane were found, by using p-benzoquinone as a radical scavenger, to be produced for the most part through the molecular mechanism.

(2) The addition of benzene, naphthalene, and anthracene to liquid cis-butene have remarkable effects on the formation of trans-2-butene; thus, the cis-trans isomerization increases at a lower concentration of additives, while it decreases at a higher concentration of additives. The radical scavenging effect cannot explain these results. From a comparison of the experimental results with the ionization potentials and electron affinities of aromatics, it has been concluded that the increase in the isomerization at lower concentrations is due to the electron capture effect of additives, while the decrease at higher concentrations is due to the charge transfer from the butene to the additives.
The Electronic Effect of the Substituents on the Intramolecular Hydrogen Bonding of o-Aryloxybenzoic Acids
Authors: \={O}ki Michinori , Hirota Minoru
Published: July 2006

The infrared hydroxyl and carbonyl absorptions of o-aryloxybenzoic acids have been reported and the assignment of each absorption band in these regions made. The higher carbonyl-stretching absorptin at about 1752 cm−1 has been attributed to the intramolecular hydrogen-bonded trans isomer from the following reasons: i) The Ai⁄Ac intensity ratio in the hydroxyl-stretching region increases as the Hammett σ-constant of the substituent decreases, and the same tendency is observed by assigning the carbonyl band at a higher frequency to the trans isomer; ii) From the measurement of the absorption intensity of 2-phenoxybenzoic acid at various temperatures, in both the hydroxyl and carbonyl regions, the authors have obtained nearly equal enthalpy difference values (1.89 and 1.78 kcal./mol. respectively) between the cis and trans isomers by assuming the above assignment.
Stability Order in Metal Chelate Compounds. II. 5-(p-Sulfophenylazo)-salicylate Complexes
Authors: Murakami Yukito , Takagi Makoto
Published: July 2006

The interaction of 5-(p-sulfophenylazo)-salicylic acid with zinc(II), copper(II), nickel-(II), cobalt(II), manganese(II), magnesium(II), calcium(II) and iron(III) has been investigated in aqueous media at 25.0±0.1°C and the ionic strength of 0.10 m. The stability constants for the 1 : 1 and 2 : 1 (ligand to metal) chelates of nickel, cobalt, manganese and magnesium, and for the 1 : 1 calcium chelate, as well as for the 2 : 1 ferric chelate, have been evaluated, and the resulting stability order with respect to the bivalent metals has been found to follow the sequence: calcium(II)<magnesium(II)<manganese(II)<(zinc(II))<copper(II)<nickel(II)<copper(II). The stability sequence, zinc(II)<nickel (II), is contrary to that observed for the catechol chelates.

A p-sulfophenylazo group demonstrated an electron-withdrawing effect, the magnitude of which was slightly greater than that of a sulfonate group. However, the effect of the former group on the chelate-stability has been found to be comparable with that of the latter.

The present salicylate derivative is also a good chelating agent for iron (III) ion, even though the chelate system somehow becomes involved in a higher pH range.
The Cationic Polymerization of Acrolein
Authors: Toi Yoshio , Hachihama Yoshikazu
Published: July 2006

The cationic polymerization of acrolein with boron trifluoride etherate at various temperatures has been studied.

(1) The polymerization rate may be given as follows: RP=K[C] [M]2, on the basis of the polymerization in an ethyl ether solution, and the activation energy of reaction is 4.5 kcal./mol.

(2) The structure of polymers depends very much on the polymerization temperature; the polymerization at the lower temperature gives a polymer containing the larger amount of the end vinyl group as a side chain, and the smaller amount of the aldehyde group.
Catalysis by Organic Semi-conductors. The Photo-oxidation of Isopropyl Alcohol in the Liquid Phase
Authors: Inoue Hiroo , Hayashi Shigeki , Imoto Eiji
Published: July 2006

The natures of organic semi-conductors have been correlated with the catalytic ability for the photo-oxidation of isopropyl alcohol to acetone with oxygen under ultraviolet or visible light irradiation. p-Type compounds are generally effective as sensitizers, but n-type compounds are ineffective. Heteroaromatic compounds are more effective than the parent aromatic compounds among p-type compounds. The molar ratio of the acetone formed to the oxygen absorbed is larger than unity in the case of p-type compounds and less than unity in the case of n-type compounds. Finally, it has been assumed that the migration of a positive hole in a p-type compound can be correlated with the migration of a hydrogen atom of isopropyl alcohol.
The Electrical Conductivity of Heterocyclic Compounds. Molecular Complexes of Phenazine
Authors: Inoue Hiroo , Hayashi Shigeki , Imoto Eiji
Published: July 2006

Some molecular complexes of the salt type have been prepared from phenazinium chloride or methosulfate and pyrene or p-hydroquinone. It has been confirmed that (1) the constitution, the color and the melting point of the molecular complexes varied with the drying conditions; (2) the ultraviolet absorption spectrum of ph-HCl-py by KBr shows a new band at about 620 mμ; (3) an unpaired electron is localized on the nitrogen atom of phenazine, and (4) the electrical conductivities of molecular complexes of the salt type are better than those of the quinhydrone type of phenazine.
The Viscometric Properties of Polyesters. II. Viscosity in the Range of Low Temperatures near the Glass Transition Point
Authors: Nakatsuka Ryuzo
Published: July 2006

The viscosities of amorphous long-chain polyesters have been measured in the range of 10∼106 poises and between −60 and 30°C, and the following results have been obtained (cf. also Part I).

(1) Within the limit of 102∼106 poises, all the polyesters are consistent with the WLF equation. At the “transition area” which was described in Part I, the observed viscosity begins to deviate from the WLF equation.

(2) The apparent activation energy for the viscous flow (E\doublebarpipe) is nearly constant within the range of 30∼5°C, and over the range of viscosity beyond 102 poises for all the polyesters.

(3) The estimated curve of the temperature dependence of the free volume fraction (f) can be divided into three straight-line parts, corresponding to the WLF liquid state, the “transition area” for viscous flow, and the Andrade liquid state respectively.

(4) The relationship between the chemical structure and the viscosity can be represented in connection with intermolecular force, intramolecular rotation and so on.
The Spectrophotometric Determination of Cadmium with Xylenol Orange
Authors: Otomo Makoto
Published: July 2006

The red cadmium - xylenol orange complex has been studied spectrophotometrically to establish the optimum conditions for determining traces of cadmium. The absorption spectrum of the colored complex showed a maximum absorption at 575 mμ when measured against a reagent blank. The reaction was carried out in a buffered solution at a pH value of 6.3. Beer’s law is obeyed over the 20 to 120 μg. range of cadmium. The sensitivity of the reaction was 0.006 μg. cadmium per cm2. Job’s method of continuous variations and the method of Newman and Hume have been applied to determine the composition of the complex. Both methods showed the existence of only one form of the complex, 1 to 1. The apparent formation constant was calculated to be 6.1×103 at a pH value of 5.5.
Electronic Spectra of Substituted Aromatic Hydrocarbons. IV. Anthramines
Authors: Suzuki Satoshi , Baba Hiroaki
Published: July 2006

Absorption and fluorescence spectra of α- and β-anthramines have been observed. The 1A→1Lb transition, which is masked by the 1A→1La in anthracene, emerges in both α- and β-anthramines because of the perturbation by the substituent. In β-anthramine, the 1Lb band is clearly separated from the 1La band. In α-derivatives, the 1Lb band exists on the higher frequency side of the 1La band. These results may be confirmed by observing the effects of hydrogen bonding on the spectra. At the liquid-nitrogen temperature remarkable changes in the absorption spectrum of α-anthramine occur in the presence of triethylamine; these changes have been interpreted as due to the co-operative effects of hydrogen bonding and the solvent. By using the band assignments proposed in this series of papers, reasonable correlation diagrams of the electronic energy levels have been presented for substituted aromatic hydrocarbons, from benzene to anthracene.
The Use of NMR Spectroscopy as a Structural Probe in Ferrocene Chemistry
Authors: Nagai Yoichiro , Hooz John , Benkeser Robert A
Published: July 2006

All of the acetylalkylferrocenes have been synthesized and obtained in a highly pure state. The infrared and NMR spectrum of each of these compounds has been determined, and the results tabulated.

It has been shown that NMR spectroscopy provides a convenient tool in elucidating the structure of substituted ferrocenes. It is particularly useful in distinguishing between 1,2-and 1,3-disubstituted structures, a situation where infrared has its greatest limitations.

A series of shielding constants has been developed for a variety of ferrocene substitu-ents. These enable one to predict with considerable precision the chemical shifts of a variety of protons bonded to the ferrocene nucleus.
The Photochemical Transformation of Some p-Quinol Ethers
Authors: Matsuura Teruo
Published: July 2006

The ultraviolet irradiation of 2,4,6-tri-t-butyl-4-methoxycyclohexa-2,5-dienone (V) in methanol and in ether has yielded a photoketone VI and 3,6-di-t-butylguaiacol (VIII) respectively. The irradiation of V in the presence of oxygen in ether has yielded VIII and the hydroperoxide of VI. Other related p-quinol ethers have also been subjected to photolysis.
The Thermal Decomposition of Ammonium Polymolybdates. II
Authors: Ma Eikoh
Published: July 2006

The thermal decomposition of ammonium di-, hepta-, tri- and octamolybdates has been investigated by means of differential thermal analysis, chemical analysis, and X-ray diffraction techniques. The steps of the decomposition may be described as follows:

Heptamolybdate

3(NH4)2O·7MoO3·4H2O\underset130°C→2(NH4)2O·

5MoO3\underset245°C→2(NH4)2O·8MoO3\underset360°C→MoO3

Dimolybdate

(NH4)2O·2MoO3\underset226°C→(NH4)2O·3MoO3

\underset225°C→2(NH4)2O·8MoO3\underset360°C→MoO3

Octamolybdate

2(NH4)2O·8MoO3·2H2O\underset287°C→2(NH4)2O

8MoO3\underset370°C→MoO3

Trimolybdate

(NH4)2O·3MoO3·xH2O\underset200°C→2(NH4)2O.

8MoO3\underset287°C→MoO3
The Monoterpene Constituents of the Essential Oil of Hinoki (Chamaecyparis Obtusa (Sieb. et Zucc.) Endl.)
Authors: Hayashi Shûichi , Yano Katsumi , Matsuura Tamon
Published: July 2006

d-α-Pinene, β-pinene, myrcene, d-limonene, dipentene, β-phellandrene, p-cymene, 1,8-cineole, camphor, l-α-terpineol, α-terpinyl acetate and bornyl acetate have been identified, and camphene, linalool and borneol have been gas-chromatographically confirmed. Of these compounds, β-pinene, myrcene, β-phellandrene, 1,8-cineole and p-cymene have been found for the first time in this work. The main constituents of the monoterpene fraction are d-α-pinene and l-α-terpineol; the former amounts to 66.3%, and the latter to 10.1%, the remaining constituents being within a few %.
Studies of Tritium-labeled Compounds. VII. The Platinum-catalyzed Exposure Reaction
Authors: Meshi Teruhiko , Sato Yoshishige
Published: July 2006

In order to elucidate the nature of the chemisorption in the platinum-catalyzed exposure reaction with tritium, the effects of the substituents upon the hydrogen-tritium exchange of the aromatic ring and upon the tritium distribution in benzoic acid, salicylic acid and benzoylvaline have been investigated. All the substituents except the hydroxyl group decrease the hydrogen-tritium exchange of the aromatic ring, and the compounds carrying those substituents poison the catalyst for the tritium incorporation of benzene. This retardation effect of the substituents upon the hydrogen-tritium exchange of the aromatic nucleus may perhaps be attributed to the preferential adsorption of the substituents on the catalyst surface. The tritium distribution in benzoic acid and salicylic acid suggests that the hydrogen-tritium exchange in the aromatic ring may follow the substitution rule for electrophilic aromatic exchange. The relative hydrogen-tritium exchange rates of benzoylvaline show that the more readily a hydrogen dissociates, the more rapidly it undergoes the exchange.
Relative Sensitivities of Elements in a Spark-Source Mass Spectrograph
Authors: Kawano Hiroyuki
Published: July 2006

The relative sensitivities of eleven elements in a spark-source mass spectrograph have been determined for monatomic singly-charged positive ions detected with Ilford Q2 plates. The results show that the elements have approximately the same sensitivities to within a factor of 3 in spite of large differences in both physical and chemical properties among them, and that the sensitivity of each element is constant in value within an uncertainty factor of 1.5, independent of changes in the bulk concentration of the element. Relative ion production rates have also been determined from the above sensitivities; they are in reasonable agreement with published values determined by electrical detection. From repeated measurements of the relative intensities of various ions, it has been suggested that relative ion yields from a spark ion source are not always constant for different elements. On the basis of these investigations, a discussion has been made of the general applicability of the sensitivity as the analytical constant in the quantitative mass spectrography of solids. Five different formulas have been used to express the “density” of mass lines, and exposures have been determined with an integrated monitor current. By trying several isotopic analyses, the calibration methods have been shown to be useful for mass spectrography.
The Electrolytic Preparation of Vanadium(II) Developers
Authors: Honda Kenichi
Published: July 2006

A systematic study of the preparation of a V2+ developer for use in the continuous automatic processing machine has been carried out.

At first the vanadyl salts, such as vanadyl sulfate and vanadyl chloride, were chemically synthesized from vanadium pentoxide with a yield of nearly 100%, while vanadyl nitrate was obtained with a yield of only 38%. The synthesizing method using oxalic acid was considered to be the most advantageous from the standpoint of the succeeding electrolytic process.

Concerning the electrolytic reduction process to obtain V2+ salt from vanadyl salt, the influence of the kind of electrodes, the combination and concentration of electrolytes, and the cathodic current density upon the yield has been studied. On the basis of these studies, the optimum conditions for the electrolysis have been established except for vanadyl nitrate.
Mixed Chelate Compounds of Titanium(III) as Studied by Electron Paramagnetic Resonance and Spectrophotometry
Authors: Fujiwara Shizuo , Nagashima Kozo , Codell Maurice
Published: July 2006

An electron-paramagenetic resonance and spectrophotometric study has been made of the composition of mixed chelate compounds of titanium(III)-ethylenediaminetetraacetic acid (EDTA) and organic acids. The existence of three titanium(III)-EDTA complexes in solution has been established. The complex formation of titanium(III)-EDTA with oxalate, tartrate, citrate and lactate has been confirmed, and the ratio of the oxalate has been established. Structures for the complexes have been proposed, probable equilibrium mixtures of complexes at various pH values have been discussed and new procedures have been proposed for the detection of chelate compounds in solution.
A Study of the Sorption of Metal Ions by Cotton Cloth
Authors: Koga Reiko , Shinozaki Yoshiharu , Meshitsuka Gisuke , Titani Toshizo
Published: July 2006

The uptakes of the metal ions, Co2+, Ca2+ and Cs+, by cotton cloth have been determined by using the tracer technique. In the acidic and the neutral media, the isotherms were the Langmuir type, and the cation exchange mechanism of the special groups (probably the carboxyl group) has been confirmed. The heat and the activation energy for the sorption of Co2+ were −2 kcal./mol. and 7.6 kcal./mol. respectively (at pH ca. 4.7). In the alkaline media, the cotton cloth showed marked uptakes. The order of the affinity of various metal ions to cotton cloth was also determined as follows:

Cu2+>Zn2+>Co2+>Ca2+>Sr2+>

Cs+, K+>Na+

The order is useful for the purpose of decontamination.
Studies of the Organic Reactions of Metal Carbonyl. IV. The Acceleration Effect of the Addition of Organic Compounds on the Reaction of Olefin Oxide with Cobalt Hydrocarbonyl and on the Hydroformylation of Olefin Oxide
Authors: Takegami Yoshinobu , Yokokawa Chikao , Watanabe Yoshihisa
Published: July 2006

It has been observed that organic compounds with various kinds of functional groups have an accelerating effect on the reaction of olefin oxide with cobalt hydrocarbonyl and on the hydroformylation of olefin oxide.

1) The addition of a relatively small amount of ethyl alcohol promotes the carbonylation of propylene oxide with cobalt hydrocarbonyl until it is about 120 times faster than that of the standard run, carried out without alcohol. The amount of the alcohol necessary for this effect is about 2.0 mol./mol. HCo(CO)4. As the reaction products, only compounds with a β-hydroxy-n-butyryl structure (ester and aldehyde) have been obtained.

2) The compounds other than ethyl alcohol, such as n- and t-butyl alcohol, ethylene chlorohydrin, acetone, tetrahydrofuran, ether, acetal, benzaldehyde, ethyl acetate and acetonitrile, also have the same effect on this reaction. Among these compounds, ethyl and butyl alcohols have the largest effect. On the other hand, phenol has no effect. The accelerating effect is considered to be due to the basicity of these compounds.

3) The reactions of styrene oxide and epichlorohydrin with cobalt hydrocarbonyl are also promoted by the addition of ethyl alcohol.A relatively small amount of the alcohol accelerates selectively, the carbonylation of styrene oxide which is comparatively readily hydrogenated with cobalt hydrocarbonyl.2) For epichlorohydrin, the following relationship was observed to exist at an early stage of the reaction: rate of the gas absorption=k[epichlorohydrin] [ethyl alcohol].

4) The hydroformylation of ethylene oxide seems to be selectively promoted by the addition of ethyl alcohol, which gives β-hydroxypropionaldehyde, in a low yield.
Pyrolysis of Fluorinated Organic Compounds. I. The Pyrolysis of 1, 2-Dibromo-1-chloro-1, 2, 2-trifluoroethane and Some Related Halogenated Ethane Derivatives
Authors: Park J D , Lamb R W , Lacher J R
Published: July 2006

The synthesis of various halogenated ethane derivatives was performed by the pyrolysis of CF2Br-CFClBr and other similar compound. The reactions were carried out in a platinumlined tube at temperatures ranging from 350°C to 600°C alone and in the presence of nitric oxide or bromine. Various products were isolated and identified. A mechanism is postulated for the reaction.
The Synthesis of Lactones from ω-Chlorocarboxylic Acids
Authors: Saotome Kazuo
Published: July 2006

1) The kinetics of the hydrolysis of δ-chlorovaleric and of ω-chloroheptanoic acids in an aqueous solution of their sodium salts has been studied. The reason for the difference between the activation entropies has been discussed.

2) The methods for the preparation of δ-valerolactone from δ-chlorovaleric acid have been established.

3) By the thermal decomposition of the polyester from ω-hydroxyheptanoic acid, the dimeric lactone of the acid has been prepared, and the formation of the monomeric lactone has also been ascertained.
Selective Reduction of Phosphatides with Lithium Aluminum Hydride. II. Reductive Cleavage of the Glycerylphosphorylcholine Linkage
Authors: Kameyama Haru , Urakami Chieko
Published: July 2006

Reduction of egg yolk lecithins with lithum aluminium hydride under the following reaction conditions resulted in release of choline in about 50% based on the total water-soluble phosphorus; mole ratios of lecithin: lithium aluminium hydride of 1 : 10 or 1 : 15 at 10–15°C for 60–120min. were used. Unexpectedly, the reaction did not give any glycerylphos-phoric acid. Instead, the analytical results indicated that a phosphorus-oxygen fission of the cholin-phosphate linkage is accompanied by reduction of the phosphate moiety.
Phosphorylation of Alcohols by the Use of Benzyldiethyl Phosphite and Monobromocyanoacetamide or N-Bromosuccinimide
Authors: Mukaiyama Teruaki , Obata Teisuke , Mitsunobu Oyo
Published: July 2006

The phosphorylation of alcohols with benzyldiethyl phosphite and monobromocyanoacetamide has been investigated. By this method, the corresponding alkyldiethyl phosphates were obtained in fairly good yields along with benzyl bromide and cyanoacetamide. Similarly, it has been established that N-bromosuccinimide can be successfully used in the place of monobromocyanoacetamide in the above phosphorylation.
p-Nitrobenzene Azochromotropic Acid (Chromotrope 2B) as a Colorimetric Reagent for Thorium
Authors: Sangal Satendra P
Published: July 2006

A method for the colorimetric determination of thorium with Chromotrope 2 B has been described. The composition of the coloured chelate (λmax 550 mμ) is Th(Ke)2. The system adheres to Beer’s law from 074 p.p.m. to 16.6 p.p.m. of thorium between pH 3.0 and 6.5 at all temperatures from 5 to 95°C. The sensitivities are 0.232 γ/cm2 (Sandell) and 2.32 γ/cm2(practical) based on an absorbance of 0.01 unit at 580 mμ. The interference of some cations and anions has also been reported.
Magnetic Properties of Bi- and Uni-Nuclear Chromium(III) Complex Compounds at Low Temperatures
Authors: Kobayashi Hanako , Haseda Taiichiro , Mori Masayasu
Published: July 2006

The experimental study of the magnetic properties of bi- and uni-nuclear chromium(III) complex compounds in the low temperature

(Remark: Graphics omitted.)

region has given the results summarized in Tables III and IV. As has been mentioned above, the results listed in Table III show the tendency expected from the superexchange interaction theories.
A Study of the Growth of Particles in Silica Sol and Hydrogel as a Factor Determining the Final Structure of Silica Gel
Authors: Otouma Hiroshi , Ukihashi Hiroshi
Published: July 2006

The growth of particles in the polymerization of silicic acid has been investigated by means of light scattering. The following results were obtained:

1) Polymerization does occur for a long period, even after gelation.

2) While the aggregation is predominant near the gelation point, it seems to occur to a lesser extent even in the initial stage. The aggregate finally grows to as much as 800Å in diameter. It is of a porous and sponge like structure, including the solvent in it.

3) Hydrogel must be understood as an entity built up of secondary particles which also consist of primary ones. Consequently, hydrogel has prime structure and a substructure, by the former three-dimensional linkages among secondary particles are meant, while by the latter are meant those among primary particles.

4) There is a linear relationship between the scattering intensity of the hydrogel and the surface area of dried gel.
The Mössbauer Spectra of Several Inorganic Iron Salts
Authors: Takashima Yoshimasa , Ohashi Shigeru
Published: July 2006

The Mössbauer spectra of a variety of asyet-unexplored iron compounds have been investigated by using 14.4 keV. gamma rays from 57Fe. The isomer shifts and the quadrupole splitting extracted from the spectra have been discussed in terms of the electronegativity of the atoms connected to the iron atom. The correlation of these values with the bond character and the chemical structure has also been discussed qualitatively. The results obtained for a series of glassy substances of iron phosphate suggest that the Mössbauer spectra may permit us to study the chemical structure of iron compounds in an amorphous substance.
Mössbauer Spectra of Various Organic Iron Chelates
Authors: Takashima Yoshimasa , Tateishi Yasuyuki
Published: July 2006

Continuing our previous studies of the Mössbauer spectra of inorganic iron compounds, we have found some characteristic features of the spectra of some organic iron compounds. There is a general tendency, in a series of related compounds, for the isomer shift and the quadrupole splitting to increase regularly with increase in the structural complexity of the compounds.

The data for iron(III) acetate, benzoate and salicylate suggest the polynuclear structure of these compounds. The observed isomer shifts for other organic iron compounds may also be interpreted in terms of the chemical binding in the molecule.

No resonance absorption was observed for a few groups of organic iron chelates (1,3 diketone derivatives, etc.). Though our interpretation is still conjectual, the reason for this is believed to rest in the high recoil probability of these compounds.
A Kinetic Study of the Catalytic Isotopic Hydrogen Exchange of Propene with Deuterium Oxide on Palladium Black
Authors: Hironaka Yoshie , Hirota Kozo
Published: July 2006

A reaction mechanism for the catalytic isotopic hydrogen exchange of propene with deuterium oxide on palladium has been offered on the basis of the observed reaction rate and activation energy.

It has been concluded from the observed similarity in the dy-distribution and infrared spectra of the products at different temperatures that the exchange rates of the six hydrogen atoms in propene are nearly equal, while their activation energies are all 9 kcal./mol.

The exchange of methyl hydrogen atoms has been estimated to occur according to the double-bond migration mechanism as well as the dissociation mechanism.

A difference in catalytic activity has been found between palladium and nickel, even when their dy-distributions are nearly the same.
The Radiolysis of Ethylene Glycol Diacetate
Authors: Isoya Toshiro , Hirota Kozo , Hatada Motoyoshi
Published: July 2006

The radiolysis of air-free ethylene glycol diacetate by 60Co γ-rays has been studied at room temperature. The following results have been obtained : a) irradiation gives five gaseous products and six liquid products; b) the G value of the total of all the gaseous products is 2.18; c) the G value of the EGDA decomposition is 2.5. The effect of DPPH addition on the radiolytic products, the relation between radiolytic products and the mass spectrum of unirradiated EGDA, and the ESR spectrum of irradiated EGDA have also been studied. No remarkable difference in the products has been found between EGDA and various monoacetates except in the gaseous products, the yields from EGDA being 1/2–1/3 of those from methyl acetate.