bluuebunny/crossref_metadata_2025 huggingface dataset:
A Study on the Yield of (γ, α) Reactions with 20 MeV Bremsstrahlung
Authors: Oka Yoshinaga , Kato Toyoaki , Nomura Koichi , Saito Tatsuya , Tsai Hui-Tuh
Published: July 2006

The yields of the (γ, α) reactions on 7 elements up to an atomic number of 49, irradiated with 20 MeV bremsstrahlung, have been obtained through gamma-ray spectrometric measurements of the resultant activities. The yield values, as measured in absolute disintegration rates at the end of irradiation per mole per roentgen, have been plotted against atomic number of the target nuclides. The yield curve shows a maximum in the region of copper and zinc, and drops rapidly with increasing atomic number. The shape of this yield curve is similar to that for the photoalpha yield as a function of atomic number. It can be seen that the yield levels off in the region of silver and indium. A mechanism such as the direct photoelectric effect is thought to be responsible for this behavior. The yield of the (γ, α) reaction of an element amounts to only a small fraction, at most a few tenths of a per cent, of the total photonuclear yield.
Convenient Method for the Preparations of Carboxylic Thiolester and Acid Anhydride
Authors: Mukaiyama Teruaki , Katsuyama Harumi
Published: July 2006

The reactions of mercuric carboxylates with bivalent sulfur compounds, such as aralkyl sulfides and mercaptoles, were investigated. When mercuric acetate and aralkyl sulfides were refluxed in benzene, mercury mercaptides and aralkyl acetates were obtained. It was made clear that the reactivity of the sulfides depends on the stability of carbonium ions given by elimination of the mercapto group. Next, it was found that acetic anhydride, benzophenone and mercury phenylmercaptide were obtained in high yields by the equimolar reaction of benzophenone diphenylmercaptole with mercuric acetate. Further, the reaction was extended to the preparative method of carboxylic acid anhydrides from free acids by treating the carboxylic acids with diphenylmercury and the mercaptole. On the other hand, S-phenyl thioacetate, benzophenone and mercury mercaptide were produced in good yields when benzophenone diphenylmercaptole (2 mol) was treated with mercuric acetate (1 mol). Further, it was established that thiolesters were exclusively produced in good yields along with benzophenone and the mercury mercaptide by the reaction of benzophenone diphenylmercaptole or bis (p-chlorophenyl) mercaptole (2 mol) with free carboxylic acids (2 mol) and diphenylmercury (1 mol).
Studies on Amino-hexoses XIV. Preparation of Partially O-Carboxymethylated Chitin and Its Component 3-O- and 6-O-Carboxymethyl-d-glucosamine, and the Corresponding Glucosaminitols
Authors: Miyazaki Tsuyoshi , Matsushima Yoshio
Published: July 2006

3-O-carboxymethyl-d-glucosamine, 6-O-carboxymethyl-d-glucosamine, and the corresponding glucosaminitols are prepared as reference compounds in a study of a lysozyme action on a partially-O-carboxymethylated chitin. The preparation of partially-O-carboxymethylated chitin, a substrate of hen-egg white lysozyme, is also described.
Selective Chemical Cleavage of Asparagine Peptides
Authors: Shiba Tetsuo , Koda Akio , Kusumoto Shoichi , Kaneko Takeo
Published: July 2006

Asparagine peptide was selectively cleaved by the Hofmann rearrangement followed by an alkaline treatment at the peptide linkage in which an amino group of the asparagine residue participated. Upon reaction of N-benzyloxycarbonyl-l-alanyl-l-asparagine with one equivalent of bromine and three equivalents of aqueous sodium hydroxide solution at 60°C, 1-(N-benzyloxycarbonyl-l-alanyl)-2-oxoimidazolidine-5-carboxylic acid was obtained in quantitative yield. When this was treated with an aqueous methanolic sodium hydroxide solution at room temperature, a cleavage reaction occurred to give N-benzyloxycarbonyl-l-alanine and 2-oxo-imidazolidine-5-carboxylic acid. Under the same condition of the rearrangement, N-benzyl-oxycarbonyl-l-asparaginyl-l-phenylalanine was converted to 1-benzyloxycarbonyl-2-oxoimidazo-lidine-5-carbonylphenylalanine. Since glutamine peptide could not give the corresponding ring compound, this cleavage reaction was found to be specific to asparagine peptide.
Electron Spin Resonance of X-Irradiated Single Crystals of Zinc Acetate Dihydrate: Hindered Rotation of Methylene Group in a Free Radical CH2COO−
Authors: Ohigashi Hiroji , Kurita Yukio
Published: July 2006

Electron spin resonance spectra of X-irradiated single crystals of zinc acetate dihydrate have been studied at 9.2 Gc in the temperature range from 77°K to 380°K. The radicals trapped at 77°K are CH3 and CH2COO−. The former disappears above 150°K. The latter is stable and persists up to 370°K. The principal values of hyperfine coupling constants for two indetical hydrogens of the radical CH2COO− have been found to be 10.5, 20.6 and 33.4G. The CH2 group in the radical undergoes restricted rotation about the C–C bond. Analysis of the ESR spectra at different temperatures with a modified Bloch equation shows the activation energy and the frequency factor for the restricted rotation to be 5.8±0.2 kcal/mol and (4.4±2.7)×1012 sec−1, respectively.
Studies on the Substrate Specificity of Egg White Lysozyme. II. Mode of the Enzymatic Action on Partially-O-carboxymethylated Chitin
Authors: Miyazaki Tsuyoshi , Matsushima Yoshio
Published: July 2006

Partially-O-carboxymethylated chitin was found to be a soluble substrate of hen egg white lysozyme. The products of the lysozyme action were analyzed by gel filtration and by ion-exchange chromatography. The reducing ends of the saccharides produced by the enzyme were the N-acetyl-glucosamine residue or the 3-O-carboxymethyl-N-acetyl-glucosamine residue. 6-O-Carboxymethyl-N-acetyl-glucosamine never appeared as a reducing end. The O-substituted disaccharide detected in the reaction products was 6′-O-carboxymethyl-di-N-acetyl-chitobiose. The results of the reducing-end analyses and the finding that none of the monomers were formed except for the unsubstituted N-acetyl-glucosamine, while an O-substituted dimer was formed as is mentioned above, are in conformity with the conformation of the enzyme-substrate complex proposed by Blake et al. as a result of their X-ray crystallographic investigations.
Diffuse Reflection Spectra of Some Dinitrobiphenyl Complexes
Authors: Abe Kunihiro , Matsunaga Yoshio , Saito Gunzi
Published: July 2006

The 4,4′-dinitrobiphenyl complexes with benzidine and tetramethylbenzidine, in which the long axes of the component molecules are known to be perpendicular to each other, were examined for the diffuse reflection spectra. The deep coloration in these complexes was found to be due to the appearance of broad, weak charge-transfer absorptions.
Polarized Absorption Spectra of Single Crystals of Ion Radical Salts. I. Molecular Compounds of 7,7,8,8-Tetracyano-p-quinodimethane with N,N,N′,N′-Tetramethyl-p-phenylenediamine and N,N-Dimethyl-p-phenylenediamine
Authors: Kuroda Haruo , Hiroma Shoji , Akamatu Hideo
Published: July 2006

Polarized absorption spectra in the 10–40 kK region were observed on single crystals of the molecular compounds of tetracyano-p-quinodimethane(TCNQ) with tetramethyl-p-phenylenediamine (TMPD) and with dimethyl-p-phenylenediamine (DMPD). These molecular compounds possess an ionic structure in the ground state. A strong, broad absorption band appears in the near-infrared region of the crystal spectra with a polarization parallel to the crystal axis along which the component ions are alternately stacked making their molecular planes parallel to each other. The absorption maximum of this band is located at 7.7 kK in TMPD·TCNQ and at 8.5 kK in DMPD·TCNQ. These bands are assigned as a one associated with the charge transfer from TCNQ− ion to the positive ion of the donor. Other absorption bands found in the spectra can be assigned as local excitation bands associated with the intramolecular transitions of the component ions. However, they are found to be considerably broadened and appreciably shifted to higher energy as compared with the solution spectrum of each component ion.
On the Isomerization of Dimers of Perchloro-(3,4-dimethylenecyclobutene) as Revealed by X-ray Methods
Authors: Furusaki Akio
Published: July 2006

The isomerization of several dimers of perchloro-(3,4-dimethylenecyclobutene) (I) has recently been reported by Fujino et al. Of these dimers, one (II) is transformed to other isomers (IIIa) and (IIIb) by means of pyrolysis at ca. 200°C. When heated to ca. 250°C, IIIa and IIIb are further converted into a fourth isomer (IV). The present X-ray study has revealed that II corresponds to perchloro-(3,4,7,8-tetramethylene-tricyclo[4.2.0.02.5]octane), as supposed from the chemical evidence, and IV, to perchloro-(4,8-dimethylene-tricyclo[3.3.2.01.5]deca-2,6-diene). It has been further established, from the results of the X-ray analysis of the dichloride of IIIa with the help of the chemical information, that IIIa and IIIb have the same two-dimensional chemical structure, perchloro-(3,4,7,8-tetramethylene-cycloocta-1,5-diene), rather than perchloro-(2,3,7,8-tetramethylene-bicyclo[4.2.0]octa-4-ene) which was speculated by Fujino et al., and that IIIa and IIIb are different from each other in the conformation of the cyclooctadiene ring. These structures for II, IIIa, IIIb, and IV give a reasonable explanation of the mechanism of the successive isomerization reactions mentioned above.
The Hydration and Crystallization of ρ-Alumina and Alumina-gel in Aqueous Solutions of Various Basic Reagents
Authors: Yamaguchi Goro , Chiu Wen-Chau
Published: July 2006

Alumina gel, boehmite gel, ρ-alumina, η-alumina, and γ-alumina were treated with aqueous solutions of various inorganic and organic reagents at temperatures below 100°C. Boehmite gel, η-alumina and γ-alumina were found to show no change upon this treatment, while alumina gel and ρ-alumina either remained unchanged or changed into fairly well-crystallized boehmite, boehmite gel, gibbsite, bayerite, or nordstrandite, according to the treating conditions. It has been newly established that water-containing pyridine and aniline, the aqueous solution of hydrazine hydrate, and the aqueous solution of o, m-phenylenediamine are effective in forming fairly well-crystallized boehmite, nordstrandite, and gibbsite respectively.
Spectroscopic Studies of Mixed Amine Carbonyl Complexes of d6 Structure. I. Visible and Ultraviolet Absorption Spectra of Diamine-tetracarbonyl Complexes of Chromium(0), Molybdenum(0) and Tungsten(0)
Authors: Saito Hide , Fujita Junnosuke , Saito Kazuo
Published: July 2006

Chromium(0), molybdenum(0) and tungsten(0) complexes of [M·(CO)4AA]0 type (AA=ethylenediamine (en), l-propylenediamine (l-pn), trimethylenediamine (tn), bipyridyl (bp), and phenanthroline (phen); l-pn and tn derivatives are new compounds) have been synthesized and their absorption spectra, rotatory dispersion (RD) and circular dichroism (CD) measured in methanol at room temperature. The nature of the absorption bands has been discussed by comparing them with one another and with those of hexacarbonyl- and piperidinepentacarbonyl complexes of these elements. The peaks in the region 23000 to 25000 cm−1 seem to be due to spinallowed d–d transition. The bands at 30000 to 33000 cm−1 appears to correspond to the metal to carbonyl charge transfer band of hexacarbonyls at ca. 36000 cm−1. Besides them, complexes of aromatic amines (bp and phen) show broad and strong bands at 21000 to 22000 cm−1 which seem to owe to metal to amine charge transfer.
Complexes of Copper Chlorides with Benzophenoneimine
Authors: Misono Akira , Osa Tetsuo , Koda Seiichiro
Published: July 2006

We tried to prepare complexes of copper chlorides with benzophenoneimine. The complex CuCl2·2Ph2C=NH and the complex CuCl·Ph2C=NH were newly prepared, and some of their properties were investigated by physico-chemical techniques. Besides these, two other complexes were obtained, but they were not completely stoichiometric compounds.
Electrometric Studies on the Reaction between Pb(II) and Alkali Meta-Vanadate
Authors: Saxena R S , Sharma C P
Published: July 2006

The reaction between Pb2+ and VO3− was investigated by means of electrometric techniques involving potentiometric, pH-metric and conductometric titrations between Pb(NO3)2 and NaVO3 at several concentrations, with each of the reagents alternately used as titrant. The sharp breaks and inflections obtained in titration curves evidenced the formation of lead metavanadate having the molecular composition PbO·V2O5 at pH range 4.25–5.25. The precipitation of the compound has been found to be almost quantitative and the titration results are very accurate and reproducible.
Asymmetric Hydrogenating Activity of Modified Raney Nickel Catalyst
Authors: Tatsumi Susumu
Published: July 2006

In the asymmetric hydrogenation of methyl acetoacetate to methyl 3-hydroxybutyrate using Raney nickel catalysts modified with optically active hydroxy dicarboxylic acids and related compounds (for example, Y. Izumi, S. Tatsumi and M. Imaida, Bull. Chem. Soc. Japan, 39, 2223 (1966)), the relationship between the asymmetric activities of the catalysts and the chemical or stereochemical structures of modifying reagents was discussed on the basis of data obtained previously. The effects of the conditions used for modification upon the asymmetric activity were also discussed inclusively. Moreover, the stability of asymmetric activity in the modified catalysts has been found to be very excellent.
The Cyclization of Malononitrile and Ketones by Ammonium Acetate
Authors: Sakurai Akio , Midorikawa Hiroshi
Published: July 2006

Hitherto various heterocyclic compounds have been synthesized by the reaction of ketones with ethyl cyanoacetate or ethyl acetoacetate in the presence of excessive ammonium acetate. On the basis of these facts, the reaction of malononitrile with ketones by ammonium acetate was carried out; aminopyridine derivatives, such as 2, 4-diamino-3, 5-dicyano-6-alkylpyridines (I) and 2-amino-3-cyano-4, 6-dialkylpyridines (II), were thus obtained.
Synthesis of Natural Human Angiotensin
Authors: Aoyagi Haruhiko , Arakawa Kikuo , Izumiya Nobuo
Published: July 2006

The synthesis of a decapeptide, H-l-Asp-l-Arg-l-Val-l-Tyr-l-Ile-l-His-l-Pro-l-Phe-l-His-l-Leu-OH, which has an amino acid sequence assumed by Arakawa et al. for natural human angiotensin I, has been performed. The chemical and biological properties of the synthetic product have shown to be in agreement with those of the natural material, thus the structure of human angiotensin I has been confirmed by the present synthesis.
The Dimerization of Butadiene by Palladium Complex Catalysts
Authors: Takahashi Shigetoshi , Shibano Toshiki , Hagihara Nobue
Published: July 2006

It has been found that palladium-phosphine complexes coordinated by dienophile and tetrakis-(triphenylphosphine) palladium catalyzed the linear dimerization of butadiene. The dimerization of butadiene with bis(triphenylphosphine)(maleic anhydride)palladium in aprotic solvents, such as benzene, tetrahydrofuran, and acetone, gave octatriene-1,3,7 selectively in good yields. In such alcohols as methanol, ethanol, and isopropanol, butadiene was converted to 1-alkoxyoctadiene-2,7 and/or octatriene-1,3,7, depending on the nature of the alcohols employed. The dimerization in secondary amines, such as morpholine, piperidine, and diisopropylamine, gave butadiene dimer-amine adducts of the R2N(C8H13) type, while that in primary amines, such as aniline and n-butylamine, gave a mixture of RNH(C8H13) and RN(C8H13)2. Phenoxy- and acetoxyoctadiene were also obtained from the reactions in phenol and acetic acid respectively.
The Zinc Oxide-Copper Catalyst for Carbon Monoxide-Shift Conversion. II. The Catalytic Activity and the Catalyst Structures
Authors: Uchida Hiroshi , Oba Masaaki , Isogai Norio , Hasegawa Toji
Published: July 2006

Structures of the zinc oxide-copper catalysts, whose catalytic activity in carbon monoxideshift conversion had been determined, were investigated by X-ray diffraction technique, mercury and helium-volume measurement, and electron microscopy. The electron microscopic observations were conducted in two ways; one on a catalyst sample after the activity test and the other on a raw sample while undergoing specified treatments in a reaction chamber attached to the electron microscope. On the basis of models of particle geometry obtained from the electron microscopic images, the results on pore volume, average diameters of pores and particles, all dependent on the method of preparation and the chemical composition, are explained. The models and the observed dependency of the specific activity of copper surface on the copper content indicate that the finer copper particles, whether patch-like or massive, show the higher specific activity. The fine copper particle is apt to be oxidized more readily than the well-grown particle.
Mössbauer Effect of the 119Sn in the Molecular Complexes of Tin Tetrachloride with Some Aliphatic Compounds
Authors: Ichiba Sumio , Mishima Mitsuo , Sakai Hiroshi , Negita Hisao
Published: July 2006

Molecular complexes of tin tetrachloride with some aliphatic compounds, such as alcohols and esters, were investigated by means of the Mössbauer effect due to 119Sn, irradiation being made by 23.8 keV γ-rays from the 119mSn in tin dioxide. Most of these complexes show quadru-pole splittings resulting from the addition of organic molecules to tin tetrachloride, although broad absorption curves are observed in some cases. The isomer shifts range from 0.30 to 0.45 mm/sec. They are much smaller than that of tin tetrachloride itself. The results are interpreted by taking account of the electronic structures of the complexes.
Effect of the Ionic Strength on the Behavior of Sodium Chondroitin Sulfate C in Aqueous Solutions
Authors: Nakagaki Masayuki , Ikeda Kiyoshi
Published: July 2006

Viscosity and light-scattering investigations were carried out in aqueous sodium chloride solutions at 25°C on a sample of sodium chondroitin sulfate C from shark cartilage. The weightaverage molecular weight of 74000 was obtained. The molecular dimensions, obtained from the viscosity-partial specific volume, from the light scattering-partial specific volume, and from the light scattering-viscosity, were found to fit well for a long-rod model with a length of about 800 Å and a diameter of about 10 Å at the infinite ionic strength.
The Solution Properties of Nonionic Oligosoaps Derived from Nonylphenol Formaldehyde Resin
Authors: Ishigami Yutaka , Narasaki Hideo
Published: July 2006

Nonionic oligosoaps (mol wt 6200 and 9700), consisting of a short polymer chain with chemically-attached soap-like groups, have been prepared from nonylphenol formaldehyde resin (mol wt 2000) by condensing 11 and 20 mol of ethylene oxide per nonylphenol ring making up the resin. Light-scattering, surface-tension, and vapor-pressure-depression measurements have been carried out. These oligosoaps formed agregates in water; the micellar weights were 81000 (11 mol condensate) and 70700 (20 mol), respectively, much as with the cationic oligosoap derived from polyallyl chloride reported elsewhere. The aggregation number, the dependence of the micellar weight on the sodium chloride concentration, the small surface area per molecule, in water, and the nonaggregation in nonaqueous solutions are discussed. It is noteworthy that these oligosoaps behave like monosoaps in various ways.
Faradaic Impedance of Fast Electrode Processes as Measured by an Impedance Bridge Using an Inductor
Authors: Tanaka Takuma , Imai Hideo
Published: July 2006

An impedance bridge using an inductor in parallel with the cell is proposed for accurate measurement of kinetic parameters of fast electrode processes. The theory and method of analysis are given in detail. Its applicability was proved up to at least 50 kc, and possibly at higher frequencies. The kinetic parameters obtained by this method for the electrode reaction Cd2++2e=Cd(Hg) in m Na2SO4 at the D. M. E. were α=0.17, and k°=0.064 cm/sec (25°C).
Chemical Studies of Minerals Containing Rarer Elements from the Far East District. LXI. Yttrofluorite from Suishoyama, Kawamatamachi, Fukushima Prefecture, Japan
Authors: Uetani Keiji , Ogimura Yoshiko , Kato Akira , Nagashima Kozo
Published: July 2006

A very rare yttrium mineral, yttrofluorite, from granite pegmatite found at Suishoyama, Fukushima Prefecture, was studied. Chemical analysis: Ca 35.50%, Σ Rare earths 18.84%, Mg 0.42%, Fe 0.34%, Al 0.15%, Mn 0.08%, F (remainder) 44.67%. Cell constant calculated from the X-ray powder data: a0=5.500 Å. Specific gravity: 3.51 (measured), 3.62 (calculated). Refractive index: n=1.454. The distribution pattern of lanthanide elements studied by the X-ray fluorescent method disclosed that the mineral is poor in cerium group lanthanide, rich in yttrium group with maxima at dysprosium and erbium. The mineral occurs as aggregates of small crystals in spessartine garnet embeded in large crystals of feldspars.
The Synthesis of Agarobiose
Authors: Hirase Susumu , Araki Choji , Arai Kiyoshi
Published: July 2006

Agarobiose, 3,6-anhydro-4-O-β-d-galactopyranosyl-l-galactose, was synthesized by a series of reactions involving the condensation of 1, 2-O-isopropylidene-3, 6-anhydro-l-galactopyranose with tetra-O-acetyl-α-d-galactosyl bromide, deacetylation with sodium methoxide, and the hydrolytic removal of the O-isopropylidene group. The resulting disaccharide, and its osazone and dimethyl acetal were identical with the corresponding authentic samples obtained naturally.
Macro Rings. I. Syntheses of a Novel Class of Compounds with a Chain of Alternating Benzene Rings and Methylene Groups
Authors: Inazu Takahiko , Yoshino Tamotsu
Published: July 2006

As starting materials for the synthesis of a macrocyclic compound, I, bridged diphenylmethane derivatives of the general formula p-XC6H4CH2(C6H4CH2)mC6H4X-p were synthesized; X is hydrogen or (CH2)nCOOR (n=0–3), m=2 or 3, and R=hydrogen or alkyl.
Azetidines. IV. The Reaction of 1-t-Butylazetidinyl-3 Tosylate with Amines and Mercaptans
Authors: Chen Teng-yueh , Kato Hiroshi , Ohta Masaki
Published: July 2006

3-Amino and 3-mercapto-azetidine derivatives were prepared by the reaction of 1-t-butylazetidinyl-3 tosylate with ammonia, primary and secondary amines, and mercaptans. Ring cleavage was observed when the tosylate was reacted with compounds of higher acidity, such as thiobenzoic acid.
A Study of the Nucleophilic Solvation Based on the Theory of Chemical Equilibrium
Authors: Kagiya Tsutomu , Sumida Yūzō , Inoue Tokuji
Published: July 2006

The nucleophilic solvation to a deuterium atom in a methanol-d molecule has been quantitatively studied by using the infrared spectroscopic data of the O–D vibrational band. The position of the O–D band did not change in spite of the variation in the methanol-d concentration in solutions of a single solvent, whereas the area of the O–D peak changed in proportion to the first-order of the methanol-d concentration. From these results, it has been concluded that the area of the O–D band corresponds to the concentration of the methanol-d solvated. In a binary solvent system, which consisted of components with substantial differences in the electron-donating power, two positions of the O–D peak were observed at positions identical to those in the component examined in a single solvent system, and the area of each O–D peak changed with the composition of the system. These results led to the conclusion that the nucleophilic solvation of each component in the binary system took place competitively and individually. From the quantitative treatment of the results on the basis of the theory of chemical equilibrium, the equilibrium constant of the nucleophilic solvation of a solvent to methanol-d was calculated. The following empirical formula was obtained between the electron-donating powers and the nucleophilic equilibrium constants of various solvents:

(Remark: Graphics omitted.)
Solvent Effects on the Proton Magnetic Resonance Spectra of 2,3-Dichlorobutane and the Problem of Rotational Isomers
Authors: Kondo Shoichi , Tagami Eijiro , Iimura Kazuyoshi , Takeda Masatami
Published: July 2006

Effect of solvent on the coupling and magnetic shielding constants of meso and racemic 2,3-dichlorobutanes has been examined using proton magnetic resonance (PMR). The iterative method of spectrum analysis is applied to the simple sub-state in order to improve the computation speed and the computer capacity. The variations in the coupling constants for the meso configuration are to some extent correlated with the population as a function of dielectric constant ε of solvent using an Onsager model. The coupling constants of the racemic configuration were almost independent of the solvent dielectric constant. The estimated chemical shift dependence on ε of the reaction field does not adequately describe the experimental data.
Rectification Effects Using Polyelectrolyte Solutions
Authors: Shimizu Kunitoshi , Sen\={o} Manabu , Nozaki Hiroshi
Published: July 2006

The rectifying properties of liquid junctions of polyelectrolyte solutions are examined and discussed. In the case of liquid junctions between aqueous solutions of poly(styrene-sulfonic acid) and poly(2-vinyl-N-n-butylpyridinium hydroxide), the rectification effects greatly depend on the concentrations of the polyelectrolytes and on the frequencies of the voltages applied, that is, rectification effects can not be found when the concentrations of polyelectrolytes are lower than 0.68×10−3 equivalents per liter and when the frequencies of the alternating voltages are higher than 200 cps. The mechanism of rectification can be explained to some extent by a semiconductor analogy. In the case of liquid junctions between poly(styrene-sulfonic acid) and poly(2-vinyl-N-n-butylpyridinium bromide), the static current versus voltage curves have strong hysteresis loops. The rectification effects can be slightly observed when alternating voltages with frequencies lower than 100 cps are applied. In this case, however, the mechanism of rectification can not be explained by the semiconductor analogy.
The Hydrogen Yields in the Radiolysis of Cysteine and Biscysteinatocobaltate(III) in 0.8 n Sulfuric Acid
Authors: Matsuura Niro , Shinohara Nobuyoshi
Published: July 2006

Radiation-induced oxidation of cysteine in an acid medium was studied by measuring the hydrogen yields at an initiation stage of radiolysis. In the deaerated system G(H2)=4.0 along with the G(–CySH)=7.1 were observed and the results can be interpreted in terms of the yields of primary radicals from the radiolysis of water in 0.8 n sulfuric acid medium. From stoichio-metric view point it is predicted that the radiolysis takes place through cysteine radical as intermediate to form cystine. In the aerated system on the other hand, the radiolysis of cysteine is much complicated. For a possible explanation satisfying all the G values obtained, 10.5 in the disappearance of cysteine, 4.0 in the formation of hydrogen peroxide and 0.4 in the hydrogen, the air oxidation of cysteine caused by the radicals, HO2 and OH which produce H2O2 and O2 by the radical recombination, is proposed as mechanism. The radiolysis of cysteine is greatly reduced by complexation with metallic ion as biscysteinatocobaltate(III) complex. The absence of hydrogen abstraction from cysteine by H atom, the isolation of cysteine from a ligand site and the extraordinary high G values in the disappearance of optical absorption of the complex can be cited as characteristics in the radiolysis of the biscysteinatocobaltate(III) complex. The intramolecular redox of the complex into Co(II) ion and cysteine is a best fit mechanism as over all reaction in the radiolysis of the biscysteinatocobaltate(III) complex.
The Gas-phase Oxidation of Propylene in an Inert Fluidized Bed Reactor under Pressure. The Effects of the Reaction Conditions on the Formation of Oxidation Products
Authors: Echigoya Etsuro , Masai Mitsuo , Morikawa Kiyoshi
Published: July 2006

The oxidation of propylene is studied in an excess-propylene atmosphere under pressure, using an inert fluidized bed reactor. The effects of the temperature, the pressure, and the concentration of oxygen on the reaction were examined. The so-called “negative temperature coefficient” is clearly observed with relation to the rate of the oxidation of propylene and the rates of the formation of acetaldehyde, propylene oxide, acrolein, carbon monoxide, methane, and ethylene. Therefore, the reaction courses involving these may be regarded as radical-chain reactions. Little effect of the pressure is observed. The molar fraction of oxygen exerts a profound effect on the yields of acetaldehyde, propylene oxide, and acrolein.
Polymerization and Isomerization of Allylbenzene and Propenylbenzene
Authors: Shimizu Akihiko , Otsu Takayuki , Imoto Minoru
Published: July 2006

In order to clarify the relationship between the isomerization and polymerization of α- and β-olefins by various types of catalysts, the isomerizations of allylbenzene and propenylbenzene during their polymerizations were studied. In the presence of cationic catalysts (AlBr3, BF3O(C2H5)2, etc), neither the polymerization nor the isomerization of allylbenzene was observed, but propenylbenzene was found to be polymerized without the isomerization of the monomer to give a solid polymer which consisted substantially of a 1,2-structure, plus a minor unit of an isomerized structure. In the cases of the Natta catalysts [TiCl3-Al(C2H5)3, Al/Ti≥2], allylbenzene could easily be polymerized to a high-molecular-weight polymer with a 1,2-structure. During this polymerization, both positional and geometrical isomerizations of the unreacted monomer were observed, indicating that the propenylbenzene obtained from the isomerization did not participate in the polymerization of allylbenzene. It was also found that the polymerization and the positional isomerization of propenylbenzene by these catalysts did not occur.
Infrared Spectra of a Few Transfer Ribonucleic Acids
Authors: Tsuboi Masamichi , Shuto Katsuichi , Takemura Shosuke , Nishimura Susumu
Published: July 2006

Infrared absorptions have been observed in the 1800–700 cm−1 region of four purified amino-acid transfer ribonucleic acids (tRNA’s): alanine tRNA and valine-I tRNA from Torulopsis utilis (torula yeast) and methionine tRNA and tyrosine tRNA from Escherichia coli in their deuterated film. Spectral features in the 1550–1750 cm−1 region of the valine, methionine, and tyrosine tRNA’s indicate that each of these tRNA’s has an amount of base-pairs, which is in accord with the “clover leaf” structure previously proposed. The relative amounts of the paired and unpaired cytosine residues are estimated on the assumption that the intensity ratio of the 1523 and 1500 cm−1bands is 0.18 for the paired cytosine residue and 0.84 for the unpaired cytosine residue. The results are also compatible with the “clover leaf” structure.
The Reaction between Hydrocarbon and Hydrogen Cyanide in Silent Electrical Discharge. III. The Reaction of Ethylene or Propylene with Hydrogen Cyanide
Authors: Kawamoto Kazuaki , Nishimura Yoshiharu
Published: July 2006

The present investigation was undertaken to find out whether or not the relative amounts of acrylonitrile obtained by the reaction between ethylene and hydrogen cyanide in a silent discharge are affected by the substances (Hg(CN)2, Cu, CuCN, Al, Zn and Fe) placed in a glass filter of the special discharge tube, and to examine the possibility of the direct introduction of a cyano radical into propylene by means of the silent discharge. The yield of acrylonitrile depended upon the packing materials in the glass filter. When the discharge wall of the glass filter was filled with Hg(CN)2, the yield of acrylonitrile was at its maximum. When a mixture of propylene and hydrogen cyanide was discharged in an ozonizer in the absence of air, the main liquid products were crotononitrile, methacrylonitrile, and n-propyl cyanide. Besides these compounds, the reaction products were confirmed to consist of isopropyl cyanide, acetonitrile, acrylonitrile, 4-methyl-1-pentene, 2,3-dimethylbutane, 1,5-hexadiene, 2-methylpentane, 1-hexene, n-hexane, and gaseous products. Judging from the relative concentration of each compound in the reaction products, it may be said that 2-methylvinyl, isopropenyl, propyl, allyl, isopropyl, and cyano radicals are the main intermediates in this reaction system.
Mechanism of Emulsification with Special Reference to Solid Stabilized Emulsions
Authors: Jain S P , Srivastava S N
Published: July 2006

Mechanism of emulsification with special reference to ferric hydroxide as emulsifier has been studied. The sol of ferric hydroxide having maximum possible stability has been prepared. Its particle size as determined by electron microscope is of 63 Å radius. The stability of the sol in presence of different amounts of electrolytes of different valencies has been studied by measuring its zeta potentials in terms of interaction energy curves. By using these different stages of partially flocculated ferric hydroxide sol as emulsifier the emulsions of toluene in water were prepared and their relative stabilities assessed by adding various electrolytes. Then the stability of the emulsions formed has been studied by the measurement of zeta potentials micro-electrophoretically in the light of the D.V.O. theory. The size of the emulsion globules as determined microphotographically is 1.1μ radius. The pH and interfacial tension measurements have also been carried out. From interfacial tensions between the disperse phase and the dispersion medium at different amounts of electrolytes, the surface charge of the emulsions has been deduced which is found to be in good agreement with the electrophoretic results. Finally a correlation has been sought between the stability of the emulsions and the corresponding partially flocculated sols used in emulsification.
Studies in Nuclear Magnetic Resonance Spectroscopy. Long-range Shielding by Triple Bonds
Authors: Jackman J M , Sarkis George Y
Published: July 2006

The magnetic shielding of nuclei due to distant chemical groups may be calculated from the knowledge of the magnetic anisotropy of the bonds in these groups. The reverse procedure, namely, the calculation of the magnetic anisotropy of bonds from NMR relative chemical shifts has been employed here to estimate the magnetic anisotropy of −C≡C, −C≡N, and −N≡C triple bonds. The paramagnetic contribution to the shielding of the acetylenic proton was estimated from the calculated value of ΔχC≡C, and from the known geometry of the molecule. The value thus obtained is compared with that calculated by quantum mechanical methods.
Exo-electron Emission from Sandblasted Steel
Authors: Tamai Yasukatsu , Momose Yoshihiro
Published: July 2006

The exo-electron glow curves up to about 250°C were measured for the sandblasted steel specimens, which had been kept in air for 2 min 30 sec, 2 hr 30 min or 13 hr after the sandblast. It was found that the plots of the integrated total counts against the keeping time in doublelogarithmic scales gave a straight line with negative slope and that the emission peak moved to higher temperatures and at the same time the emission intensity decreased with the keeping time. It was also found that at the higher heating rate the peak intensity became larger and the peak temperature became higher than at the lower heating rate and that the remaining counts above a given temperature in the glow curve was linearly related with the temperature in semi-logarithmic scales, regardless of the heating rate. Comparing the behavior of exo-electron emission with that of the thermoluminescence of phosphors, it is supposed that electron traps are distributed on or in the deformed solid surface.
The Crystal and Molecular Structure of N-(p-Bromophenyl)-α-d-ribopyranosylamine 2,4-Phenylboronate
Authors: Shimanouchi Hirotaka , Saito Norio , Sasada Yoshio
Published: July 2006

Crystals of N-(p-bromophenyl)-α-d-ribopyranosylamine 2,4-phenylboronate, C17H17O4NBBr, are monoclinic, with two molecules in a unit cell of the dimensions, a=12.98, b=10.80, c=6.34Å, and β=99.4°, and with the space group of P21. The intensity data were collected by a photographic method and the structure was solved by the heavy atom method. The final R factor is 0.100. The absolute configuration was also determined.
A Theoretical Interpretation of Substituent Effects on the H–H and 13C–H Spin Coupling Constants for CH3X, (CH2)2X, and CH2=CHX Derivatives
Authors: Yonezawa Teijiro , Morishima Isao , Fujii Mutsuo , Kato Hiroshi
Published: July 2006

An attempt has been made to explain the experimental trend of H–H and 13C–H nuclear spin coupling constants for CH3X, (CH2)2X, and CH2=CHX systems on the basis of the Pople and Santry expression for the contact term. The calculated magnitudes of the coupling constants are parallel with the observed values, but are uniformly lower by a factor of between 1.5 and 2. The variation in the calculated coupling constants with the electronegativity (Ex) of the substituent, X, follows the well-acknowledged observed tendency for directly-bonded 13C–H, geminal H–H, and vicinal cis and trans H–H coupling constants. Theoretical calculations also predict the Ex dependency of the directly-bonded 13C–H coupling constants for two geminal C–H bonds in the 13CH2=CHX fragment. The difference between two geminal 13C-C-H coupling constants in the CH2=13CHX system is also obtained by calculation. Discussions of the factors which dominate the couplings are also presented.
Microwave Spectrum of Cyclohexene
Authors: Ogata Teruhiko , Kozima Kunio
Published: July 2006

The microwave spectrum of cyclohexene has been investigated in the frequency region from 7.3 to 27 Gc/sec with a conventional Stark modulation spectrometer, and the spectrum in the ground vibrational state has been assigned. The dipole moment lies entirely along the b-principal axis; its value, as obtained from the Stark displacements, is 0.332±0.012D. From the rotational constants and the orientation of the dipole moment, it can be concluded that the equilibrium conformation is a “half-chair” form. Its most probable structure has been determined.
Kinetic Studies of Oxygen Exchange and Racemization Reactions of Diaryl Sulfoxides in Sulfuric Acid of Various Concentrations
Authors: Kunieda Norio , Oae Shigeru
Published: July 2006

When 18O-labeled and optically active sulfoxides are dissolved in a concentrated sulfuric acid, one observes the concurrent oxygen exchange and racemization reactions of the sulfoxides, and these reactions were found to proceed through the SN1-like path (S. Oae et al., Bull. Chem. Soc. Japan, 38, 546 (1965); 41, 696 (1968)). We have found that the concurrent oxygen exchangeand racemization reactions also take place even in less concentrated sulfuric acid at somewhat higher temperature, i. e. 70% sulfuric acid at 30°C, and proceed through a different mechanistic route, very likely an SN2-like path. Kinetic investigation on these reactions in sulfuric acid of various concentrations (66.5–96.3%) suggests there is a gradual change of mechanism of the reaction, i. e. from SN2 type in 66.5% to SN1 type in 96.3% with the increase of the concentration of sulfuric acid.
The Structure of Copolymers of l-Proline with γ-Benzyl-l-glutamate in Organic Solvents
Authors: Sakai Rume , Ikeda Shoichi , Isemura Toshizo
Published: July 2006

The equilibrium conformations of three copolymers of l-proline with β-benzyl-l-glutamate were studied in 1,2-dichloroethane, m-cresol, and dichloroacetic acid by measuring the optical rotatory dispersion and the infrared absorption spectra. In m-cresol and dichloroacetic acid, the proline residues take the trans-configuration. In m-cresol their incorporation into copolymers destroys the right-handed-α-helical conformation of glutamate residues. In 1,2-dichloroethane, the proline residues assume the cis-configuration if the sequence of proline residues is long enough. If it is short, they are in the trans-configuration. The poly-l-proline-I-helix can never coexist with the α-helix.
Spiro Compound Formation. III. The Formation of Spiro Compounds by the Rearrangement of Bicyclo[5.4.0]-undecene(1,7) and Cyclopentylcyclohexene
Authors: Nojima Masatomo , Tokura Niichiro
Published: July 2006

The isomerizations of bicyclo[5.4.0]undecene-(1,7) (IV), spiro[5.5]undecene-1 (V), and 1-cyclopentylcyclohexene (VI) were examined with equivalent amounts of perchloric acid in acetic acid or in ethanol at 75°C. In acetic acid, IV, V, and VI all rearranged to form spiro[5.5]-undecan-1-yl acetate (VII) and spiro[5.5]undecan-2-yl acetate (VIII), together with the three olefins IV, V, and VI. No rearranged product has been obtained by the same procedure in ethanol.
Effect of Pressure on Graphitization of Carbon. VI. Normal Pressure Heat Treatment of Soft Carbon Pre-Heat-Treated under High Pressure
Authors: Kamiya Kan-ichi , Inagaki Michio , Saito Hajime
Published: July 2006

Three different samples of polyvinylchloride coke (designated as N-1, N-2, and N-3 which were pre-heat-treated at 1470, 1590, and 1620°C, respectively, under 5 kbar) were heat-treated in a flow of nitrogen under normal pressure. Process of graphitization in these samples was investigated by analyzing (004) diffraction profile. Sample N-1 has a symmetrical profile and consists only of the trubostratic component As. Samples N-2 and N-3 have a composite profile and are composed of the turbostratic component As and the graphitic component Gs. Only the profiles corresponding to the turbostratic component As of these samples shift gradually to higher angle together with sharpening when the heat treatment temperature under normal pressure increases. Changes in c0-spacing and crystallite size Lc of the component As with heat treatment temperature follow the same course of change as in those of the original polyvinylchloride coke. However, heat treatment of the sample under normal pressure did not affect the quality and quantity of the component Gs which had been formed by the pre-heat-treatment under high pressure. These results indicate that the pre-heat-treatment of soft carbon under high pressure has no accelerating effect on the graphitization of the carbon in the subsequent heat treatment under normal pressure.
Moderator Effects on the Reactions of 82Br Activated by the Isomeric Transition with Gaseous Methyl Bromide
Authors: Okamoto Jiro , Tachikawa Enzo
Published: July 2006

82Br obtained via the (I. T.) process has been reacted with methyl bromide. In the gaseous phase, only CH382Br and CH282BrBr are observed as major products, whereas in the solid phase other products, such as CH82BrBr2 and C2H582Br, have also been observed. Moderator experiments using He or Xe indicate that the formations of both CH382Br and CH282BrBr involve the reactions of the energetic 82Br atom. This is in great contrast to the early observations of the Br2-CH4 system, where the ionic as well as the energetic reactions of 82Br play a role in the formation of the C-82Br bond. Comparisons of these results with those found in the reactions of the 80Br obtained via the (n, γ) process suggest that the Br atom obtained via the (n, γ) process is more electronically excited than that from the (I. T.) process. The kinetic analysis of the present results gives the following relative α-values: αHe, 1.0; αXe, 8.8; αCH3Br, 10.3. It is suggested that, during the cooling-down process of 82Br, a high inelasticity is involved in the collision of 82Br, even with monatomic molecules.
Measurement of Negative Ions Formed by Electron Impact. III. The Ionization Efficiency Curves of Negative Ions of m⁄e 26 and 42 from Nitroalkanes
Authors: Tsuda Satoru , Yokohata Akira , Kawai Michihiro
Published: July 2006

The studies of this series were extended to the negative ions of m⁄e 26 and 42 obtained from nitroalkanes; nitromethane, nitroethane, 1-nitropropane, and 2-nitropropane. For m⁄e 26 (probably, CN−) ions, the contribution of three or two processes in the range from zero to ∼20 eV of electron energy was observed for nitromethane or other samples. On the basis of ΔHf values of the reactants and products, and of the value of EA(CN), the plausible reactions to be assigned to each process were presented. For the first process, CH3NO2+e−→CN−+H2O+OH, RNO2+e−→CN−+R1OH+OH. For the second process, CH3NO2+e−→CN−+H2O+O+H, CH3NO2+e−→CN−+H2+O2+H, RNO2+e−→CN−+R1+HO2+H, and C3H7NO2+e→CN−+C2H4+H2+O+OH irrespective of kind of nitropropane. For the third process, CH3NO2+e−→CN−+3H+O2. For m⁄e 42 (probably, CNO−) ions, the contribution of two processes was observed. By taking ΔHf (CNO)=x (eV), EA(CNO)=y (eV), and also combining the observed onset values with the calculated values of appearance potential of reactions to be assigned for each process — for the first process, CH3NO2+e→CNO−+H2+OH, RNO2+e−→CNO−+R1OH+H; for the second process, CH3NO2+e−→CNO−+HO+2H, CH3NO2+e−→CNO−+H2+O+H, RNO2+e−→CNO−+R1O+2H– a relation of x−y\simeq2(eV) was derived.
Chromium(III) Complexes with N,N′-Ethylenediaminediacetic Acid
Authors: Fujii Yuki , Kyuno Eishin , Tsuchiya Ryokichi
Published: July 2006

The following chromium(III) complexes containing N,N′-ethylenediaminediacetic acid (EDDA) were newly prepared: [Cr(Hedda)2]Cl·3H2O (red) (I), [Cr2(OH)2(edda)2]·6H2O (purple) (II), H[Cr(edda)(ox)]·2H2O (purple) (III), [Cr(edda)(dip)]I·5H2O (orange) (IV), K[Cr(NCS)2(edda)]·H2O (reddish purple) (V) and [Cr(Cl)(edda)(H2O)]·3H2O (bluish purple) (VI), where edda, ox and dip are the abbreviations of the N,N′-ethylenediaminediacetate and oxalate anions, and α,α′-dipyridyl respectively. On the basis of the experimental results, it was concluded that EDDA is coordinated as a terdentate ligand in complex I and as a quadridentate in the other complexes prepared in the present work. Furthermore, it was also suggested that complex II has a dimer structure and complex V has trans configuration (with respect to the coordinated carboxylate oxygen).
The Kinetics of Substitution Reactions Involving Metal Complexes. XIII. Reactions of Zinc(II) with meso-Butylenediaminetetraacetatocobaltatet(II) and with Propylenediaminetetraacetatocobaltate(II)
Authors: Ogino Hiroshi , Baba Toshiyuki , Tanaka Nobuyuki
Published: July 2006

Kinetics of the substitution reactions of zinc(II) with meso-butylenediaminetetraacetatocobaltate(II) (cobalt(II)-meso-BDTA) and propylenediaminetetraacetatocobaltate(II) (cobalt(II)-PDTA) have been studied. The reaction of zinc(II) with cobalt(II)-meso-BDTA complex proceeds through two simultaneous reaction paths involving the acid dissociation reactions of the cobalt(II) complex. On the other hand, the reaction of zinc(II) with cobalt(II)-PDTA proceeds through four simultaneous reaction paths, of which two involve electrophilic substitution reactions and the others, the acid dissociation reactions of the cobalt(II) complex. This kinetic behavior is discussed on the basis of the natures of the ligands.
Anionic Copolymerization of Isoprene and 1,1-Diphenylethylene
Authors: Yuki Heimei , Okamoto Yoshio
Published: July 2006

Anionic copolymerization of isoprene (M1) and 1,1-diphenylethylene (M2) was carried out in tetrahydrofuran (THF), dioxane, benzene, and n-heptane by using n-butyllithium (n-BuLi), Na-naphthalene, Na- and K-dispersions as initiators. An alternating copolymer was obtained in the copolymerization in THF, which proceeded without a chain transfer and a termination. Monomer reactivity ratios, r1 obtained by assuming the rate constant k22=0, were 0.12 (Li+), 0.11 (Na+), and 0.11 (K+) in THF at 0°C. The r1 value in benzene at 40°C, however, was affected by the counter ion as follows: 37 (Li+), 0.38 (Na+), and 0.05 (K+). With Li+ counter ion the values were 0.50 in dioxane at 30°C and 29 in n-heptane at 40°C. The order of rate constants in the copolymerization in THF with n-BuLi at 0°C, was k12>k11>k21, the last of which was 2.64×10−3l/mol sec.