BUNSEKI KAGAKU
Print ISSN : 0525-1931
Volume 17, Issue 5
Displaying 1-23 of 23 articles from this issue
  • Studies on analysis of mixed pharmaceutical preparations. VII
    Masayoshi TATSUZAWA, Michitoshi SHIMODA
    1968 Volume 17 Issue 5 Pages 551-555
    Published: May 05, 1968
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    Phenylephrine hydrochloride (I) reacts with dimethyl-p-phenylenediamine and K3Fe (CN) 6 in an alkaline medium (borate buffer : pH 9.0) to give a green color (indophenol dye). The latter can be extracted into chloroform, which shows an absorption maximum at 610 mμ.
    A new spectrophotometric method for (I) based on this color reaction was established, and was applied to the determination of (I) in pharmaceutical preparations. The influences of 48 compounds on the determination were investigated, among which those by acetaminophene, salicylamide, sulpyrine, ascorbic acid etc. were eliminated by chloroform extraction from an acidic medium.
    The analytical procedure was as follows. Take the sample containing 6 mg of (I) in a separatory funnel. Add 20 ml of water and 10 ml of 10% HCl, and extract 3 times with 30 ml portions of chloroform. Transfer the aqueous layer to a 100 ml volumetric flask, and add water to make up to exactly 100 ml. Take 50 ml of this solution into another 100 ml volumetric flask, and add water to make up to 100 ml.
    Transfer a 2 ml aliquot into a 25 ml glass-stoppered test tube, and add 5 ml of 0.2M borate buffer, 3 ml of 0.05% dimethyl-p-phenylenediamine solution, 10 ml of chloroform and 1 ml of 1% K3Fe (CN) 6 solution.
    Shake for about 5 min., and allow to separate the chloroform layer.
    Add Na2SO4 to dehydrate the chloroform layer. Filter, and measure the absorbance at 610 mμ (ET) against chloroform. At the same time, the absorbance of the standard solution (ES) is determined and the amount of (I) is calculated by ET/ES.
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  • Studies on analysis of mixed pharmaceutical preparations. IX
    Masayoshi TATSUZAWA, Shigeko HASHIBA, Michitoshi SHIMODA
    1968 Volume 17 Issue 5 Pages 555-559
    Published: May 05, 1968
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    Aminopropyrone (I) react with CuSO4 and pyridine to give a light-green color (Cu complex) with λmax absorption at 410 mμ.
    A new spectrophotometric method for (I) based on this color reaction was established, and applied to the determination of (I) in pharmaceutical preparations.
    The influences of 48 compounds on the determination were investigated, among which those by sulpyrine, N-methylaminoantipyrine, salicylates, theophylline, barbiturates, amino acids, ascorbic acid, sodium citrate etc. could be eliminated by chloroform extraction in an alkaline medium.
    The recommended analytical procedure was as follows. Take the sample containing 50 mg of (I) in a separatory funnel. Add 20 ml of water and 10 ml of 0.1N NaOH, and extract 5 times with 30 ml portions of chloroform. Combine the chloroform extracts and evaporate on a water bath.
    Dissolve the residue in 50 ml of water. Transfer the solution to a 100 ml volumetric flask, and make up to volume exactry with water.
    Transfer a 5 ml aliquot into a 30 ml glass-stoppered test tube, and add 5 ml of 0.1% CuSO4-pyridine solution. Add water to make up to 25 ml, and measure the absorbance at 410 mμ (ET) against water.
    At the same time, the absorbance of the standard solution (ES) is determined and the amount of (I) is calculated by ET /ES.
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  • Nobuhisa MATANO, Katsumi ONO, Takayuki FUJII
    1968 Volume 17 Issue 5 Pages 560-565
    Published: May 05, 1968
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    From 0.11 to 0.98% of sodium oxide in alumina as raw material of aluminum was determined by fluorescent X-ray analysis with a standard error of 0.03%.
    It was inevitable that only very feeble Na-Kα line was obtained by any standard set of fluorescent X-ray spectrometer, and a reason of this was attributed to a too low transmissivity of the window of the detector for Na-Kα line. A substitution of this by a 1 μ, polypropylene film multiplied sevenfold the measured intensity of Na-Kα line.
    Statistical examinations were also carried out on the counting time, the method of counting, the statistical variation of results, etc.
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  • Toshioki AMEMIYA, Hiroshi HIRATA
    1968 Volume 17 Issue 5 Pages 565-569
    Published: May 05, 1968
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    Complexes of titanium and niobium with hydrogen peroxide are similarly formed in a dilute sulfuric acid solution, but their reactivities with potassium permanganate are distinctly different from each other against the concentration of sulfuric acid. Titaniumhydrogen peroxide complex readily reacts with potassium permanganate. Niobium complex (Nb : H2O2= 1 : 1) does not react in the sulfuric acid concentration less than 3 M, but does completely in that more than 8 M. On the other hand, no complex of zirconium is formed with hydrogen peroxide.
    The recommended procedure for determination of niobium is as follows. One gram of sample (mixture of oxides of titanium, niobium and zirconium) is heated to dissolve in the mixture of 5 ml of 98% sulfuric acid and 3 g of ammonium sulfate, and diluted to 100 ml with distilled water. An aliquot of this solution is mixed with 5 ml of 0.1 M hydrogen peroxide, and titrated with 0.04 M potassium permanganate solution. The amount of niobium is calculated from the difference of the added and titrated volumes of hydrogen peroxide. To the above titrated solution is then added gradually the same volume of 98% sulfuric acid in an ice-water bath, and the titration is carried out at below 20°C. The amount of niobium is also calculated from this titer. One ml of 0.04 M KMnO4 corresponds to 9.29 mg of niobium.
    A number of samples can be analyzed by the proposed method rapidly and conveniently without any special equipment or chemicals.
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  • Eiji FUTAMURA, Hiromu KUROKI
    1968 Volume 17 Issue 5 Pages 569-574
    Published: May 05, 1968
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    It has been found that phytin reacts with titanium (IV), zirconium (IV), niobium (V), tantalum (V), tin (IV), and thorium (IV) to give white precipitates from boiling acidic solutions. The reaction is more complete in a perchloric acid solution than in a hydrochloric or sulfuric acid solution, and is 100 per cent or nearly 100 per cent quantitative in the presence of ferrous ion. The amount of coprecipitated iron is small.
    This reaction can possibly be applied to the isolation of above mentioned elements in the analysis of iron and steel.
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  • Hitoshi KAMADA, Nobuhiko KOKUBUN
    1968 Volume 17 Issue 5 Pages 575-579
    Published: May 05, 1968
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    A new type of gas chromatograph detector was developed. The high frequency discharge tube was connected with the exit of a gas chromatograph column. Argon was used as the carrier gas. The intensity of the emission spectrum originated from the organic compounds eluted into the discharge tube was measured photoelectrically.
    Good reproducibility and linearity between the concentration of a compound and the intensity of its spectrum were obtained in the range of 10-6 mol and 10-8 mol for ethanol, ethyl ether, acetone, and toluene. The coefficient of standard deviation was 1 %. The detectable limits were 2 × 10-11 mol/sec in ethanol, 1 × 10-11 mol/sec in propanol, and 4 × 10-13mol/sec in benzene with CH band, 4 × 10-9 mol/sec in carbon tetrachloride with CCl band, and 5 × 10-11 mol/sec in carbon disulfide with CS band.
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  • Saburo YANAGISAWA, Shumpo MITSUZAWA, Masaki MORI
    1968 Volume 17 Issue 5 Pages 580-583
    Published: May 05, 1968
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    Continuous determination of sulfur dioxide in the atmospheric air by the use of a modified p-rosaniline-formaldehyde reagent has been described. The measurement was made intermittently once every 60 min. by an automatic analyzer equipped with a singlepath colorimeter. The discoloration of the reagent with temperature was avoided by a specially designed bubbler in a constant-temperature chamber. The transmittance ratio method employed gave accurate results even at high blank values, hence the reagent was used repeatedly by circulation only to measure the difference in its coloration before and after the absorption of sulfur dioxide, and the analyzer could be used for long without feeding new reagent. The lower limit of the determination of sulfur dioxide with this instrument was 0.3 pphm.
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  • Studies on the Auto Exhaust Analysis. I
    Fumito NAKASHIMA, Masato TAKEUCHI
    1968 Volume 17 Issue 5 Pages 584-589
    Published: May 05, 1968
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    Infrared spectrophotometric method of analysis of auto exhaust has been studied in order to perform a continuous determinations of carbon monoxide, carbon dioxide, and hydrocarbons in accordance with the changes of the driving modes of automobiles. A small volume cell of 10 cm light path and a continuous recording-scale expansion attachment were used so that the continuous, high response, and sensitive measurement at a given wavelength might be possible. Sample gas was introduced into the cell after drying by passing through the condenser, the filter, and the desiccant. The pressure in the cell was always maintained at an atmospheric pressure by using an automatic pressure control valve at the inlet of the cell. Absorption peaks at 4.6 and 2.7 μ were used for the determinations of carbon monoxide and carbon dioxide, respectively. Although the exhaust gas contains more than several tens of hydrocarbons, most of them give an absorption peak at 3.4 μ. Hydrocarbons were, therefore, determined at 3.4 μ by calibrating with n-hexane for convenience. The ranges of measurement are 0.115% for carbon monoxide, 0.316% for carbon dioxide, and 504000 ppm as n-hexane for hydrocarbons. The recorder indication up to 95% of equilibrium takes about 2 sec. Methane and ethylene could also be determined by the present method.
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  • Kyoji TÔEI, Toshiko KOBATAKE
    1968 Volume 17 Issue 5 Pages 589-592
    Published: May 05, 1968
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    Direct volumetric determination of sulfate by barium salt encountered a difficulty in somewhat slow rate of formation of barium sulfate. The authors carried out the titration with an addition of an anionic sufactant to enhance the formation of barium sulfate, and the results were compared with those obtained with an addition of acetone or ethanol. Sulfonazo III was used as the indicator, its color changing from pink to blue at the end point.
    The method was applied to the determination of sulfate in several samples including sodium sulfates, solutions of sulfuric acid, and sea water. Nearly satisfactory results were obtained except for the sea water.
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  • Shozo YAMADA, Tsugio BABA
    1968 Volume 17 Issue 5 Pages 593-597
    Published: May 05, 1968
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    Separation and identification of salicylaldehyde-test-positive substances from commercial samples of potassium sorbate are described. Carbonyl compounds in the sample were separated as 2, 4-dinitrophenyl-hydrazones, which were divided into acidic and neutral components. Identification was performed by thin-layer chromatography and by visible and infrared spectroscopy. Acetaldehyde, one of the test-positive substances, was identified. Fumaraldehydic acid, being considered to be another moiety of oxidative degradation products of potassium sorbate, was also identified.
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  • Shizuya MAEKAWA, Kiyotoshi KATO
    1968 Volume 17 Issue 5 Pages 597-602
    Published: May 05, 1968
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    A photometric method for the determination of 0.00001 to about 0.005% of phosphorus in pure iron with molybdenum blue-methyl-isobutyl ketone (MIBK) extraction has been studied. This method is highly sensitive, rapid and simple. Beer's law is obeyed up to 10 μg of phosphorus in 10.0 ml of MIBK. The established procedure is as follows.
    The sample (0.21.0 g) is decomposed with hydrochloric acid and hydrogen peroxide (30 v/v%), and interfering elements are removed by extraction with MIBK from 7 N hydrochloric acid solution. Three milliliters of perchloric acid is added to the aqueous layer, and it is evaporated strong fumes of perchloric acid expel off hydrochloric acid. The residue is diluted to approximately 20 ml with water. Two milliliters of 10% sodium bisulfite solution and 10 ml of ammonium molybdatehydrazine sulfate composite solution in 1 N sulphuric acid are added, and the solution is heated for 7 to 8 min. on a hot plate. After being cooled, the solution is shaken for 30 sec. with 10.0 ml of MIBK to extract molybdenum blue.
    Transfer an aliquot to an absorption cell, and the absorbance is measured at 740 mμ against MIBK.
    The time required for an analysis is about 50 min.
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  • Hisashi KOIKE, Kaoru OHASHI, Masaaki MATSUO, Atsuko KAWASAKI
    1968 Volume 17 Issue 5 Pages 603-608
    Published: May 05, 1968
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    Diphenhydramine, an antihistaminate, reacts with Plasmocorinth B (abbreviated as PCB) to form a product extractable in chloroform. The extractability reaches maximum at pH between 2.0 and 3.0, and the extarct shows absorption maxima at 540 mμ and 567 mμ. The amount of PCB should be more than 10 times that of equivalent, whereby the absorbance at 540 mμ obeys Beer's law.
    Influences of temperature and time together with various extracting conditions were examined, and a satisfactory procedure for the determination has been established. The method is relatively simple and quite accurate.
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  • Hisashi KOIKE, Kaoru OHASHI, Akira MIYAKATA, Masaaki MATSUO
    1968 Volume 17 Issue 5 Pages 608-612
    Published: May 05, 1968
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    Spectrophotometric determination of diphenylpyraline with a metal indicator NN has been presented.
    Diphenylpyraline reacts with NN [2-Hydroxy-1- (2-hydroxy-4-sulfo-1-napthylazo) -3-naphthoic acid] in acidic medium, whereby the reaction product alone is extractable into organic solvents. The extractability is highest with tetrachloroethane, and the extract shows absorption maxima at 586 and 627mμ.
    Examination of fundamental conditions for the determination has revealed that Beer's law is obeyed for 864μg/ml of diphenylpyraline solution.
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  • Tatsuaki HORI, Genichiro YASUE, Yoshitaka KOBAYASHI
    1968 Volume 17 Issue 5 Pages 613-615
    Published: May 05, 1968
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    Conventional methods for determining small amount of hydrogen cyanide in air are incovenient and timeconsuming. For the rapid determination of HCN, several granular gels which would change colors when exposed to air containing HCN were looked for. A detector reagent consisted of purified silica gel impregnated with HgCl2 and Methyl Orange was found to have high sensitivity and stability in the determination of HCN in air. The gel was packed in a glass tube, and the sample air was drawn through it with a constant flow rate (1 ml/sec). Quantitative estimation was possible by measuring the colored length of the column. The range of determination is 1100 ppm HCN, and detecting limit is about 0.2 ppm. Mean relative error was below ± 5%. The results agreed well with those by the conventional colorimetric method.
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  • Hitoshi KOHARA, Nobuhiko ISHIBASHI, Akira YOSHIDA
    1968 Volume 17 Issue 5 Pages 616-621
    Published: May 05, 1968
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    Extractability of iron (III) complexes with ο-dihydroxy derivatives containing-SO3H group has been investigated in the presence of quaternary ammonium ions.
    In the presence of dialkyl monomethyl benzylammonium chloride as quaternary ammonium salt, the complex having iron (III) -ligand mole ratio of 1 : 2 or 1 : 3 can be extracted into organic solvents, but the complex of 1 : 1 composition can not. Absorption spectrum of the complex in organic phase is similar to that in aqueous phase. Sulfonic anion is more beneficial than carboxylic anion among the functional groups used for the extraction of the complex, and these organic acid anions combine stoichiometrically with quaternary ammonium ion. The effect of ClO4-is greater than Cl-.
    The complex can be extracted into various organic solvents with dialkyl monomethyl benzylammonium ion, but can not with trimethyl benzylammonium ion. With tetradecyl dimethyl benzylammonium ion, the extractability of the complex depends on polarity of solvents and increases with increasing polarity.
    This result is applicable to the separation of molybdenum (VI) from iron (III), titanium (IV) and vanadium (V), and the spectrophotometric determination of molybdenum (VI) in the presence of tungsten (VI).
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  • Keiichiro HOZUMI, Hideo TAMURA
    1968 Volume 17 Issue 5 Pages 622-628
    Published: May 05, 1968
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    For refining the operative conditions in connection with the automatic recording analyzer for organic oxygen, in that the Unterzaucher's principle has been combined with a new technique of optical integration along the vapor phase iodine introduced in a long gas cell kept at 120°C, further investigations have been carried out on the following items.
    Maximum absorbance of the vapor phase iodine was observed at the fixed wavelength of 525 mμ during a change of temperature between 100180°C, while the transmittance at the same wavelength changed with a rate of 0.04%/°C at around 70% transmittance.The flow rate of carrier gas was allowed within a range of 1070 ml/min, but 2050 ml/min was suggested for the normal operation. With the gaschromatographic observations, sulfur-containing fractions produced in the thermal decomposition tube were perfectly trapped by a net of reduced copper instead of by metallic silver. No hydrocarbon was detected from various organic samples, except for methane which did not react with iodine pentoxide. The cause of the blank value was therefore attributed to some oxygen-containing impurities and/or water adsorbed on samples. The reproducibility of calibration line was highest when the different standard samples were taken in approximately the same weight, e.g. 1.51.7 mg. The weight of unknown samples in routine analysis should be also limited within this regular blank range.
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  • Studies on analysis of mixed pharmaceutical preparations. VIII
    Masayoshi TATSUZAWA, Shigeko HASHIBA
    1968 Volume 17 Issue 5 Pages 629-632
    Published: May 05, 1968
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    Isopropylantipyrine (I) reacts with Fe (NO3) 3 in acidic medium to give a red violet color with maximum absorption at 510 mμ.
    A new spectrophotometric method, based on this color reaction, has been established to the determination of (I) in pharmaceutical preparations.
    Influences of 47 compounds on the determination were examined. The interferences from sulpyrine, aminopyrine, aminopropyrone, antipyrine, salicylate, ribofravine phosphate, codeine phosphate, etc. are eliminated by the chloroform extraction, either in an acidic or an alkaline medium.
    The procedure recommended is as follows. A sample {containing 50 mg of (I)} is taken into a separatory funnel. To this is added 10 ml of water and 10 ml of 10% H2SO4 solution, and it is extracted 6 times with 30 ml portions of chloroform. The combined extract is evaporated on a water bath, and the residue is dissolved in 10 ml of ethanol. It is then diluted with water exactly to 100 ml.
    A 10 ml aliquot is transfered to a 25 ml volumetric flask. Ten milliliter of 20% Fe (NO3) 3 solution is added, and it is diluted to 25 ml with water.
    The absorbance is measured at 510 mμ (ET) against blank. At the same time, the absorbance of standard solution (ES) is determined, and the amount of (I) is calculated by ET/ES.
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  • Teruo KAJIURA
    1968 Volume 17 Issue 5 Pages 632-634
    Published: May 05, 1968
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    The Raman spectrum of minute amount of CCl4 was obtained in an extremely short time, by employing the oscillation line at 4880 Å of argon-ion laser for the excitation. The output of the laser was kept on less than 250 mW throughout the measurement. A light prism spectrograph for convenience of the photographic measurement and a simple optical system around Raman cell characterized the apparatus.
    Amount of the sample used was 330 μl, and the exposure time was 315 min. with Eastman Kodak 103a-F plate. An overtone of 760 cm-1 line was observed at 1539 cm-1 by elongated exposure. In the case of an extremely small amount of the sample, oscillation lines of the laser other than 4880 Å must be screened by an interference filter.
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  • Synthetic and analytical studies on color reagents. XI
    Kyoji TÔEI, Toshiko KOBATAKE
    1968 Volume 17 Issue 5 Pages 634-637
    Published: May 05, 1968
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    Of several hundreds of compounds synthesized by the authors and their collaborator, ο-sulphono-ο'-hydroxyazo compounds are found to be color reagents for barium, among which, especially, the bisazo compounds of chromotropic acid are excellent. The colors of the reagents themselves are violet in a slightly acidic medium and their barium complexes are blue.
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  • Kazuo KAWAMURA, Shiro WATANABE, Takashi OTSUBO, Syunsuke GOTO
    1968 Volume 17 Issue 5 Pages 637-639
    Published: May 05, 1968
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    Error sources in the digestion steam distillation procedure for the nitrogen analysis of steel were studied. When steel samples were dissolved in glass beakers, the results were affected by the adsorption of nitrogeneous compounds on the inner surface of beakers. This sort of adsorption was seen during the distillation procedure, whereby a fraction of distilled ammonia was adsorbed on the inner surfaces of the distillation flask and the condenser. Against these interference, beakers should be reserved in a vacuum desiccator or filled with distilled water, the distillation flask should be made of teflon, and the condenser should be as small as possible or the steam with distilled ammonia should be condensed directly in a modified receiver. Better results were obtained by these improvements.
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  • Katsuya SATO, Masami MATSUI, Nobuo IKEKAWA
    1968 Volume 17 Issue 5 Pages 639-643
    Published: May 05, 1968
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    The separation of polynuclear aromatic hydrocarbons by gas chromatography was described.
    The retention times of 14 kinds polynuclear aromatic hydrocarbons and methyl cholanthrene were measured on SE-30, SE-52, JXR, XE-60, cyclohexanedimethanol succinate (CHDMS) and neopentylglycol succinate (NGS) columns, and the operating conditions were investigated for the compounds which were difficult to be separated. Using a 2% SE-30 column at the column temperature of 90°C, phenanthrene and anthracene were separated almost satisfactorily.
    The possibility of the use of inorganic material as a stationary phase was discussed. A mixture of lithium nitrate and SE-30 was found to be very satisfactory for the separation of polynuclear aromatic hydrocarbons.
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  • [in Japanese]
    1968 Volume 17 Issue 5 Pages 644-650
    Published: May 05, 1968
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
  • [in Japanese]
    1968 Volume 17 Issue 5 Pages 651-658
    Published: May 05, 1968
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
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