BUNSEKI KAGAKU
Print ISSN : 0525-1931
Volume 40, Issue 8
Displaying 1-14 of 14 articles from this issue
  • Takaho WATANABE, Chang-quig LIN, Shu-ming CHEN, Yoshihiro YOSHIMURA, K ...
    1991 Volume 40 Issue 8 Pages 373-376
    Published: August 05, 1991
    Released on J-STAGE: January 18, 2010
    JOURNAL FREE ACCESS
    Trace amounts of chlorine dioxide in water were determined by spectrophotometric procedures based on the reduction of Cresol Red (CR), a pH indicator. A linear relation was obtained between the absorbance and the amount of chlorine dioxide in the range of 0.004 to 1.36 ppm. The optimum pH for the reaction of chlorine dioxide with CR was 3.0 and the optimum pH for the absorbance measurement was 13.0. The reaction of CR with chlorine dioxide was very specific, and not influenced very much by such ions as iron(III), sodium, potassium, copper(I I), magnesium, zinc, manganese, sulfurous and lead ions. The lower limit of determination of this method was 4 ppb.
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  • Yuji SUZUKI, Yoshikatsu SAKAGISHI
    1991 Volume 40 Issue 8 Pages 377-381
    Published: August 05, 1991
    Released on J-STAGE: June 19, 2009
    JOURNAL FREE ACCESS
    We studied the diazo coupling reaction of biliverdin using twelve kinds of diazonium salts to determine serum bilirubin concentration accurately. It was found that biliverdin reacted with various diazonium salts to form red-violet colored products with the absorption maximum at about 510 to 550 nm, and the rate constant of the reaction ranged from 1.80 × 10-4 to 1.22× 10-5 s-1 at 25°C under acidic condition. The rate of reaction with the diazonium salt of 3-, 4-nitroaniline and 4-nitroaniline-2-sulfonic acid was comparatively fast, while with 4-bromoaniline and sulfanilic acid was extremely slow. By increasing pH of the reaction mixture by addition of sodium hydroxide, the reaction rate increased significantly. In this reaction, it seemed that one mole of biliverdin formed one mole of azobilirubin unlike the diazo coupling reaction of bilirubin. It was considered that serum bilirubin concentration can be determined more accurately by use of the diazonium salt which reacts readily with biliverdin.
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  • Hideaki KINOSHITA, Toshiaki USUI
    1991 Volume 40 Issue 8 Pages 383-387
    Published: August 05, 1991
    Released on J-STAGE: June 19, 2009
    JOURNAL FREE ACCESS
    A dialysis membrane-covered, graphite paste electrode was prepared and tested as a detecting electrode for uric acid in serum. The current magnitude of uric acid on the linear sweep voltammograms was proportional to the concentration of uric acid ranging from 1 μM to 200 μM. Protein, which fouls the surface of bare electrode and worsens the property of the electrode, did not affect the anodic current of uric acid at the membrane-covered electrode. Oxidizable compounds in serum except ascorbic acid did not interfere with the current of uric acid measured at 0.5-0.6 V in the acidic solutions by this electrode. The magnitude of the anodic current of a serum solution measured in pH 3-4 could be corrected for the effect of ascorbic acid to obtain the current due to uric acid. Values of uric acid content in serum measured by this method agreed with those by a photometric uricase-peroxidase procedure.
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  • Toshiyuki MITSUI, Syuji OKUYAMA, Yoshikazu FUJIMURA
    1991 Volume 40 Issue 8 Pages 389-394
    Published: August 05, 1991
    Released on J-STAGE: June 19, 2009
    JOURNAL FREE ACCESS
    When a mixture of gasoline and kerosene was measured by gas chromatography, we could not accurately judge whether the measured material was gasoline or kerosene because the respective chromatograms overlapped. Therefore, to analyze the blend composition ratio (w/w) of gasoline to kerosene, some chromatograms were made using mixtures of gasoline and kerosene with known blend composition ratios. Each peak in the chromatograms was expressed by relative value to provide a data base. Next, the blend composition ratio was calculated more finely by factor score and multiple regression analysis. By this method, the blend composition ratios of gasoline-kerosene mixtures can be determined with a high degree of accuracy.
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  • Masako MIZUNO, Kenji TOCHIGI, Masahito ITO, Junkichi MIURA
    1991 Volume 40 Issue 8 Pages 395-400
    Published: August 05, 1991
    Released on J-STAGE: January 18, 2010
    JOURNAL FREE ACCESS
    Glycated hemoglobins (GHb) are composed of A1a, A1b, labile-A1c (1-A1c), stable-A1c (s-A1c) and others. The concentration of s-A1c can be used as an index of the average blood glucose value for the preceding 2 months. Therefore, determination of s-A1c is useful for the assessment of long-term control of diabetes mellitus. A rapid analysis method of s-A1c by HPLC was discussed. Packings with 5 μm and 3.5 μm diameter polymethacrylate gel modified with carboxymethyl groups, were prepared, and a correlation between particle diameter of the packings and chromatographic performances, such as number of theoretical plates (N), retention time (tR), pressure drop (ΔP) were studied. N increased as the particle diameter of packings was decreased. The N for s-A1c by linear gradient elution was 2× 103 plates for 3.5 μm diameter packing, which was five times larger than that of 5 μm diameter packings. Using 3.5 μm packings, s-A1c was well separated from 1-A1c by the optimization of analytical conditions, such as the concen-tration of the initial eluent. Using the column (4.6 mm i.d. × 35 mm) packed with 3.5 μm packings, six hemoglobin components, A1a, A1b, HbF, 1-A1c, s-A1c and A0, were separated in a 3.5 min cycle by three step gradient elution, thereby reducing analysis time.
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  • Koichi YAMAMOTO, Shoji MOTOMIZU
    1991 Volume 40 Issue 8 Pages 401-405
    Published: August 05, 1991
    Released on J-STAGE: June 19, 2009
    JOURNAL FREE ACCESS
    In an aqueous solution buffered at pH 8, Bromocresol Purple reacts with a quaternary ammonium ion containing a long-chain alkyl group to change color from blue to light yellow. This color change, however, is inhibited in the presence of alcohols such as methanol, ethanol, propanol and butanol. This phenomenon was used to determine ethanol content in aqueous solutions. The calibration curve obtained by the batchwise manual method was not a straight line. In the FIA method, a linear relationship between the peak heights and the ethanol concentrations was obtained up to 60 v/v% of ethanol, and the relative standard deviations were 1.5 and 0.2% for the determinations (n = 5) of 4 and 20 v/v % of ethanol, respectively. FIA made it possible to analyze about 35 samples per hour. This proposed method can be used as a rapid and simple method for the determination of ethanol content in alcoholic liquors.
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  • Tatsuya TAKAGI, Akihiro NODA, Hironobu MAEZAKI, Ken-ichi MATSUMURA, Hi ...
    1991 Volume 40 Issue 8 Pages 407-412
    Published: August 05, 1991
    Released on J-STAGE: June 19, 2009
    JOURNAL FREE ACCESS
    Monte Carlo simulations for the 12-crown-4 plus Li+ system in dimethyl ether were carried out. The distances between the Li+ and the center of the four oxygen atoms in 12-crown-4 were set to 0.05, 0.45 or 0.85 nm. In order to express the densities and the orientations of the solvent molecules, a widely utilizable color graphic interface program, GRICE (GRaphic Interface for Computer Experiments), was developed. The figures indicate that the solvation sphere is more widely extended in the case of x = 0.85 nm than in the case of x =0.05 nm. Hence, the solvent-solvent interaction energy in the case of x =0.85 nm was thought to be more unstable than in the case of x = 0.05 and 0.45 nm. The calculated results on the components of the interaction energies agreed with the above-mentioned estimation. Thus, the driving force of the inclusion phenomena occuring between crown ethers and alkaline metal cations was suggested to be variation of solvent-solvent interactions.
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  • Koji MATSUSAKI
    1991 Volume 40 Issue 8 Pages 413-415
    Published: August 05, 1991
    Released on J-STAGE: June 19, 2009
    JOURNAL FREE ACCESS
    A mixture of nickel nitrate and EDTA tetraammonium salt was very suitable as a matrix modifier for the determination of thallium by graphite furnace AAS. The chloride interference could be eliminated because chloride formation of thallium and other metal cations was prevented by EDTA. Addition of nickel nitrate suppressed the EDTA-caused sensitivity loss in atomic absorption of the analyte thus permitting the addition of a large amount of EDTA to the sample solution. This effect depends on the EDTA complex of nickel acting as a thermal stabilizer for the analyte during the ashing step in the furnace.
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  • Toshiaki NOMURA, Saeko YUMOTO
    1991 Volume 40 Issue 8 Pages 417-420
    Published: August 05, 1991
    Released on J-STAGE: January 18, 2010
    JOURNAL FREE ACCESS
    Cobalt(II) reacts with α-nitroso-β-naphthol to form an insoluble complex in water. The precipitate adsorbed on a piezoelectric quartz crystal shifted the frequency. The frequency shifts were proportional to the amounts adsorbed. Acetic acid (10 mM) and α-nitroso-β-naphthol (1.5 mM) solutions were passed through the quartz mass sensor to get constant frequency (F1). And then instead of the stream of the acetic acid solution, the cobalt(II) sample in 10 mM acetic acid solution was passed. After exactly 5 min, the stream was changed to the acetic acid solution to get a constant frequency (F2). The frequency change resulting from the adsorption of cobalt(II) complex was calculated as the difference, F1-F2. The concentration range (260) μM of cobalt(II) could be determined from the calibration curve with good reproducibility. Cobalt(II) complex adhered could be removed from the sensor with acetic acid.
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  • Shogo SUZUKI, Natsuko KATSURAGI, Shoji HIRAI
    1991 Volume 40 Issue 8 Pages 421-424
    Published: August 05, 1991
    Released on J-STAGE: June 19, 2009
    JOURNAL FREE ACCESS
    Trace elements in a certified reference material No. 11 Fish Tissue (Sea Bass), prepared by the National Institute for Environmental Studies of Japan (NIES), were determined by instrumental neutron activation analysis (INAA). Portions of the Fish Tissue sample (ca.400-1000 mg) were irradiated either for a short time (30 s) at a thermal neutron flux of 1.5×1012 n cm -2s-1 or for a long time (5 h) at a thermal neutron flux of 3.8×1012 n cm -2s-1 in the Musashi Institute of Technology Research Reactor (MITRR). Gamma-ray spectra for the irradiated samples were measured with a coaxial Ge detector coupled to a multichannel analyzer. Concentrations of 24 elements (Sn, Na, Mg, Al, S, Cl, K, Ca, Sc, Cr, Mn, Fe, Co, Ni, Zn, As, Se, Br, Rb, Sr, Sb, I, Cs and Hg) were determined by this method. The lower limits of determination for 53 elements were also calculated. For example the concentration of Sn obtained was 2.3±0.3 ppm which was in good agreement with the NIES certified value.
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  • Teruo TAKENAKA
    1991 Volume 40 Issue 8 Pages 425-428
    Published: August 05, 1991
    Released on J-STAGE: June 19, 2009
    JOURNAL FREE ACCESS
    A new FIA system was developed for the continuous determination of total silica in natural water. The system includes the conversion of polymerized silica into its monomer. A sample (20μI) sandwiched between two 100 μl layers of alkaline reagent is introduced into a stream of distilled water at a flow rate of 1.3 ml/min. The polymerized silica in the sample is decomposed to monomer in 10 m Teflon tubing heated in an air bath at 145°C. The sample is merged with a stream of acidic molybdate reagent at a flow rate of 0.6 ml/min, and then is heated at 90°C to produce yellow molybdosilicate. The absorbance of the yellow complex is measured at 400 nm. The silica, ranging from 0.5 to 100 mgSi/l, could be determined at a sampling rate of 30 samples/h. The precision of the method is 1.5% (RSD) for 50 mgSi/l. The flow injection method proposed here was applied to the quantitative analyses of total silica in several geothermal water and colloidal silica samples. The results obtained by the proposed FIA were in good agreement with those obtained by the conventional method (PS K 0101).
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  • Suwaru HOSHI, Shin KATO, Masashi NARA, Mutsuya MATSUBARA
    1991 Volume 40 Issue 8 Pages 429-432
    Published: August 05, 1991
    Released on J-STAGE: June 19, 2009
    JOURNAL FREE ACCESS
    The complex formation of palladium(II) and platinum(II) with glyoxal bis(4-phenyl-3-thiosemicarbazone) (GBS), methylglyoxal bis(4-phenyl-3-thiosemicarbazone) (MBS), dimethylglyoxal bis(4-phenyl-3-thiosemicarbazone) (DMBS) and methylethylglyoxal bis(4-phenyl-3-thiosemicarbazone) (MEBS) were studied in 80 v/v% N, N-dimethyl-formamide-water mixture. And reversed-phase HPLC with a spectrophotomertric de-tection was applied to the separation of their Pd-and Pt-chelates by using an ODS col-umn (6 mm i.d.×250 mm in length). Palladium(II) and platinum(II) formed stable chelates with each reagent in weak acidic medium, though it needed to be heated at 80°C for 15 min on the formation of Pt-chelate. The elution peaks of Pd and Pt-chelates on their chromatogram were not successfully separated by using methanol-water and acetonitrile-water as mobile phases. The resolved separation of Pd- and Pt-chelates were achieved by using an acetone-water mobile phase. The Pt-chelates were eluted more rapidly than the Pd-chelates in all reagent systems. In both metal systems, the retention time of each metal chelate was longer in order of GBS, MBS, DMBS and MEBS. The linear relationship was found between the logarithms of capacity factor (log k') of Pdand Pt-chelates and all alkyl carbon number of glyoxal residue in dithiosemicarbazone compounds.
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  • Jun FUJIWARA, Kazuhiro YOSHIHARA
    1991 Volume 40 Issue 8 Pages T151-T155
    Published: August 05, 1991
    Released on J-STAGE: January 18, 2010
    JOURNAL FREE ACCESS
    The measurement conditions have been studied for the international projects on the improvements of the quantitative Auger electron spectroscopy using Co-Ni alloys as standard reference test specimens. The measurements of Auger electron intensity were carried out with a PHI 660 Microscopy. The curve fitting method was applied to the calculation of the composition of alloys. The specimens were sputtered by argon ion with 1 kV of accelerating voltage. The primary electron beam energy was 5 kV; and beam current was 1μA. The focus point of the analyzer was determined as the maximum point of the elastic peak intensity of electron beam. The specimens were accurately placed at the focus point of CMA. Under these measurement conditions, errors of quantitative analysis were within 4%.
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  • Takeshi EZAKI, Kouji KAMINISHI, Katsumi TAMAOKU
    1991 Volume 40 Issue 8 Pages T157-T161
    Published: August 05, 1991
    Released on J-STAGE: June 19, 2009
    JOURNAL FREE ACCESS
    The loss of chromium during pretreatment of water samples was investigated. The standard samples containing known amounts of chromium were treated by the wet digestion method under various conditions according to JIS K 0102, to compare the recoveries of chromium. The digestion with perchloric acid resulted in a substantial loss of chro mium, and the digestion with hydrochloric acid, with heating to complete dryness, also resulted in loss. The addition of sulfuric acid to perchloric acid reduced the loss, but the recovery was not quantitative. Any significant loss was observed after digestion using nitric acid with hydrogen peroxide.
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