BUNSEKI KAGAKU
Print ISSN : 0525-1931
Volume 38, Issue 12
Displaying 1-16 of 16 articles from this issue
  • Junko IIDA, Seiji TAKAHASHI
    1989 Volume 38 Issue 12 Pages 659-666
    Published: December 05, 1989
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    Neither multidimensional gas chromatography (MDGC) nor multidimensional gas chromatography/mass spectrometry (MDGC/MS) has been used for biomedical research as often as desirable because suitable equipment has not been available. Simple pre-cutting techniques were investigated for MDGC/MS systems. Precutting allows high boiling-point compounds, not objects of interest for analysis, to be expelled, and has many advantages for GC/MS analysis, such as avoiding contamination of the ion source and lengthening the life span of the analytical column, shortening analysis time and simplifying pretreatment. Drugs in serum extracts were determined using packed and capillary columns as precolumns. Although some drugs could be run clearly through a packed precolumn, polar compounds such as acetaminophen could not be, resulting in peak distortion. The use of a capillary precolumn was effective for such compounds because of minimal adsorption, resulting in improved peak shape. An analgesic, anticonvulsants and tranquilizers extracted from serum were analyzed within 25 min.
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  • Shoji HIRAI, Kazuyuki MAEDA
    1989 Volume 38 Issue 12 Pages 667-673
    Published: December 05, 1989
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    Recently, many kinds of iron remains have been excavated by an archaeological investigation. In this study, iron remains-an iron sand, a granular iron mass, an iron outflowed and residual slag, an iron lump, a small sword and an arrowhead-were analyzed by an instrumental neutron activation analysis to identify the production and processing techniques of iron and ironware. As a result, a total of 38 elements in the various iron remains were determined over the range of concentration from several ppm to several 10%. The concentrations of elements except rare earth elements, Hf and Th in the granular iron mass were similar to those of the iron sand. The concentrations of elements except K and Co in the outflowed and residual slag were homogeneous in the every slag. The concentrations of elements in a metallic iron of the iron lump and ironware were quite different from those of elements in a rust. The concentrations of Fe, Co, Ga, As, Cu, Sb and W in the metallic iron decreased with increase of the rust, whereas those of Na, Al, Sc, Ti, V, Mn, rare earth elements, Hf and Th in the metallic iron incresed with the rust.
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  • Izuo AOKI, Yasuo YUKAMI, Kunihiro WATANABE
    1989 Volume 38 Issue 12 Pages 674-680
    Published: December 05, 1989
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    The reactions of salicylaldehyde with primary amines and metal ions to form Schiff-base complexes were investigated for the analysis of amines. ο-Aminophenol (OAP) emits a strong fluorescence in the presence of aluminium(III) by yielding an aluminium complex with salicylidene-ο-aminophenol. The fluorometric determination procedure of OAP using the aluminium complex was established. The recommended procedure is as follows: Take 1 ml of a sample solution containing less than 2×10-7 mol of OAP, add 3 ml of the reagent solution {0.01 M salicylaldehyde in methanol: 0.01 M Al(NO3)3·9H2O in water: 20% sodium acetate-HCl buffer (pH 5.3)=1:1:1}, and allow to stand for 30 min at room temperature (2035°C). Then dilute the mixture to 25 ml with water. Measure the relative fluorescence intensity at 495 nm with an excitation wavelength of 400 nm using (0.22)μg/ml uranine aqueous solution as the reference standard. OAP can be determined in the range of (4×10-92×10-7)mol/25 ml within a relative standard deviation of 3%. The detection limit of OAP is 5×10-10mol/25 ml. According to this procedure, only OAP related compounds showed a fluorescence among the 17 aromatic amines examined. m- and p-Aminophenol, and aniline at 100-fold concentration of OAP did not interfere with the determination of OAP. Aliphatic amines did not interfere at a 1000-fold excess.
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  • Hiroshi WATANABE, Yasushi KAYAWAKE
    1989 Volume 38 Issue 12 Pages 681-685
    Published: December 05, 1989
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    The separation of trivalent aluminium and gallium by extraction from sodium hydroxide solutions in the presence of tartrate ion was investigated using trioctylmethylammonium chloride (TOMAC). When the simultaneous extraction of aluminium and gallium was carried out from alkaline solutions containing tartrate at a molar concentration ratio of [Tar2-]/([Al]+[Ga])=8, the separation factor(Sf) increased with aqueous pH, but at [Tar2-]/([Al]+[Ga])≤5 it decreased with increase in aqueous pH. The distribution ratios of aluminium in the simultaneous extraction exceeded that in the individual extraction of aluminium while for gallium, these ratios decreased. This enhancement in selectivity for aluminium may arise from an exchange reaction between an aluminium species in an aqueous phase and an extracted gallium in an organic phase. The separation factor (Y=Sf) is related to the molar concentration ratio of aluminium and gallium (X=[Al]/[Ga]) as Y=A exp{-B×(X-9.38)2}+C, where A, B and C are variables that vary according to aqueous pH, and were determined by the least squares method.
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  • Yukiya MINAMI, Kazuhiko HAYASHI, Yukiko DOKIYA, Shin-ichi BESSHO
    1989 Volume 38 Issue 12 Pages 686-690
    Published: December 05, 1989
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    Since acid rain is a very serious problem in air chemistry, simultaneous sample collections over a wide area or remote sites is often necessary. For this purpose, simple and less expensive samplers are preferable. In this study, a polypropylene cylinder of 117 mm dia. was used to examine for the samplers of total chemical deposition (wet and dry deposition) for one month and in regard to the following: 1) size of sampler, 2) amount of water previously added, 3) height of sampler, 4) sampling period and others. It was concluded that this sampler could be satisfactorily used fbr the field determination of sodium, chloride and sulfate ions. A comparison was made for 22 sites throughout Japan, using this sampler in the observation fields of meteorological observatories, in June and October, 1987. The amount of nss-sulfate {SO42--Na+×SO42-(seasalt)/Na+(seasalt)} was calculated for each site. It was found high in industrialized areas of the Pacific side of Honshu I, and at Kagoshima, where amounts of nss-chloride are also high, possibly indicating the effect of volcanic debris from Mt. Sakurajima.
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  • Kunihiro WATANABE, Akane TSUTSUMI, Nobuyuki KOURA
    1989 Volume 38 Issue 12 Pages 691-696
    Published: December 05, 1989
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    Color-fading of Amide Black 10B (AB10) based on the catalytic reaction of Co and Cu has been applied to the determination of Co. The decomposition reaction of AB10 with hydrogen peroxide was catalyzed by cobalt and copper in alkaline medium. Tiron accelerated the catalytic reaction of cobalt, however, the effect of the activator was not significant for copper. The recommended procedure is as follows: Take a sample solution containing from 0.25 to 1.5 μg Co(II), adjust the concentration of hydrogen peroxide to 0.25%, AB10 to 5×10-5 M, and Tiron to 6×10-3 M in the final solution (50 ml). When stable absorbance (at 600 nm) is obtained for the circulating sample solution, add 2 ml of 2 M sodium hydroxide solution. A calibration curve was made between ln(A1/A6) and the concentration of cobalt or copper, where A1 and A6, were the absorbances of AB 10 at 1 min and 6 min, respectively. The values of ln(A1/A6) were nearly proportional to 30 ppb of Co and to 40 ppb of Cu. The R.S.D. was 2.5% (n=6) at 30 ppb of Co(II), but the R.S.D. of copper determination was 17% under the same conditions. Among diverse ions, 300-fold V, 30-fold Zn and 3-fold Fe relative to Co interfered with the determination of cobalt. The proposed method was successfully applied to the determination of cobalt (0.020.3%) contained in nickel chemical reagents.
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  • Koichi ITO, Shigeru KUBOYAMA, Hiroshi OGURO, Seiji NAKAMURA, Masayo MU ...
    1989 Volume 38 Issue 12 Pages 697-700
    Published: December 05, 1989
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    The accuracy and precision in isotope ratio measurements of lead by an ICP-MS were studied. The results of ICP-MS measurement obtained for the NBS SRM 981 lead standard were compared with the those by thermal ionization mass spectrometry (TIMS) and the NBS certified values. The precision of isotope ratio measurements with ICP-MS was worse than that with TIMS, but the values of ratio obtained by ICP-MS showed a good agreement with the values obtained by TIMS and certified ones by NBS. The isotope dilution ICP-MS was applied to the micro determination of lead in nickel alloys. A good agreement was obtained between the determined values and the certified values of lead in NBS SRM 897, 898, 899 nickel alloy standards with the precision of 1.02.1%, which was superior than that obtained by a calibration method.
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  • Kunihiro WATANABE, Hiroaki MURAKAMI
    1989 Volume 38 Issue 12 Pages 701-706
    Published: December 05, 1989
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    The suppression of extraction of micro-elements with an extractable macro-elements was investigated. The separation of micro-elements (ca. 10-4 M) was carried out based on the phenomena explained as common ions effect. Cadmium and zinc were used as the macro-elements. The maximum suppression effect was observed with 0.09 M Cd(II) and 0.5 M Zn(II) in 3.5 M HCl solution. Tributylphosphate (TBP) was used as an extraction solvent. Zinc and cadmium are extracted as chloro metal-acid complexes (H2ZnCl4 and H2CdCl4), which dissociated in the TBP phase after extraction from HCl solution. When the chloro metal-acid complexes formed with micro-elements also dissociated in the organic phase, the extraction of micro-elements was suppressed by macro-elements, while undissociated acid complexes were not suppressed. Therefore, the former can be separated from the latter. The dissociation of chloro metal-acid complexes was observed by measurement of specific conductivity in the organic phase. Sb(III), Ga(III), Mo(VI) and Fe(III) were extracted with 5 ml of TBP from 3.0 M HCl solution, separated from V(V) and Cu(II) remained in aqueous phase (25 ml) by addition of Cd(II) as macro-element. On the other hand, Zr(IV) was separated from Co(II) under conditions of 7 M HCl solution and 0.18 M Cd(II).
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  • Yoshiaki SASAKI, Shoji TAGASHIRA, Yoshiko MURAKAMI, Kazuhiko OKADA, Ke ...
    1989 Volume 38 Issue 12 Pages 707-711
    Published: December 05, 1989
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    The extraction behavior of zinc(II) and cadmium(II) complexes of O, O'-dialkyldithiophosphate(R2dtp-) with chloroform was investigated in a medium with constant ionic strength at 25°C. Four kinds of R2dtp- were examined, i.e., dimethyl(Me2dtp-), diethyl(Et2dtp-), dipropyl(Pr2dtp-) and dibutyl(Bu2dtp-) derivatives. The distribution ratio, D, of metal ion was calculated from the extracted metal ion concentration which was determined by AAS after the oxidative decomposition of the extracted complex with an NH4I-I2 solution. The composition, overall formation constant(β2), and distribution constant(KD) of the complex extracted were determined by analyzing a logarithmic plot of D vs. [R2dtp-] by a curve-fitting method. The species extracted was [M(R2dtp)2](M=Zn, Cd) in all cases. The values of KD increased in the order Me2dtp-<Et2dtp-<Pr2dtp-≈Bu2dtp- and the values of β2 increased in the order Me2dtp-<Et2dtp-<Pr2dtp-<Bu2dtp-.The cadmium complex was always more stable than the corresponding zinc complex.
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  • Kenjiro WATABE, Hiroshi KIKAWA, Taro KAWAMURA, Tomoyuki MIYAZAKI, Masa ...
    1989 Volume 38 Issue 12 Pages 712-717
    Published: December 05, 1989
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    A. method for the determination of zeranol, 17β-estradiol and diethylstilbestrol in beef has been developed by HPLC with an amperometric detection using column switching. These anabolic hormones were extracted from beef with acetonitrile and reextracted into dichloromethane. The concentrated extract was purified by a Bond Elut Silica, fbllowed by a Bond Elute Aminopropyl. The sample was injected onto a precolumn(30×5 mm i.d.), dry-packed with μ Bondapak C18(particle size 55105 μm). Polar components in the sample were removed from the precolumn by injection of 2 ml of 50 mM phosphate buffer-acetonitrile (80:20). Retained substances were desorbed by backflush with mobile phase onto a 5 μm Nucleosil C18 column (250×4 mm i.d.), separated with phosphate buffer-acetonitrile (50:50) at a flow rate of 0.7 ml/min, and monitored with an amperometric detector. The mean recoveries of zeranol, 17β-estradiol and diethylstilbestrol from beef spiked at 10 ng/g were 92.8, 92.6 and 80.2%, respectively. Detection limits of each hormone were 0.5 ng/g.
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  • Yoshihito SUZUKI, Hitoshi KOIZUMI
    1989 Volume 38 Issue 12 Pages 718-723
    Published: December 05, 1989
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    Addition reaction of iodine-halogen to olefinic compounds is used for the determination of iodine value, although the value obtained by Hanus method is lower than that by wijs method. In this study, unsaturated compounds such as oleic acid, linoleic acid and styrene were reacted with IBr, ICl and Br2. For UV monitor, halogen adducts of fatty acids were derivatized with phenacyl bromide. Separation of halogen adducts was investigated with a reversed phase HPLC system. In styrene, halogen adducts were separated each other, but IBr addition resulted in the formation of two bromine adducts. The halogen adducts of long chain unsaturated fatty acids were fractionated by preparative HPLC, because their HPLC separation was difficult. Fractionated halogen adducts were converted to halide ion by the oxygen combustion flask method. Halogen species were identified by the retention time of anion exchange chromatography and their abundances were determined by peak area. In the case of IBr addition reaction, only bromine adduct was observed for both oleic acid and linoleic acid.
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  • Tatsuhiko TANAKA, Kazuhiko WATAKABE, Kazumi KUROOKA, Takayoshi YOSHIMO ...
    1989 Volume 38 Issue 12 Pages 724-728
    Published: December 05, 1989
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    High-precision coulometric titration was developed for accurate evaluation of the deviation from stoichiometry of gallium arsenide crystal. Gallium(III) was allowed to react with a definite and excess amount of previously assayed EDTA, and the excess portion of EDTA was back-titrated with cadmium(II) ion generated electrolytically from an amalgamated cadmium anode. Arsenic(V) was reduced to the trivalent state with sodium sulfite by heating at about 40°C. The arsenic (III) was then titrated with electrogenerated iodine. The end points of the titrations were detected amperometrically. A high-purity arsenic metal was first assayed and the optimum conditions for determining arsenic were decided. Slight deviation from stoichiometry was confirmed in four gallium arsenide crystals. The standard deviations obtained by the proposed methods were of the order of 10-410-5 as an atomic fraction.
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  • Eiko NAKAMURA, Rumi SASAI, Hiroshi NAMIKI
    1989 Volume 38 Issue 12 Pages 729-733
    Published: December 05, 1989
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    Effects of concentrations of ammonium molybdate and sulfuric acid for the formation of molybdosilicic acid (Si-Mo) and heteropoly blue (Si-Mo blue), as well as for the extraction of Si-Mo blue, were investigated in detail. Under the concentrations suitable for the formation of Si-Mo, molybdate added in excess was also reduced to blue substance with ascorbic acid. Selective reduction of Si-Mo only, was carried out by increasing the acidity of the solution after the formation of Si-Mo blue, it was found that the concentration of sulfuric acid had to be raised above 1 M. The procedure of the experiment is as follows. Fifty milliliters of a sample solution containing silicate (up to 40 μg SiO2) in a 100 ml separating funnel is added with 1 ml of an ammonium molybdate (20%)-H2SO4 (2.5 M) solution. The solution is left standing for 20 min to form Si-Mo completely. After 5 ml of H2SO4 (2+1) and 1 ml of L-ascorbic acid solution (5%) are added, the solution is left standing for 10 min. Twenty milliliters of 1-butanol is added to the solution which is shaken for 2 min. An absorbance of the organic layer is mesured at 800 nm. The accuracy of the method is about 2.1% for 5 μg of SiO2.
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  • Tomiyuki MAEDA, Miho NAKATANI, Yasuaki TANIMOTO
    1989 Volume 38 Issue 12 Pages 734-736
    Published: December 05, 1989
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    An addition of oxygen gas to graphite furnace during the first ashing stage (20 s, 0.51 min-1) of AAS determination of Cd and Pb greatly decreased the background absorption due to sample matrices such as milk, orange juice and blood. In case of Pb determination, the intensity of background absorption due to blood matrix decreased to one-tenth of that without oxygen gas treatment. The addition of oxygen gas also prevented the signal depression of Cd and Pb by the sample matrices.
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  • Shunsuke IDE, Toshihide HARAGUCHI, Chiaki HATANAKA, Kouji NISHIMIYA
    1989 Volume 38 Issue 12 Pages 737-739
    Published: December 05, 1989
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    Water-insoluble polyacrylamide (PAAM) was synthesized by plasma-initiated polymerization of acrylamide and methylenebisacrylamide, and was studied for adsorption of Pd(II), Fe(III), Cu(II), Ni(II), Co(II), Zn(II) and Cd(II) from acidic solution. These metal ions were quantitatively adsorbed onto the PAAM. The reproducibility of the adsorption was confirmed by using PAAM of different lots. Ability of adsorption of the PAAM was not decreased even after five repetition of adsorption and desorption. It is expected that the polymers which have the ability of selective adsorption for various metal ions are obtained according to the choice of appropriate monomers in the plasma-initiated polymerization method.
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  • Yûetsu DANZAKI
    1989 Volume 38 Issue 12 Pages T191-T195
    Published: December 05, 1989
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    Vanadium content in zirconium-nickel-vanadium alloys was determined by hydrogen peroxide spectrophotometry following dissolution in nitric-hydrofluoric acids and fluoride ion masking with boric acid. Interference from coexisting elements was corrected for. Procedure: a sample (<about 1 g) containing vanadium less than 140 mg was digested with 10 ml of nitric acid (1+1) and 2 ml of hydrofluoric acid in a platinum dish and 40 ml of saturated boric acid solution were added. The solution was diluted to 100 ml with water. A 10 ml aliquot of this solution was mixed with 10 ml of sulfuric acid (1+1) and 10 ml of water, and was cooled in running water. One ml excess potassium permanganate solution (0.3 w/v%) was added. After standing for 5 min, 0.7 ml of a sodium nitrite solution (3 w/v%) was added with vigorously stirring in the presence of 4 ml of urea solution (50 w/v%). Absorbance was immediately measured at 450 nm after adding 3 ml of hydrogen peroxide (3%) and diluting to 50 ml with water.
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