BUNSEKI KAGAKU
Print ISSN : 0525-1931
Volume 49, Issue 7
Displaying 1-12 of 12 articles from this issue
Review
Research Papers
  • Toshihiro YAMADA, Satoshi HIRANO, Kazuhiro KOBAYASHI, Takanobu SAKURAI ...
    2000 Volume 49 Issue 7 Pages 493-501
    Published: 2000
    Released on J-STAGE: June 29, 2001
    JOURNAL FREE ACCESS
    The presence of unidentified styrene trimers(NST-12-1 and NST-12-2)was confirmed in the eluted substance of polystyrene.Both compounds were two diastereomers of 1-phenyl-4-(2-phenylethyl)tetralin, which were proved to be the 1, 4-cis(NST-12-1)and 1, 4-trans(NST-12-2)configuration by instrumental analysis and chemical synthesis.The content and miglation of NST-12 in polystyrene products were determined by GC/MS(SIM).Furthermore, the endocrine-disrupting effects of NST-12 were tested by in vivo and in vitro assays.It appeared that NST-12 has no such effects.
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  • Keiji OHE, Fumiyo KUSU
    2000 Volume 49 Issue 7 Pages 503-508
    Published: 2000
    Released on J-STAGE: June 29, 2001
    JOURNAL FREE ACCESS
    In artificial saliva, the surface corrosion of precious dental alloys containing Au, Ag and Cu was studied by in situ specular reflection spectroscopy.The rest potentials of the alloys in contact with artificial saliva were about −0.1V∼0.1V vs.SCE.It was found from the cyclic voltammograms of the alloys, that AgCl and/or CuCl were formed on the alloy at more positive potential than 0.1V.The formation of AgCl and/or CuCl was also observed as a reflectivity-potential change using specular reflection spectroscopy.For an alloy containing a large amount of Au, Cl ion was adsorbed on the alloy surface.Since the formation of AgCl and/or CuCl and the adsorption of Cl ion occurred at a more positive potential than the rest potential of alloy.It seemed that these alloys were stable in the artificial saliva.To confirm the surface corrosion of the dental alloys, this in situ analytical method is thus sufficiently sensitive and useful.
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  • Takashi SHINKAWA, Shunsuke YAMAZAKI, Hiroshi KAKISHIMA
    2000 Volume 49 Issue 7 Pages 509-513
    Published: 2000
    Released on J-STAGE: June 29, 2001
    JOURNAL FREE ACCESS
    The determination of the polymerase chain-reaction(PCR)products by fluorescence detection HPLC which using a post-column reaction was developed.The optimum conditions were;reactive solution, 0.5M NaCl-20mM Tris-HCl(pH9.0)containing SYBR Green(1/25000);flow rate of a reactive solution, 0.3ml/min.A reactive solution was stable for 24 hours.Under the optimized analytical conditions, the peak intensity of DNA was proportional not to the size of the base-pair, but to the concentration.The calibration curve was linear over the range 10pg∼50ng.The relative standard deviation for 10 standard DNA solutions(500bp-100pg)was 1.01%.The PCR products made from mice, which sensitized with 2, 4-dinitro-1-fluorobenzene(DNFB), was measured, and we succeeded in a high-sensitivity determination analysis.
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  • [in Japanese], [in Japanese], [in Japanese]
    2000 Volume 49 Issue 7 Pages 515-521
    Published: 2000
    Released on J-STAGE: June 29, 2001
    JOURNAL FREE ACCESS
    The preconcentration of copper and iron using a Teflon tube in the line-adsorption method was investigated for flow-injection analysis(FIA).A Teflon tube treated with an alkaline solution was used as an adsorbent(inner diameter, 0.5mm;length, 6.00m).Moreover, the conditions on the determination of copper and iron and the flow system on the FIA were examined after separation with a 0.5M HCl solution(0.15ml)from the concentration Teflon tube.The copper and iron were determined with 2-(5-bromo-2-pyridylazo)-5-[N-n-propyl-N-(3-sulfo-propyl)amino]aniline(5-Br-PSAA)by spectrophotometry at 558nm.Copper(II)was determined directly after elution.On the other hand, iron(III)was determined with 5-Br-PSAA after reduction to Fe(II)with ascorbic acid.The chemical species on the adsorption was estimated to be a metal-hydroxide cation based on the elution behavior.The optimum conditions were as follows:concentration pH, 11;adsorption flow rate, 0.6ml min-1;adsorption time, 30min;concentration tube length, 6m;5-Br-PSSA, 2.0×10-4M(0.4ml min-1);ascorbic acid, 0.01M(0.2ml min-1); carrier, 0.1M HCl(0.6ml min-1).The copper(II)was determined over the range 0.3∼16ppb;iron(III)was 0.6∼16ppb.The results of trace-amount determinations of copper(II)and iron(III)in tap water showed good agreement with the values obtained by graphite-furnace AAS and ICP-AES.
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  • Tomomi IWAMURA, Kiwao KADOKAMI, Daisuke JIN-YA, Kyoko TANADA
    2000 Volume 49 Issue 7 Pages 523-528
    Published: 2000
    Released on J-STAGE: June 29, 2001
    JOURNAL FREE ACCESS
    A method for the simultaneous determination of organotins(monobutyl-, dibutyl-, tributyl-, monophenyl-, diphenyl- and triphenyltin) in biological samples has been developed using ethyl derivatization and isotope dilution GC/MS.After the addition of deuterated organotins as internal standards to a homogenized biological sample, organotin compounds were extracted with 1M HBr-methanol/ethyl acetate(1:1);the extract was filtered and added to a saturated NaBr solution.The sample solution was then extracted with ethyl acetate/hexane(3:2), and the extract was mixed with hexane.The organic layer was dehydrated and concentrated.The concentrate was mixed with a buffer solution(pH5.0) and NaBEt4 solution to derivatize target organotins.Then, 1M KOH-ethanol was added to the derivatized sample solution and the mixture was shaken for 1 hour to decompose any fat.After saponification, ethylated organotins were extracted with hexane, and the extract was first dehydrated and then concentrated.The sample was cleaned up using a florisil cartridge column.Determination was carried out by GC/MS-SIM.The results of overall recovery tests at μg/kg levels showed that the mean recovery was 123% and their mean relative standard deviation was 12.5%.The detection limits of the method ranged from 0.13 to 6.6μg/kg.
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Technical Papers
  • Kyue-Hyung LEE, Mitsuko OSHIMA, Shoji MOTOMIZU
    2000 Volume 49 Issue 7 Pages 529-536
    Published: 2000
    Released on J-STAGE: June 29, 2001
    JOURNAL FREE ACCESS
    Ultratrace elements in natural water samples were determined simultaneously by air-segmented flow-injection/inductively coupled plasma-mass spectrometry(SFI/ICP-MS).A small volume of the sample solutions(80μl) was introduced into a nebulizer by an air-segmented flow-injection(SFI) system, and a maximum of fifteen elements were measured during each run.A chitosan-based chelating resin containing functional groups of iminodiacetate was used to separate and enrich analyte metal ions.A 50-fold preconcentration using 50ml of sample solutions was achieved by the proposed method, where 1ml of 0.1M nitric acid was added to residues after drying the chelating column effluent.At pH6, several heavy metals(Fe, Ni, Co, Cu, Zn, Ag, Cd, Pb and U) and rare earth elements(REEs) were quantitatively retained on the chelating resin column, whereas alkali and alkaline earth metals were eluted from the column by rinsing with 5ml of a 0.2M ammonium acetate solution.Metals adsorbed on the chelating resin column were recovered by elution with 10ml of 1M nitric acid.The proposed method was applied to the determination of trace elements in several natural water samples, such as river water and mineral drinking water.
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  • Toshiaki HIYAMA, Tomio KAGEYAMA
    2000 Volume 49 Issue 7 Pages 537-541
    Published: 2000
    Released on J-STAGE: June 29, 2001
    JOURNAL FREE ACCESS
    A controlled-potential coulometry is proposed for the determination of plutonium in the presence of iron.Iron interferes because the differences in the formal potentials of the Fe2+-Fe3+ and Pu3+-Pu4+ couples are very small in sulfuric acid.Even small quantities of iron relative to plutonium can cause an appreciable error in the analysis, since the equivalent weight ratio of Pu:Fe is about 4:1.In order to remove the interference of iron, 1, 10-phenanthroline was used as a complexing agent with iron.1, 10-phenanthroline reacts with iron(II) to form the complex, and the start of the oxidation potential was shifted to the positive side of about 100mV from that of iron.To obtain the most accurate result, the mole ratio of 1, 10-phenanthroline to iron was required to be more than 20-fold.The relative standard deviation was less than 0.3%.
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Notes
  • Zhidong CHEN, Tsutomu NAGAOKA
    2000 Volume 49 Issue 7 Pages 543-545
    Published: 2000
    Released on J-STAGE: June 29, 2001
    JOURNAL FREE ACCESS
    In this paper, we present a novel way to design a self-assembled monolayer, based on molecular imprinting protocols, for the selective recognition of hydrophobic molecules.A monolayer of octadecanethiol, templated with n-hexadecane, was fabricated on a gold substrate, and its voltammetric behavior was examined with vitamin K1 and K3.The monolayer film showed a voltammetric response only to hydrophobic vitamin K1 molecules, while a film without the hexadecane template showed neither a peak assigned to vitamin K1 nor K3.The results demonstrate that the present technique can be used as a simple and highly selective surface-designing tool for the fabrication of a self-assembled monolayer based electrode.
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  • Hajime GOTO, Jin-Ming LIN, Masaaki YAMADA
    2000 Volume 49 Issue 7 Pages 547-550
    Published: 2000
    Released on J-STAGE: June 29, 2001
    JOURNAL FREE ACCESS
    New heterogeneous chemiluminescence(CL)reaction media based on barium oxide(BaO)CL reaction system were developed using peroxomonosulfate(KHSO5)and hydrogen peroxide(H2O2)and nitrite(NO2-).It is known that KHSO5, an oxidizing agent, is decomposed by a metal ion catalyst(Co2+)to yield reactive species(Co3+, SO4-, etc.), which are strong oxidizing agents.On the other hand, peroxynitriteONOO- and nitrogen dioxide radical(NO2)obtained by reaction between H2O2 and NO2- are also powerful oxidizing agents.We have thus tried to immobilized these active species on the surface of BaO in order to improve the capabilities of BaO as not only CL, but also various reaction media.
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  • Keiji GAMOH, Hiyoshizo KOTSUKI
    2000 Volume 49 Issue 7 Pages 551-556
    Published: 2000
    Released on J-STAGE: June 29, 2001
    JOURNAL FREE ACCESS
    A method of the formation of a molecular template on bovine serum albumin(BSA)under a high-pressure condition has been developed.The BSA-adsorbed aminopropylsilica gel(APS-BSA)was suspended with cholestenone(4-cholesten-3-one)as a template molecule in aqueous ethanol, and the suspension was left standing under 200-800MPa for 4-12hrs.The solid residue was thoroughly washed with THF and ethyl acetate to extract cholestenone.The “templated”-APS-BSA gel selectively adsorbed cholestenone as the substrate in the suspended solution, including cholestenone.Also, the gel was used as a liquid-chromatographic packing material to examine its substrate- or structure-selectivity for some steroid compounds.A large-capacity factor for cholestenone was observed when an aqueous methanol solution was used as a mobile phase.This shows that the templated-APS-BSA gel has an appreciable molecular-recognition ability, and can be used as a selective adsorbent for a chromatographic separation.The selectivity has persisted for several months after intermittent applications.Furthermore, the templated-APS-BSA gel was analyzed using an IAsys plus, bio-molecule interaction analysis system by a resonant-mirror detector, to observe the binding amounts of the substrate.Only cholestenone showed an extremely higher value of the binding efficiency with the gel compared to any other steroid compounds tested.It has thus been shown that high pressure can be a parameter for molecular template formation on BSA, which means that a packing material with a highly selective molecular recognition site could be conveniently produced.
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Technical Letters
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