Analytical Sciences
Online ISSN : 1348-2246
Print ISSN : 0910-6340
ISSN-L : 0910-6340
Volume 5 , Issue 3
Showing 1-24 articles out of 24 articles from the selected issue
  • Toshikazu TARUTANI
    1989 Volume 5 Issue 3 Pages 245-252
    Published: June 10, 1989
    Released: June 30, 2006
    JOURNALS FREE ACCESS
    Useful information on the polymerization of silicic acid is obtained from a combined use of (1) spectrophotometry based on the formation of yellow molybdosilicic acid, (2) trimethylsilylation of silicic acid and determination of trimethylsilyl derivatives by gas-liquid chromatography and (3) gel permeation chromatography of silicic acid. The polymerization of silicic acid is divided into three processes: (1) the formation of polysilicic acid by the reaction between molybdate reactive silicic acids (MRS acid), (2) the particle growth of polysilicic acid by the reaction between MRS acid and polysilicic acid, and (3) the particle growth of polysilicic acid by the reaction between polysilicic acids. The pH value giving maximum rate of polymerization of silicic acid is different among these three processes. Fluoride promotes processes (1) and (2); the effect of fluoride on the process (3) is relatively small.
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  • Yoshio KOSUGI
    1989 Volume 5 Issue 3 Pages 253-255
    Published: June 10, 1989
    Released: June 30, 2006
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    The sulfur-33 nuclear magnetic resonance (NMR) spectra of thirteen kinds of benzenesulfonates have been obtained. Their chemical shifts varied qualitatively with the substitutent parameters. The spectral line width relative to that of benzenesulfonate reflects a change in the spherical configuration around the sulfur atom, which is related to a chemical shift deviation from the additivity calculation for carbon-13 NMR. Substitution with SO3- or CO2- does not change the line width, in spite of a large deviation of the carbon-13 NMR chemical shifts, the cause has been deduced as being interactions between negatively charged substituents. Quinoid structures distort the spherically more symmetrical configuration of the SO3- group, resulting in an extremely large broadening of the spectra of sodium salts of para- and meta-phenolsulfonic acids. The spectrum of the former is not observed with accumulation for three days.
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  • Tokuro NANBA, Itaru YASUI
    1989 Volume 5 Issue 3 Pages 257-262
    Published: June 10, 1989
    Released: June 30, 2006
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    The X-ray diffraction intensity obtained using a thin-film diffractometer has a special angular dependence as a result of its optical arrangement, owing to the absorption of X-rays by a thin-film specimen. In this study we examined in detail the influence of a secondary soller slit and developed a method of date correction so as to produce good agreement between the observed and calculated dependence. This method has been successfully applied to a structural study of WO3 evaporated film specimens.
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  • Atsushi UDAGAWA, Tomoko MATSUI, Shigeyuki TANAKA
    1989 Volume 5 Issue 3 Pages 263-267
    Published: June 10, 1989
    Released: June 30, 2006
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    The intensity and band shape of Fourier transform infrared reflection absorption (RA) spectroscopy have been studied for the analysis of an organic thin film formed on a SiO2 substrate. The optimum experimental condition to obtain the RA spectra with the best S/N ratio was theoretically determined for perpendicular polarization at an incidence angle of 76° on the basis of Fresnel equations using a model of a three-phase system consisting of air, a thin film and an inorganic substrate. The RA spectrum calculated from the dispersions of complex refractive indexes of a thin film and a SiO2 substrate was in good agreement with the experimental spectrum. The peak intensity of the thin film was linear up to about a film thickness of 100nm under these conditions. The calculation suggested both band distortion and a peak shift in the RA spectra.
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  • Kojiro MIKI, Tokuji IKEDA, Setsuko TODORIKI, Mitsugi SENDA
    1989 Volume 5 Issue 3 Pages 269-274
    Published: June 10, 1989
    Released: June 30, 2006
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    Department of Agricultural Chemistry, Faculty of Agriculture, Kyoto University, Kyoto 606, Japan Diaphorase-immobilized carbon paste electrodes with an entrapped mediator were fabricated by covering the enzyme layer formed on the electrode surface with a dialysis membrane. The mediator (2-methyl-1, 4-naphthoquinone (VK), 1, 4-benzoquinone and ferrocene) was mixed in the carbon paste electrode. These diaphorase-modified electrodes with an entrapped mediator were able to oxidize NADH catalytically at low applied potential. Some characteristics of film-coated diaphorase-immobilized carbon paste electrodes with entrapped VK were investigated. Then, NAD+-dependent dehydrogenase (for glucose-6-phosphate, lactate, glycerol and ethanol) and diaphorase were co-immobilized on a carbon paste electrode containing both NAD+ and VK. The film-coated dehydrogenase and diaphorase co-immobilized electrodes with entrapped NAD+ and mediator (VK) gave the current response to the substrate of the immobilized dehydrogenase at low applied potential.
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  • Kiyoshi HASEBE, Mitsuhiko TAGA, Namiko OSANAI, Janet G. OSTERYOUNG
    1989 Volume 5 Issue 3 Pages 275-279
    Published: June 10, 1989
    Released: June 30, 2006
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    The polarographic determination of 5-chloro-7-iodo-8-quinolinol (ClIoxine) and its homologues has been carried out in N, N-dimethylformamide. ClIoxine and its related compounds each give at least one irreversible reduction wave. ClIoxine itself has three reduction waves in d.c. polarography and the corresponding reduction peaks in square wave polarography. The first reduction wave shows a two-electron reduction step, and the subsequent ones have one-electron steps. The wave height of the first d.c. wave is proportional to the concentration of ClIoxine down to 10-4mol/dm3, and the square-wave peak is also proportional to the concentration in the range 6×10-6-1.7×10-4mol/dm3. The related compounds 5-chloro-8-quinolinol and Ferron can be determined in the same manner.
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  • Yong-Moon LEE, Hiroshi NAKAMURA, Terumi NAKAJIMA
    1989 Volume 5 Issue 3 Pages 281-284
    Published: June 10, 1989
    Released: June 30, 2006
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    The simultaneous separation of fluorescent 4-N, N-dimethylamino-1-naphthylthiohydantoin (DNTH) amino acids was attained by high performance liquid chromatography (HPLC); they were separated in 35min on a reversedphase TSK-gel 80 TM (C18) column with a linear gradient elution using 35mM of sodium acetate buffer (pH 5.0)-acetonitrile (65:35, v/v) and acetonitrile. An enhanced detection capability of DNTH-amino acids (E×345nm, Em 425nm) was achieved by the postcolumn addition of 7.5% tetraethylammonium hydroxide in dimethylsulfoxide. The established HPLC system permitted the detection of DNTH-amino acids in quanitities of 0.5pmol. The application of this method to the sequence analysis of human GRF is also described.
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  • Tsuyoshi TSUJIYAMA, Yozo HAMACHI, Takeo KURIKI, Nobuo SUZUKI, Misao TS ...
    1989 Volume 5 Issue 3 Pages 285-288
    Published: June 10, 1989
    Released: June 30, 2006
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    An ion-pair chromatographic method for separation of enantiomers of nomifensine maleate was established. Chiral separation was achieved by chromatography for N trifluoroacetylated nomifensine maleate enantiomers on Supherisorb Silica 5μm, a normal phase column, using a mixture of chloroform, methanol and water (100:3:0.15) containing a chiral counter ion, (+)-camphor-10-sulfonic acid (2×10-3mol l-1) as the mobile phase. The standard curve obtained was straight line passing through the orgin; this extended from 25ng to 25μg of the injected material. The results suggested that the proposed method is simple and rapid enough to be applied for the purity test of nomifensine maleate enantiomers.
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  • Masaaki KAI, Mutsuko NAKANO, Guo-Qing ZHANG, Yosuke OHKURA
    1989 Volume 5 Issue 3 Pages 289-293
    Published: June 10, 1989
    Released: June 30, 2006
    JOURNALS FREE ACCESS
    Fluorometrically reactive peptides of leucine- and methionine-enkephalins in rat brain tissues such as cortex, striatum and hypothalamus were simultaneously assayed by reversed-phase high performance liquid chromatography with fluorometric detection, based on precolumn derivatization specific for N-terminal tyrosine-containing peptides. The enkephalin peptides extracted from the tissues were converted into fluorescent derivatives by reaction with hydroxylamine, cobalt(II) ion and borate in a weakly alkaline aqueous solution (pH 8.5). The fluorescent derivatives of the peptides were separated on a reversed-phase column (TSKgel ODS-120T) by gradient elution of acetonitrile in the mobile phase containing borate buffer (pH 8.5) and tetrabutylammonium chloride, and then determined by fluorometry. The peaks of both the enkephalins in the tissue sample were not observed in the chromatogram after the enzymatic degradation with carboxypeptidase A. The determined concentrations of the leucine- and methionine-enkepalins in the tissues were 20-238pmol and 80-75pmol per g of the tissue, respectively. The method was sensitive enough to determine the endogenous enkephalins at concentrations as low as Ca. 6pmol per g of the brain tissues.
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  • Ichiro KOSHIISHI, Toshio IMANARI
    1989 Volume 5 Issue 3 Pages 295-299
    Published: June 10, 1989
    Released: June 30, 2006
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    A reliable method for determination of the homocitrullin (N-carbamyl lysine) residue in plasma proteins is presented. The principle of this method is based on the nitrosylation of N-carbamyl group by nitrite in acidic solution, and degradation of nitrosourea to cyanate ion in alkali solution. The liberated cyanate ion is determined by a cyanate ion analyzer. The standard protein sample for determination of the homocitrullin residue was prepared using cyanate-treated bovine serum albumin (BSA). The standardization method was as follows: after hydrolysis in acidic solution, homocitrullin in hydrolysate was determined against standard homocitrullin by the present method. Under physiological conditions, cyanate ion preferentially reacts with ε-amino group in plasma proteins.
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  • Satoshi KAWAI, Ryota NISHIOKA, Masaharu NAKAHIGASHI, Kazuko KONDO, Yuz ...
    1989 Volume 5 Issue 3 Pages 301-304
    Published: June 10, 1989
    Released: June 30, 2006
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    A simple and rapid determination of 3-keto-valproate (3-keto-VPA) in urine is described by a metal capillary gas chromatography (GC) with a flame ionization detector (FID). 3-Keto-VPA was converted to 3-heptanone under acidic condition. 3-Keto-VPA-glucuronide was hydrolyzed to 3-keto-VPA by means of β-D-glucuronidase. 3-Heptanone thus formed was extracted with hexane and determined by GC. Suitable conditions for decarboxylation of 3-keto-VPA and hydrolysis of 3-keto-VPA ethyl ester (3-keto-VPA-Et) were also investigated. The present procedure does not require any derivatization or complicated separation techniques. Classifiable determinations of free 3-heptanone, free 3-keto-VPA and 3-keto-VPA-glucuronide were possible. A deactivated metal capillary column was applied for the determination of urinary 3-keto-VPA; its minimum detectable amount was about 0.1μg/ml in urine. The column was suitably inert, mechanically tough, and easier to handle than a fused silica one; the peaks on the chromatogram were almost symmetrical without any tailing or leading.
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  • Yu YOKOYAMA, Teruo HINOUE, Kazuhiro MORITA, Takashi OHBAYASHI
    1989 Volume 5 Issue 3 Pages 305-310
    Published: June 10, 1989
    Released: June 30, 2006
    JOURNALS FREE ACCESS
    A thermal diffusion equation has been solved using a spherical particle model, and could well explain the behavior of photoacoustic signals of a powdered sample. The solutions show the following: (1) That the optical absorption coefficient, the thermal diffusion coefficient, and the particle size have significant influences on the photoacoustic signals. (2) That the difference in photoacoustic signal among different particle sizes is caused primarily by an effect related to the surface area of a particle for a small optical absorption coefficient. (3) That, further, the effect of the surface temperature of a particle becomes important as the optical absorption coefficient increases. These consequences have been verified by experiments with powdered samples of chromium(III) potassium sulfate 12-water, CrK(SO4)2•12H2O, and its mixed crystals with aluminum potassium sulfate 12-water, AIK(SO4)2•12H2O.
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  • Tadashi MOCHIZUKI, Akiko SAKASHITA, Hideo IWATA, Yoichi ISHIBASHI, Nao ...
    1989 Volume 5 Issue 3 Pages 311-317
    Published: June 10, 1989
    Released: June 30, 2006
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    Direct analysis of silicate samples for the rare earth elements (REEs) by inductively coupled plasma mass spectrometry (ICP-MS) has been performed. Each finely ground sample (particle size <3μm) was dispersed in 0.1% aqueous Triton X-100 solution and nebulized into an inductively coupled plasma. The resulting ions were detected by mass spectrometry. Parameters such as particle size, slurry concentration and argon carrier flow rate exercised a great influence on sensitivity, precision and accuracy of slurry nebulization/ICP-MS. Calibration curves were constructed using aqueous standard solutions. The extended dynamic range (EDR) detection system allowed the use of matrix element as an internal standard; this procedure was effective to correct the differences in sensitivity between the solution and the slurry methods. The optimum procedure was applied to the determination of REEs in standard silicate rocks of the Geological Survey of Japan. The precision ranged from 0.8 to 6.3 (RSD, %) for REEs contents of 0.13-38ppm. Detection limits of REEs were excellent (0.002-0.02ppm at the effective integrating time of 10s).
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  • Akihiko HARUTA, Ken MATSUMOTO, Kikuo TERADA
    1989 Volume 5 Issue 3 Pages 319-322
    Published: June 10, 1989
    Released: June 30, 2006
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    2-Mercapto-N-2-naphthylacetamide (thionalide)-loaded silica gel is used for preconcentration of bismuth(III) in lower concentration than μg l-1 from water samples. Bismuth(III) is quantitatively retained on the loaded gel from 0.1-1.0M (mol l-1) nitric acid or 0.1M hydrochloric acid solutions in batch experiments. Equilibration is achieved within 2min. The retention capacity of the gel is 2μmol Bi(III) g-1 at 0.25M nitric acid. The maximum flow velocity for quantitative retention is 2.8cm min-1. Bismuth retained on the column is completely eluted with 10ml of 4.0M hydrochloric acid at flow velocity 1.3cm min-1. Bismuth in the effluent is determined by atomic absorption spectrometry with hydride generation; the detection limit is 1.0ng of bismuth.
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  • Shuko FUJIEDA, Nobue NISHI
    1989 Volume 5 Issue 3 Pages 323-328
    Published: June 10, 1989
    Released: June 30, 2006
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    An intelligent potentiometric titrator is described which can carry out automatic precipitation titrations under optimum conditions and minimum time. The buret tip is not immersed in the titrand solution as is usually the case, but is held above the solution so as to prevent the titrant from leaking and reacting with the titrand solution during waiting intervals. The titrant is added drop by drop with a motor-driven buret. After each drop of titrant has been added, the buret is stopped and values of the potential difference obtained with predetermined short time intervals (e.g. 1s) are stored in a microcomputer. From the convergence of several successive values, the microcomputer determines whether there has been a substantial attainment of the precipitation equilibrium, stores the final value in the memory and sends a control signal to the buret to resume titrant addition. These operations are repeated until the equivalence point is passed. The exact equivalence point could be evaluated by any common method. Particularly, Gran′s plot method is preferred. The appropriateness of the system, including hardware and software, has been demonstrated by titration of silver ions with chloride, which gave very reasonable results.
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  • Yuzuru HAYASHI, Sumie YOSHIOKA, Yasushi TAKEDA
    1989 Volume 5 Issue 3 Pages 329-334
    Published: June 10, 1989
    Released: June 30, 2006
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    A function (FUMI) which describes the Shannon mutual information in chromatography is derived. FUMI covers two subjects in one formula: (i) the degree of peak overlap and the noise level; (ii) the mathematical formalism of peak deconvolution and quantitation based on the one-dimensional Kalman filter for peak resolution. Computer simulation demonstrates that a sufficient amount of mutual information can be retrieved from overlapped peaks (Gaussian) through (i) observation and (ii) data processing. A practical advantage of FUMI is logical evaluation and optimization of chromatographic experiments without resort to experience: the optimal can be defined as the chromatogram which can transmit the maximal amount of mutual information in a unit time.
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  • Akira NOMURA, Joseph YAMADA, Kin-ichi TSUNODA, Kohichi FUKUSHIMA, Kazu ...
    1989 Volume 5 Issue 3 Pages 335-338
    Published: June 10, 1989
    Released: June 30, 2006
    JOURNALS FREE ACCESS
    Retention of polar and non-polar compounds on ODS-silica gel columns was investigated in terms of the pore structure of silica gel and surface modification. The purpose was to develop inert columns for supercritical fluid chromatography (SFC) using carbon dioxide as a mobile phase without a modifier. Utilization of silica gel having larger pore diameter and sufficient end-capping of residual silanol groups after primary surface modification promoted the preparation of inert packings. Three types of ODS-silica gel columns: without end-capping, end-capped in a liquid phase and end-capped in a vapor phase, were compared by applying each to the separation of carrot extract with supercritical CO2.
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  • Hideyuki NISHIZAWA, Yukako WATANABE, Sakiko OKIMURA, Yoshihiro ABE
    1989 Volume 5 Issue 3 Pages 339-343
    Published: June 10, 1989
    Released: June 30, 2006
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    An improved apparatus for dual-flow countercurrent extraction was constructed. Further, a simple method to evaluate the extractor was developed, by which the effective plate number could be calculated by a couple of measurements of fractional recoveries. To find the optimum operation condition, an apparatus with a shorter column (10cm in length) was prepared, the efficiency of which was evaluated as being about one plate per cm of the column length by the method. It was also shown that the distribution constant of a compound could be calculated from the fractional recoveries measured by dual-flow countercurrent extraction. The distribution constants, thus obtained, agreed with values determined independently by liquid-liquid chromatography, which settled theoretical correlations between chromatography and extraction.
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  • Hideyuki NISHIZAWA, Yukako WATANABE, Sakiko OKIMURA, Yoshihiro ABE
    1989 Volume 5 Issue 3 Pages 345-350
    Published: June 10, 1989
    Released: June 30, 2006
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    A new separation system in dual-flow countercurrent extraction has been established. As a result, a two-component mixture could be separated with the improved apparatus, liquid particle extractor, whose working principle is the same as that in liquid particle chromatography (LPC). Liquid particle chromatography has been used as a means to determine the distribution constants of components in a sample, which were necessary for setting the operating condition of the extractor. The optimum condition for the best separation of two compounds (distribution constant of D1 and D2) was deduced theoretically. Thus, the flow rate of the aqueous phase (H) could be determined by a calculation using the flow rates of the sample feed (A, fed as an organic solution) and the organic phase (S) by the relation; H=(S+A/2)√<D1×D2>. With the extractor, a continuous and complete separation of phenyl-β-D-glucopyranoside (D=1.17) and esculin (D=1.58) in a 100mg-scale (100mg each in 20ml of water saturated 1-butanol) could be executed in 14h. A precise separation of a mixture with a separation factor (D1/D2) of 1.23 was also accomplished.
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  • Shunsuke IDE, Makoto TAKAGI
    1989 Volume 5 Issue 3 Pages 351-354
    Published: June 10, 1989
    Released: June 30, 2006
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    Liquid-liquid extractions of Cu(II), Zn(II), Co(II), Ni(II) and Cd(II) were studied in an alkaline media using a bissulfonamido-type bidentate extractant bis(octanesulfonamido)benzene (BOB). Iminodiacetic acid(IDA) was used in an aqueous solution to prevent metal hydroxide precipitation. Though Zn(II) and Cu(II) were extracted quantitatively, extractions of the other ions were poor. To attatin more efficiency, trioctylmethylammonium chloride (TOMC) and bathophenanthroline (B-ph) were studied as synergists. Complete metal extraction was obtained by using either one of these synergists. In addition to IDA, citric acid or EDTA was also usable as a complexing agent in an aqueous solution, which simultaneously gave a variation or modification in metal extraction selectivity and extraction pH.
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  • Jun YOSHINAGA, Minato NAKAZAWA, Tsuguyoshi SUZUKI, Masatoshi MORITA
    1989 Volume 5 Issue 3 Pages 355-358
    Published: 1989
    Released: July 27, 2007
    JOURNALS FREE ACCESS
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  • Tamio KAMIDATE, Kazuyuki YOSHIDA, Tadashi SEGAWA, Hiroto WATANABE
    1989 Volume 5 Issue 3 Pages 359-360
    Published: 1989
    Released: July 27, 2007
    JOURNALS FREE ACCESS
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  • Shigeru NARITA, Takayasu KITAGAWA
    1989 Volume 5 Issue 3 Pages 361-362
    Published: 1989
    Released: July 27, 2007
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  • Tsutomu NOMIZU, Masaki SANJI, Masataka HIRAIDE, Atsushi MIZUIKE
    1989 Volume 5 Issue 3 Pages 363-365
    Published: 1989
    Released: July 27, 2007
    JOURNALS FREE ACCESS
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