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Kenji SAKURAI, Atsuo IIDA, Yohichi GOHSHI
1988 Volume 4 Issue 1 Pages
3-7
Published: February 10, 1988
Released on J-STAGE: June 27, 2006
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The signal to background (S/B) ratio in energy dispersive X-ray fluorescence using synchrotron radiation (SR) was quantitatively analyzed. The S/B ratio, which has been significantly improved by taking advantage of the polarized nature of SR, was found to be strongly dependent on geometrical factors of the measurement system. From the analysis on the origin of the scattered background, the dependence of the S/B ratio on the geometry was quantitatively explained, mainly by the polarization properties of SR. Experimental conditions could be optimized by adjusting the degree of polarization of the incident beam and the detector solid angle.
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Sachiko SAKURA, Hideo IMAI
1988 Volume 4 Issue 1 Pages
9-12
Published: February 10, 1988
Released on J-STAGE: June 27, 2006
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An electrochemiluminescence method was developed for determination of sub-nmol hydrogen peroxide in aqueous solution. Luminol was electrochemically oxidized, then reacted with hydrogen peroxide; it emitted light of the maximum wavelength of 436nm with a half-life of less than 0.2s from the electrode surface. In flow injection analysis a carrier solution (phosphate buffer, pH 7-9) containing 17μM luminol was delivered at the flow rate of 0.5ml/min. The luminescence was detected by a photon counter in a spiral cell under the applied potential of 0.7V vs. SCE. A straight line calibration plot was obtained with good reproducibility [RSD 1.6% (
n=5)] in the concentration range of 0.066 to 0.6nmol.
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Abdulrahman S. ATTIYAT, Gary D. CHRISTIAN
1988 Volume 4 Issue 1 Pages
13-16
Published: February 10, 1988
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The potentiometric selectivities of two 14-crown-4 ethers incorporated in PVC membrane electrodes were determined for lithium with respect to sodium and potassium in different solvents and in different carrier solutions using flow injection analysis. Four methods for calculating selectivity coefficients were compared. A correlation is made between the relative levels of the interfering ion and primary ion and the numerical values of the selectivity coefficients calculated by the different methods. An increased level of sodium causes divergence among the values of the selectivity obtained by different methods, increases the selectivity of lithium over sodium, decreases the sensitivity and the slope of the calibration graph, and distorts the linearity of the curve.
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Masashi GOTO, Ken SHIMADA, Toyohide TAKEUCHI, Daido ISHII
1988 Volume 4 Issue 1 Pages
17-20
Published: February 10, 1988
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A tubular electrolytic cell of ultra micro volume, made of a single carbon fiber (7μm o.d., 15mm length) as the working electrode material and a fused silica tube (50μm i.d.) as the flow cell part, was designed for use as the electrochemical detector in micro high performance liquid chromatography (micro HPLC). The effective cell volume is about 0.03μl. This detector with carbon fiber was useful for detection of catecholamines and their metabolites. Their detection limits were about 1-2pg and the linear dynamic range was about 10
3. The detector was successfully applied to urinary catecholamine analysis by micro HPLC and to rapid detection of electroactive species in fast micro HPLC.
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Chiyozo TAKAYAMA, Mototsugu YOSHIDA, Yoshikatsu MIYASHITA, Haruo IMAJO ...
1988 Volume 4 Issue 1 Pages
21-24
Published: February 10, 1988
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A computer program called PREHAC was developed. This aids in the prediction of highly bioactive compounds among congeners in series of aliphatic monosubstituted derivatives and aromatic mono-, di- and tri-substituted ones, based on the Hansch-Fujita method. The PREHAC program is applicable to two phases included in the computer-assisted lead optimization: the development of a QSAR equation and the decision about the direction of structural modification based on the correlation, that is, the selection of substituent. This program was designed to search the Master Data file of 13 sets of physicochemical parameter values for 408 useful substituents. From the input of substituent names, activity values, and information on the combination of parameters, or from the input of the coefficients and intercept of the QSAR equation, the predicted high-ranking derivatives will be printed out. An example is given.
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Shin-ichi NISHIKIORI, Toschitake IWAMOTO
1988 Volume 4 Issue 1 Pages
25-30
Published: February 10, 1988
Released on J-STAGE: June 27, 2006
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Inclusion selectivity has been examined for xylene isomers and benzene in the Hofmann-dma-type Cd[NH- (CH
3)
2]
2Ni(CN)
4 metal complex host. This has a layered structure of a two-dimensionally extended cyanometal complex network with the dimethylamine ligands protruding up and down from the network. The o-isomer is preferentially enclathrated in the metal complex host from the mixtures of xylene isomers, but the presence of benzene in the mixture makes the
p-isomer more preferable. Benzene is enriched from the mixtures with xylene isomers at very low concentrations. The selectivity behavior is discussed based on the crystal structures of the relevant clathrates.
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Totaro IMASAKA, Katsunori TANAKA, Nobuhiko ISHIBASHI
1988 Volume 4 Issue 1 Pages
31-35
Published: February 10, 1988
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A supersonic jet fluorimeter with a spectrometric multichannel analyzer allows repetitive measurements of a fluorescence spectrum for gas chromatograph effluents. A three-dimensional chromatogram is measured for a sample containing chloroanthracene derivatives by adjusting the excitation wavelength to that of a pure electronic transition for a specified molecule. By using this method, the sample molecule can readily be identified from well-resolved spectral features in the fluorescence spectrum. The detection limits are several hundred ng for l- and 9-chloroanthracenes.
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Kenji SAKURAI, Atsuo IIDA, Yohichi GOHSHI
1988 Volume 4 Issue 1 Pages
37-42
Published: February 10, 1988
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Tunable monochromatic X-rays obtained from synchrotron radiation was used for the selectively induced X-ray emission spectroscopy (SIXES), which is an analytical technique with X-ray fluorescence detection and is based on the selective excitation of specific chemical species. The near edge absorption spectra of iron were measured by SIXES using an energy dispersive detection system with a Si(Li) detector. The present method, compared with the conventional transmission method, is particularly suitable for the chemical state analysis of trace systems of less than 10
-10g because of its high sensitivity. A mixture containing several chemical species could be analyzed within ±6% precision by SIXES.
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Yuko YAMASHOJI, Takayuki MATSUSHITA, Toshiyuki SHONO
1988 Volume 4 Issue 1 Pages
43-47
Published: February 10, 1988
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A series of bis(diphenylphosphinyl)alkanes (DPPO)
2R, where R can be p-xylene-α, α′-diyl and (CH
2)
n(
n=1-6, 8 and 10), has been prepared and employed to investigate the solvent extraction of gallium(III) from hydrochloric acid solutions. These bis-type ligands have been found to be more effective than the monodentate ligand, triphenylphosphine oxide (TPPO). The percentage extraction of gallium(III) with these ligands increases with increasing the acidity of the aqueous phase. The extractabilities of the bis-type ligands (DPPO)
2(CH
2)
n depend on the methylene length and increase in the order n=1<2<3_??_6, 8 and 10. The molar ratios of the extractant to gallium(III) in the extracted species are determined to be 1:1 for TPPO and 2:1 as well as 1:1 for the bis-type ligands. These ratios depend on the initial extractant concentration in the organic phase. The extraction constants are log
Kex=2.5, 5.4 and 4.8 for TPPO, (DPPO)
2(p-xyl) and (DPPO)
2(CH
2)
3, respectively.
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Shinkichi YAMADA, Hidetake ANMA, Akira MURATA
1988 Volume 4 Issue 1 Pages
49-52
Published: February 10, 1988
Released on J-STAGE: June 27, 2006
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The rates of the ligand substitution reactions of niobium and tantalum complexes involving oxalate, tartrate, citrate or nitrilotriacetate as an auxiliary complexing agent with 4-(2-pyridylazo)resorcinol have been studied spectrophotometrically in acidic media. In the citrate system at pH 5, the maximum difference in rate of substitution between the niobium and the tantalum complexes was achieved. Under the chosen conditions, where the total concentrations of citrate and 4-(2-pyridylazo)resorcinol are 2×10
-2 and 1×10
-4mol dm
-3 respectively, the absorbance change during the reaction progress can be kinetically separated for each metal ion and less reactive tantalum in the range 10
-6-10
-5mol dm
-3 can be determined by a logarithmic extrapolation method. In the determination of 5×10
-6mol dm
-3 of tantalum, the presence of 5-fold amounts (by molarity) of niobium can be tolerated. The effects of 52 diverse ions were examined.
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Kuniyuki KITAGAWA, Hidekatsu KIKUCHI
1988 Volume 4 Issue 1 Pages
53-57
Published: February 10, 1988
Released on J-STAGE: June 27, 2006
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The Fraunhofer diffraction of laser radiation was applied to the correction of physical interference in a nebulizer used for atomic absorption spectrometry. A chamber with windows was mounted between the nebulizer system and the burner head. A He-Ne laser beam passing through the chamber was diffracted by droplets and constructed an image. The diffraction image received by a linear image sensor of 1024 elements was processed by a microcomputer to obtain the size distribution and the total volume of the droplets. The correction was made by dividing the absorbance by the total volume.
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Kenji KATO, Yoshinori SUGITANI
1988 Volume 4 Issue 1 Pages
59-62
Published: February 10, 1988
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Correlation photoacoustic spectroscopy was carried out in X-ray region using synchrotron radiation(SR) as an exciting source. Thermal diffusion in copper foils and in laminated samples was investigated. The characteristic rise and fall times of correlation spectra, τ
0 and τ
f, respectively, were found to be influenced by sample thickness with the maximum values at intermediate thicknesses (10 and 50μm) for copper samples. This was interpreted as arising from the competing effect between the thermal diffusion within the sample and the thermal radiation from the sample surface. For the laminated samples, increases of τ
0 and τ
f were observed with the increase of thickness of polymer layer on the copper substrate.
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Amalia MASANA, Manuel VALIENTE
1988 Volume 4 Issue 1 Pages
63-68
Published: February 10, 1988
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The study of the chemical equilibria involved in the solvent extraction of ZnCl
2 by trilaurylammonium chloride (TLAHCL) in toluene has been carried out at three different aqueous chloride concentrations, l (l=1.0, 2.0 and 3.0mol dm
-3). The experimental data, obtained by measurement of the metal distribution as a function of the extractant concentration, have been treated using numerical methods. The extraction process is explained by the following extraction reactions: Zn
2++2Cl
-+2TLAHCl(org)_??_ZnCl
2(TLAHCl)
2(org),
K2; Zn
2++2Cl
-+3TLAHCl(org)_??_ ZnCl
2(TLAHCL)
3(org),
K3; 3Zn
2++6Cl
-+6TLAHCl(org)_??_Zn
3Cl
6(TLAHCL)
6(org),
K6. The species formed in the organic phase seems to be independent of the aqueous chloride concentration, while the values of the extraction constants are different for each chloride concentration (l=1.0, log
K2=4.38, log
K3=6.06, log
K6=15.1; l=2.0, log
K2=4.51; log
K3=6.17, log
K6=14.9; l=3.0, log
K2=4.37, log
K3=5.81). The values obtained were correlated using the specific-interaction theory.
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Isao YOSHIDA, Fumio SAGARA, Keihei UENO
1988 Volume 4 Issue 1 Pages
69-72
Published: February 10, 1988
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The first and second protonation constants of 2-nitroso-5-(
N-propyl-3-sulfopropylamino)phenol (NPSAP, H
2L) and the stability constants of the metal ion complexes formed by NPSAP with some divalent and tervalent metal ions such as magnesium(II), calcium(II), cobalt(II), nickel(II), copper(II), zinc(II), aluminium(III), iron(III) and gallium-(III) have been determined potentiometrically in aqueous solution at 25°C (μ=0.1 with KNO
3).
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Hajime ISHII, Tsugikatsu ODASHIMA, Takashi HASHIMOTO
1988 Volume 4 Issue 1 Pages
73-76
Published: February 10, 1988
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The equilibria and kinetics of the extraction of nickel ion with benzene solutions of 2-pyridinecarbaldehyde 2-(5-substituted)pyridylhydrazones have been studied at 25±0.1°C and an ionic strength of 0.2. The extracted species was found to be Nil
2 for each hydrazone, where L denotes the undissociable part of the hydrazone. Partition constants of the hydrazones and extraction constants of their nickel complexes between an aqueous and a benzene phase were determined. The rate of extraction was found to be best described by a two-term expression, both terms being first order in nickel ion and HL concentrations. The first term has zero dependence on hydrogen ion concentration, whereas the second is inversely first order with respect to hydrogen ion concentration. These results support the hypothesis that the rate-determining steps involve two concurrent reactions of nickel ion with neutral and anionic forms of the hydrazones. Kinetic data and activation parameters for the first reaction were determined, but those for the second one involving the anion could not be obtained.
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Mair TAKAHASHI, Kazuyoshi TAKIYAMA
1988 Volume 4 Issue 1 Pages
77-80
Published: February 10, 1988
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The atomic absorption of aluminum with air-acetylene flame was interfered by the formation of involatile compounds in the flame. Amines promoted the atomization of aluminum in the flame. Aluminum could be determined by atomic absorption spectrometry with an air-acetylene flame. The absorption of aluminum increased and then attained a constant value as the concentration of amines increased. The enhancement effect of amines was attributed to the reducing action of the CN, NH and CH radicals formed in the flame by decomposition of amines. It seems that these radicals acted in the same way as those formed in the nitrous oxide-acetylene flame. The present method was applied to the determination of aluminum in food concomitant substances with satisfactory results.
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Tadashi IWACHIDO, Kenji ISHIMARU, Shoji MOTOMIZU
1988 Volume 4 Issue 1 Pages
81-85
Published: February 10, 1988
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Alkali metal cations were shown to be separable on a silica gel column by cation exchange. Factors affecting the separation of these cations were investigated. Among them, type and concentration of the mobile phase electrolytes profoundly affected the retention of the analyte. The alkali metal cations were well separated on a 150 mm long Zorbax SIL column with 2.1mm i.d., using an aqueous 0.01mol dm
-3 lithium acetate as the mobile phase. Sodium and potassium in river water were determined rapidly with satisfactory accuracy.
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Masashi GOTO, Shunji KUMAGAI, Daido ISHII
1988 Volume 4 Issue 1 Pages
87-90
Published: February 10, 1988
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An automated continuous monitoring system for total mercury at sub-ppb level based on cold-vapor atomic absorption spectrometry-"continuous micro flow analysis" is described. The method uses continuous flow sample digestion, reduction and extraction in small bore tubes (0.25mm i.d.) at very slow flow rates of reagents (17-23μl min
-1). On descrete injection of sample (180μl), analytical time for the determination of total mercury was about 4min per one sample. The detection limit of mercury(II) was about 0.15μg l
-1 (
S/N=3) using a gas flow cell with 40mm lightpass length; the relative standard deviation for the measurement at 2μg l
-1 level was 1.2% (
n=5). On continuous micro flow injection of sample at a flow rate of 180μl min
-1, the system was successfully applied to the completely continuous monitoring of total mercury in wastewater.
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U. K. UNDERBERG-CHITOE, W. J. M. UNDERBERG, H. LINGEMAN
1988 Volume 4 Issue 1 Pages
91-96
Published: February 10, 1988
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Chromatography of basic solutes has been described on non-modified silica and alumina using aqueous buffers with suitable modifiers. On these packing materials selectivity and retention of the compounds are influenced in various ways; by the modifier content, the electrolyte concentration and the pH. Generally, only cationic species are retained on these sorbents. Their retention decreases with increasing electrolyte concentration. The relationship between retention and modifier content is more complicated and, moreover, different for the two packing materials. The differences in selectivity will be illustrated by comparing the chromatography of combinations of basic drugs (
e.
g. phenylethylamines, alkaloids), the analysis of basic drugs in pharmaceutical formulations (
e.
g. prednisolone, physostigmine) and the detection of basic drug metabolites (
e.
g. amphoteric glucuronides) on silica and alumina. The aqueous nature of the eluent allows the combination of these packing materials and the use of column switching systems.
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Takashi SHIMOKOBE, Toshinori WATANABE, Tadayasu TOGAWA, Toshio IMANARI
1988 Volume 4 Issue 1 Pages
97-100
Published: February 10, 1988
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A simple and selective method for the determination of thiocyano group was established. The principle of this method is as follows: Thiocyano group is reduced by dithiothreitol to thiol and cyanide; the latter is converted to hydrogen cyanide by acidification, and then it is absorbed to alkali solution by microdiffusion method. Then cyanide is determined according to our HPLC method with fluorometric detection based on König reaction. The calibration curve for the thiocyano group was linear over the range of 0.05 to 50μM. The present method permitted the determination of thiocyano group in bovine serum albumin and rabbit plasma treated with cyanide.
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Tadayasu TOGAWA, Masahiro KATO, Noriko NACAI, Toshio IMANARI
1988 Volume 4 Issue 1 Pages
101-104
Published: February 10, 1988
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A simultaneous fluorometric determination method of
S-sulfocysteine and
S-sulfoglutathione was established by HPLC using 7-fluoro-4-nitrobenzo-2-oxa-1, 3-diazole (NBD-F) as a prelabeling reagent. Chromatographic conditions were as follows: Column, TSK gel NH
2-60 (150mm×4 mm i.d.); eluent, 0.1M citrate buffer (pH 3.0) containing 10% methanol; flow rate, 1.0ml/min; sample size, 100μl; detection, Ex 475, Em 545nm. Calibration curves for
S-sulfocysteine and
S-sulfoglutathione were linear over the range of 0.1 to 10nmol.
S-Sulfoglutathione was identified as an endogenous compound in rabbit red blood cells by the use of the present method. This method was also applied to the determination of
S-sulfocysteine and
S-sulfoglutathione in rabbit plasma and red blood cells after injection of sodium bisulfite.
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Kunishige NAITO, Shizuo WADA, Shinsuke TAKEI
1988 Volume 4 Issue 1 Pages
105-109
Published: February 10, 1988
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A mechanism of the solute retention in gas-liquid chromatography has been studied in the nonpolar hydrocarbon solute-polar stationary liquid phase system.
N,
N,
N′,
N′-tetrakis(2-hydroxyethyl)ethylene diamine (THEED) was used as a polar stationary liquid phase. A dependence of the retention volume of the solutes and of the specific surface area of the liquid-coated, modified alumina upon the liquid loading was successfully interpreted on the basis of a previous model for distribution of the liquid phase on the modified alumina. The appearance of a maximum on the retention volume vs. liquid loading curve for the saturated hydrocarbon can be understood as a formation of the 1:1 solute-THEED adduct through the lateral interaction between the two molecules adsorbed on the modified alumina.
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Shinobu KUDOH, Hiroshi NAKAMURA
1988 Volume 4 Issue 1 Pages
111-113
Published: 1988
Released on J-STAGE: July 27, 2007
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Shin TSUGE, Kazuhiko NISHIMURA, Makoto SUZUKI, Hisao HAYASHI
1988 Volume 4 Issue 1 Pages
115-116
Published: 1988
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Jun-ichi ITOH, Masashi KOMATA
1988 Volume 4 Issue 1 Pages
117-118
Published: 1988
Released on J-STAGE: July 27, 2007
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