Analytical Sciences
Online ISSN : 1348-2246
Print ISSN : 0910-6340
ISSN-L : 0910-6340
Volume 20 , Issue 4
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  • Subbiah THANGADURAI
    2004 Volume 20 Issue 4 Pages 595-601
    Published: 2004
    Released: October 08, 2004
    JOURNALS FREE ACCESS
    The Human Genome Project (HGP) is the most ambitious and important effort in the history of biology. It has provided a complete genetic blueprint for human life, and will provide important insights into human health and development. HGP involves a huge amount of data that is stored on computers all over the world. More than just vast amounts of DNA sequences, the project is about developing sets of integrated maps that involve genetic, physical, and sequence data. The data can be sorted, annotated and organized in many different ways using different types of database software, different analysis algorithms and different forms of interfaces. The genomic sequences of the human and the substantial portions of the mouse genome are expected to be finished by 2005. Analytical chemists took the opportunity, addressing the problem of achieving a high throughput with good sensitivity. This paper discusses how analytical chemists saved the Human Genome Project or at least gave it a helping hand.
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  • Wenjun ZHANG, Genxi LI
    2004 Volume 20 Issue 4 Pages 603-609
    Published: 2004
    Released: October 08, 2004
    JOURNALS FREE ACCESS
    Recent progress in third-generation electrochemical biosensors based on the direct electron transfer of proteins is reviewed. The development of three generations of electrochemical biosensors is also simply addressed. Special attention is paid to protein-film voltammetry, which is a powerful way to obtain the direct electron transfer of proteins. Research activities on various kinds of biosensors are discussed according to the proteins (enzymes) used in the specific work.
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The Best Paper in Bunseki Kagaku, 2002
  • Kazunobu ASANO, Atsushi ONO, Setsuko HASHIMOTO, Tohru INOUE, Jun KANNO
    2004 Volume 20 Issue 4 Pages 611-616
    Published: 2004
    Released: October 08, 2004
    JOURNALS FREE ACCESS
    Because concern over endocrine disrupting reactions caused by chemicals to humans and animals is growing, a rapid and reliable screening assay for endocrine disrupting chemicals is required. We have developed an in vitro screening assay based on a hormone receptor mechanism using a surface plasmon resonance (SPR) sensor. The interaction between an estrogen receptor α(ER) and an estrogen response element (ERE) is monitored in real time, when ER is injected over the SPR sensor chip on which a DNA fragment containing ERE is immobilized. In the presence of a chemical with estrogenic activity, the ER-ERE interaction is enhanced and the kinetic parameters are altered. We have validated the assay in terms of its specificity, dose dependency, optimal reaction conditions and reproducibility. It has been shown that the assay is very reliable as a rapid and quantitative screening method to judge the estrogenic activities of chemicals.
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Original Papers
  • Takeshi OHNO, Atsuko SHINOHARA, Ichitaro KOHGE, Momoko CHIBA, Takafumi ...
    2004 Volume 20 Issue 4 Pages 617-621
    Published: 2004
    Released: October 08, 2004
    JOURNALS FREE ACCESS
    Precise 56Fe/54Fe and 57Fe/54Fe isotopic ratios on human red blood cell (RBC) samples have been measured using multiple collector-ICP-mass spectrometry (MC-ICPMS). The mass spectrometric interferences on Fe isotopes (e.g., 56ArO+ and 57ArOH+) were successfully minimized by a dry plasma condition achieved by a desolvating nebulizer sample-introduction technique. In order to eliminate possible variations in the measured isotopic ratios due to non-mass spectrometric interferences, Fe was separated from remaining organic compounds and major co-existing elements using an ion chromatographic technique. The resulting precisions of the 56Fe/54Fe and 57Fe/54Fe ratio measurements were 0.12‰ and 0.20‰, respectively, which were high enough to detect the isotopic variation of Fe in nature. For an interlaboratory comparison, all of the Fe isotopic ratio data were normalized by the ratios for the IRMM-014 international isotopic standard. A series of 12 RBC samples were collected from one person through monthly-based sampling over a period of one year. These were analyzed to test possible seasonal changes in the 56Fe/54Fe and 57Fe/54Fe ratios. Moreover, in order to test possible variations in the 56Fe/54Fe and 57Fe/54Fe ratios among different people, RBC samples were collected from five volunteers (four males and one female). The 56Fe/54Fe and 57Fe/54Fe ratios for a series of 12 RBC samples collected over a one-year period show 3.06‰ and 4.51‰ lower than the values of IRMM-014, and no significant seasonal change could be found in the ratios. The lack in seasonal changes in the Fe isotopic ratios could be explained by a small contribution of the daily net-intake of Fe (1 - 2 mg/day) onto the total amount of Fe in the human body (2 - 4 g). The 56Fe/54Fe and 57Fe/54Fe ratios for RBC samples collected from four male samples did not vary measurably, whereas the Fe isotopic ratios for a female RBC were 0.3‰/amu heavier than the mean value of four male samples. This difference in Fe isotopes among the individuals can be the result of a difference in uptake efficiency of the Fe through a dietary process from the digestive tract. The data obtained here demonstrate that the isotopic ratios of trace metals can provide new information about metabolic efficiencies of the metallic elements.
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  • Lu TIAN, Wan-zhi WEI, You-an MAO
    2004 Volume 20 Issue 4 Pages 623-627
    Published: 2004
    Released: October 08, 2004
    JOURNALS FREE ACCESS
    The adsorption of human serum albumin onto hydroxyapatite-modified silver electrodes has been in situ investigated by utilizing the piezoelectric quartz crystal impedance technique. The changes of equivalent circuit parameters were used to interpret the adsorption process. A kinetic model of two consecutive steps was derived to describe the process and compared with a first-order kinetic model by using residual analysis. The experimental data of frequency shift fitted to the model and kinetics parameters, k1, k2, ψ1, ψ2 and qr, were obtained. All fitted results were in reasonable agreement with the corresponding experimental results. Two adsorption constants (7.19 kJ mol-1 and 22.89 kJ mol-1) were calculated according to the Arrhenius formula.
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  • Junwei DI, Shuping BI
    2004 Volume 20 Issue 4 Pages 629-634
    Published: 2004
    Released: October 08, 2004
    JOURNALS FREE ACCESS
    Aluminum, a trivalent cation unable to undergo redox reactions, is shown to faciliate iron-initiated DOPA oxidation in the melanin pathway under acidic condition of pH 5.5, which is a favored medium for aluminum facilitation of iron-induced lipid peroxidation. In the process of oxidation of DOPA to melanin in the presence of the metal ions, Fe3+ and H2O2 oxidize DOPA to dopachrome (DC), then Al3+ catalyzes the conversion of DC to 5,6-dihydroxyindole (DHI) and finally Fe3+ oxidizes DHI to indole-5,6-quinone (IQ), which polymerizes immediately to melanochrome and melanin. The reactions involve the intermediate complexes of metal ions and DOPA or its derivative. The present results indicate that aluminum can enhance the oxidative stress on iron-mediated DOPA oxidation in melanin pathway under acidic condition through the cooperation of iron and aluminum ions.
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  • Liang WANG, Zhuobin YUAN
    2004 Volume 20 Issue 4 Pages 635-638
    Published: 2004
    Released: October 08, 2004
    JOURNALS FREE ACCESS
    The direct electrochemistry of xanthine oxidase (XOD) was accomplished at a gold electrode modified with single-wall carbon nanotubes (SWNTs). A pair of well-defined redox peaks was obtained for XOD with the reduction peak potential at -0.478 V and a peak potential separation of 28 mV at pH 7.0. Both FT-IR spectra and the dependence of the reduction peak current on the scan rate revealed that XOD adsorbed onto the SWNT surfaces. The redox wave corresponds to the redox center of the flavin adenine dinucleotide (FAD) of the XOD adsorbate. Compared to other types of carbonaceous electrode materials, the electron transfer rate of XOD redox reaction was greatly enhanced at the SWNT-modified electrode. The peak potential was shown to be pH dependent. Spectral methods verified that the attachment of XOD onto SWNTs does not perturb the XOD conformations drastically.
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  • Biljana NIGOVIC
    2004 Volume 20 Issue 4 Pages 639-643
    Published: 2004
    Released: October 08, 2004
    JOURNALS FREE ACCESS
    The adsorptive and electrochemical behaviors of azithromycin were investigated on a glassy carbon electrode that was electrochemically treated by anodic oxidation at +1.8 V, following potential cycling in the potential range from -0.8 to +1.0 V. The resulting electrode showed good activity to improve the electrochemical response of the drug. An adsorptive stripping voltammetric method for the determination of azithromycin at an electrochemically activated glassy carbon electrode has been developed. Azithromycin was accumulated in phosphate buffer, pH 6, at a potential of +0.3 V (vs. Ag/AgCl electrode) for a certain time, and then determined by differential pulse voltammetry. The oxidative peak current at +0.82 V, at a scan rate of 20 mV s-1, was a linear function of the concentration in the ranges of 0.25 - 2 µg mL-1 and 1 - 10 µg mL-1 using a 240 or 60 s preconcentration time, respectively. Application of the method to the determination of azithromycin in pharmaceuticals resulted in an acceptable deviation from the stated concentration. The preconcentration medium-exchange approach was utilized for the selective determination of the drug in spiked urine samples with satisfactory results. The peak current was linear with the drug concentration in the range of 0.5 - 3.5 µg per mL urine. The detection limit was 0.2 µg mL-1 urine. The recovery levels of the method reached 96.3%.
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  • Ali A. ENSAFI, Mansour ARAB CHAMJANGALI, Hassan RAHIMI MANSOUR
    2004 Volume 20 Issue 4 Pages 645-650
    Published: 2004
    Released: October 08, 2004
    JOURNALS FREE ACCESS
    A flow injection procedure for the sequential spectrophotometric determination of iron(II) and iron(III) in pharmaceutical products is described. The method is based on the catalytic effect of iron(II) on the oxidation of iodide by bromate at pH = 4.0. The reaction was monitored spectrophotometrically by measuring the absorbance of produced triiodide ion at 352 nm. The activating effect for the catalysis of iron(II) was extremely exhibited in the presence of oxalate ions, while oxalate acted as a masking agent for iron(III). The iron(III) in a sample solution could be determined by passing through a Cd-Hg reductor column introduced in the FIA system to reduce iron(III) to iron(II), which allows total iron determination. Under the optimum conditions, iron(II) and iron(III) could be determined over the range of 0.05 - 5.0 and 0.10 - 5.0 µg ml-1, respectively with a sampling rate of 17 ± 5 h-1. The experimental limits of detection were 0.03 and 0.04 µg ml-1 for iron(II) and iron(III), respectively. The proposed method was successfully applied to the speciation of iron in pharmaceutical products.
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  • A. M. OTHMAN, N. M. H. RIZKA, M. S. EL-SHAHAWI
    2004 Volume 20 Issue 4 Pages 651-655
    Published: 2004
    Released: October 08, 2004
    JOURNALS FREE ACCESS
    Two simple, rapid and sensitive sensors for the assay of dopamine hydrochloride have been developed. The methods are based upon the formation of the membrane sensors 12-crown-4-phosphotungestic acid (crown ether-PTA)-dopamine and 12-crown-4-tetraphenylborate (crown ether-TPB)-dopamine as neutral carriers. The sensors were stable and showed fast potential responses of 10 s, and near-Nernstian cationic slopes of 53.3 - 56.2 mV/decade of activity between pH 2.2 - 6 for the monovalent dopamine cation over a wide range concentrations 1 × 10-5 - 1 × 10-1 M. The selectivity coefficients of the developed sensors indicated excellent selectivity for dopamine over a large number of organic and inorganic species and pharmaceutical excipients. The mediator o-nitrophenyloctyl ether significantly affected the lifetime of the fabricated sensors of dopamine. Satisfactory results were obtained for the determination of dopamine in dosage form by the proposed sensors with an average recovery of 99.85% for the nominal concentration.
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  • Takashi YOKOYAMA, Hirokazu TSUJI, Takaomi AKAMATSU, Michio ZENKI
    2004 Volume 20 Issue 4 Pages 657-662
    Published: 2004
    Released: October 08, 2004
    JOURNALS FREE ACCESS
    The capillary electrophoretic behavior of 44 aromatic organic ions was investigated. The observed ionic radii (robs0) for the aromatic organic ions were obtained from the electrophoretic mobilities of sodium tetraborate (pH 9.2), potassium tetraborate (pH 9.2), ammonium borate (pH 9.2), and trisodium phosphate (pH 11.7) buffers with zero ionic strength. The linear relationships between the robs0 values and the ionic radii (rcalc), calculated by either the AM1 or PM3 method, were determined for benzyltrialkylammonium and aromatic sulfonate ions. However, the robs0 values were constant for the aromatic carboxylate ions in buffers, in spite of the different rcalc values. This indicates that aromatic carboxylate ions, such as benzenecarboxylate, pyridinecarboxylate, naphthalenecarboxylate, and anthracenecarboxylate ions, migrate as planar ions in buffers, whereas aromatic sulfonate ions could migrate as approximately spherical ions.
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  • Rusong ZHAO, Shaogang CHU, Xiaobai XU
    2004 Volume 20 Issue 4 Pages 663-666
    Published: 2004
    Released: October 08, 2004
    JOURNALS FREE ACCESS
    In the present work, a novel method for the determination of nitrobenzenes in water has been described. It is based on nonequilibrium liquid-phase microextraction and gas chromatography-electron capture detection (GC-ECD). Extraction conditions such as solvent selection, organic solvent dropsize, stirring rate, content of NaCl and extraction time were found to have significant influence on extraction efficiency. The optimized conditions were 1.5 µl toluene and 20 min extraction time at 400 rpm stirring rate without NaCl addition. The linear range was 0.1 - 50 µg l-1 for most nitrobenzenes. The limits of detection (LODs) ranged from 0.02 µg l-1 (for 2.6-DNT) to 0.4 µg l-1 (for NB); and relative standard deviations (RSD) for most of the nitrobenzenes at the 10 µg l-1 level, except for 2,6-DNT in 3 µg l-1, were below 10%. Natural samples collected from Miyun Reservoir and tap water samples from a laboratory were successfully analyzed using the proposed method, but none of the analytes were detected. The relative recoveries of spiked water samples (at the 10 µg l-1 level except for 2,6-DNT in 3 µg l-1) were from 82.6 to 118.7%.
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  • Yuling HU, Yuexing ZHENG, Gongke LI
    2004 Volume 20 Issue 4 Pages 667-671
    Published: 2004
    Released: October 08, 2004
    JOURNALS FREE ACCESS
    A novel solid-phase microextraction (SPME) fiber was prepared by coating an HPLC β-cyclodextrin bonded silica stationary phase (CDS) on the surface of a fused-silica fiber. The fiber was evaluated for the determination of five phenol compounds (phenol, 2,4-dimethylphenol, 4-nitrophenol, 3-chlorophenol, 4-methylphenol). Compared with commercially available polymer coatings, the CDS coating showed high sensitivity and fast velocity of mass transfer for phenol compounds because of its porous structure and a unique molecular structure of β-cyclodextrin. In addition, the CDS coating was proved to be very stable at a relatively high temperature (up to 300°C). The method was suitable for the determination of phenol compounds in aqueous samples. The determination of 4-nitrophenol in soil by microwave-assisted extraction (MAE) coupled to solid-phase microextraction was also investigated.
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  • Zhao-Sheng LIU, Yan-Li XU, Hefang WANG, Chao YAN, Ru-Yu GAO
    2004 Volume 20 Issue 4 Pages 673-678
    Published: 2004
    Released: October 08, 2004
    JOURNALS FREE ACCESS
    A novel enantioseparational monolithic stationary phase for binaphthol based on a molecular imprinting method was introduced and evaluated in capillary electrochromatography (CEC). The monolithic stationary was prepared by the in situ copolymerization of methacrylic acid and ethylene glycol dimethacrylate in a porogenic solvent (toluene or toluene-isooctane) in the presence of an imprinting molecule, (R)-1,1′-bi-2,2′-naphthol. Such stationary phases could separate the enantiomers of binaphthol. The influence of several parameters on the column permeability was investigated. These parameters included the polymerization time, the molar ratio of the functional monomer to the imprinting molecule and the content of porogen. The influence of the polymerization condition and the electrochromatographic parameters on the enantiomer separation was also studied. Initial studies showed that a higher molecular ratio of the imprinted molecule to the functional monomer, a higher content of porogen, a higher content of acetonitrile, a higher pH, as well as the addition of Tween 20, gave a higher enantiomer selectivity.
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  • Nestor Zárate ARACAMA, Alberto N. ARAÚJO, Ricardo PEREZ- ...
    2004 Volume 20 Issue 4 Pages 679-682
    Published: 2004
    Released: October 08, 2004
    JOURNALS FREE ACCESS
    The development of a sequential injection analysis manifold for the colorimetric determination of lead in water samples is described. The concentration of lead was assessed from its catalytic effect on the reaction of resazurine reduction caused by sulfide in an alkali medium. To that effect, the reaction zone was stopped at the detector, and the time interval required for the attainment of an absorbance decrease of 0.800 at the wavelength of 610 nm was estimated. Interference of other transition metals of the samples was minimized by adding potassium iodide to the sample and retaining the iodocomplexes formed in an on-line anionic resin (AG1 X8). Elution was made with a 2 mol/L sodium hydroxide solution. The relationship [SIA] µg/L = 0.99 (±0.11) × [ETAAS] µg/L + 0 (±4) was obtained upon comparing the results given by the proposed system and by electrothermal atomization atomic absorption spectrometry (ETAAS) after the analysis of ten water samples.
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  • Hiroaki MINAMISAWA, Shinpei IIZIMA, Mayumi MINAMISAWA, Satoshi TANAKA, ...
    2004 Volume 20 Issue 4 Pages 683-687
    Published: 2004
    Released: October 08, 2004
    JOURNALS FREE ACCESS
    Synthetic zeolites were dissolved in nitric acid, and the resulting solution used as a coprecipitant for the preconcentration of trace amounts of gallium in water samples prior to determination by electrothermal atomic absorption spectrometry (ETAAS). The gallium preconcentration conditions and the ETAAS measurement conditions were optimized. Gallium was quantitatively concentrated with the zeolites coprecipitate from pH 6.0 to 8.0. The coprecipitate was easily dissolved in nitric acid, and an aliquot of the resulting solution was introduced directly into a tungsten metal furnace. The atomic absorbance of gallium in the resulting solution was measured by ETAAS. An ashing temperature of 400°C and an atomizing temperature of 2600°C were selected. The calibration curve was linear up to 3.0 µg of gallium and passed through the origin. The detection limit (S/N ≥ 3) for gallium was 0.08 µg/100 cm3. The relative standard deviation at 1.0 µg/100 cm3 was 3.0% (n = 5). The proposed method has been successfully applied to trace gallium analysis in environmental water samples.
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  • Masaru MITSUSHIO, Morihide HIGO
    2004 Volume 20 Issue 4 Pages 689-694
    Published: 2004
    Released: October 08, 2004
    JOURNALS FREE ACCESS
    The structure of the sensing element of a gold-deposited optical fiber sensor was simplified and quantitative analyses of various alcohols with the sensor showed improvement of the performance. The sensor uses surface plasmon resonance (SPR) at the interface of a sample solution and a thin (10 - 70 nm) gold film deposited on half of the exposed core of the optical fiber. The sensor with a film thickness of 45 nm can detect a small change of 5.6 × 10-5 refractive index (RI) units in the refractivity. The response time is less than 0.5 min and the relative standard deviation for measurements is less than or equal to 1%. A straight line with a correlation coefficient of 0.9995 was obtained below 10%, v/v in the calibration curve for methanol solutions of benzyl alcohol. The minimum of the response curve due to the maximum excitation of SPR in the refractivity range from 1.33 to 1.44 RI units shifts to a lower refractivity as the film becomes thicker. The response curves of the sensors were calculated from SPR theoretical equations while considering of the distribution in the thickness of the deposited gold films. The improvement in the performance of the sensor is discussed.
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  • H. INCE, S. AKMAN
    2004 Volume 20 Issue 4 Pages 695-699
    Published: 2004
    Released: October 08, 2004
    JOURNALS FREE ACCESS
    In this study, the interference effects of Al3+, Mg2+, Cl- and SO42- ions on the determination of manganese by graphite furnace atomic absorption spectrometry (GFAAS) were investigated. At first, the interferences caused by Al2(SO4)3, AlCl3, MgCl2 and MgSO4, which are the most possible major compounds for the combinations of the ions mixed, were individually considered. Then, the effects caused by mixtures containing various amounts of MgSO4 and AlCl3 were studied. If the pyrolysis temperature is below 800°C, AlCl3 changes the vaporization mechanism of manganese. These interferences disappear at higher pyrolysis temperatures. At the same time, aluminum salts may cause the formation of refractory compounds between aluminum and manganese (like spinel MnAl2O4) that shift the absorption signals of manganese to higher temperatures. Magnesium sulfate, by itself, does not cause any depression of manganese signals. In fact, it acts as a modifier, preventing volatilization losses of manganese during the pyrolysis step. A conclusion was reached that detailed investigation of the interferences in a complex media is a very difficult experimental and theoretical task. To solve practical problems, one may better follow the general notions developed in GFAAS toward complex matrices.
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  • Masaki OHATA, Naoki FURUTA
    2004 Volume 20 Issue 4 Pages 701-706
    Published: 2004
    Released: October 08, 2004
    JOURNALS FREE ACCESS
    The ablation interaction between a laser and solid samples, which affects the analytical performance for laser ablation inductively coupled plasma atomic emission spectrometry (LA-ICP-AES), was studied. The emission intensities of elements observed by LA-ICP-AES (LA-ICP-AES element signal intensities) for different solid samples were measured under different laser defocusing conditions with a fixed laser output energy. It was found that the optimum laser defocusing conditions were dependent on the different solid samples with different sample characteristics, and also on the different elements with different elemental characteristics in each solid sample. A low-alloy steel, pellets containing different Fe concentrations (0 - 100% Fe pellet), and a pond sediment pellet were used as different solid samples. The variations of the LA-ICP-AES Fe signal intensities observed under different laser defocus conditions were completely different between the low-alloy steel and the pond sediment pellet. The changes in the LA-ICP-AES Fe signal intensities for 90 and 100% Fe pellets were similar to that of the low-alloy steel. However, pellets with lower Fe concentrations (less than 70%) showed different trends and the defocusing behavior became closer to that of the pond sediment pellet. The LA-ICP-AES signal intensities of other elements were also evaluated, and were compared for different solid samples and different defocusing behavior. It was observed that the changes in the LA-ICP-AES signal intensities of almost all elements in the pond sediment pellet showed a similar trend to those of Fe for different laser defocus positions; that is, the elemental fractionation for these elements in the pond sediment pellet seemed to be relatively small. On the contrary, it was found that the LA-ICP-AES Si, Ti, and Zr signal intensities for low-alloy steel showed different trends compared to those of other elements, including Fe, under different defocusing conditions; that is, the elemental fractionation observed for the low-alloy steel was larger than that of the pond sediment pellet. From these results, different ablation interactions between the laser and the different solid samples were considered, and attributed to the sample characteristics, such as the matrix, hardness, and conductivity. Elemental fractionation was attempted to be explained by using elemental characteristics, such as the melting point and ionization energy of the elements.
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  • Junichi ODO, Kozue MATSUMOTO, Eri SHINMOTO, Yoko HATAE, Atsushi SHIOZA ...
    2004 Volume 20 Issue 4 Pages 707-710
    Published: 2004
    Released: October 08, 2004
    JOURNALS FREE ACCESS
    The peroxidase-like catalytic activity of metal complexes of thiacalix[4]arenetetrasulfonate (TCAS[4]) on a modified anion-exchanger (Men+-TCAS[4]A-500; Men+ = H2, Fe3+, Fe2+, Mn3+, Co3+, Co2+, Cu2+, Zn2+, Ni2+) for the oxidation of p-hydroxyphenyl derivatives to produce fluorescent substances in the presence of hydrogen peroxide has been investigated. Among the Men+-TCAS[4]A-500 tested, Fe3+-TCAS[4]A-500 exhibited the highest level of catalytic activity for the oxidation of p-acetoamidophenol in a carbonate buffer solution of pH 10. The catalytic activity of Fe3+-TCAS[4]A-500 was then used for the spectrofluorometric determination of hydrogen peroxide. The calibration curve for the Fe3+-TCAS[4]A-500 method was linear over a range spanning from 0.1 to 5.0 µg of hydrogen peroxide in a 1.0 ml sample solution.
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  • Naokazu YOSHIKAWA, Jun SAKAMOTO, Takeko MATSUMURA-INOUE, Hiroshi TAKAS ...
    2004 Volume 20 Issue 4 Pages 711-716
    Published: 2004
    Released: October 08, 2004
    JOURNALS FREE ACCESS
    Four useful polypyridine iridium(III) complexes in the form of [IrCl2L2]+ were prepared and their spectroscopic and electrochemical properties as well as X-ray crystallography were investigated. The ligands used were L = 2,2′-bipyridine, 4,4′-dimethyl-2,2′-bipyridine, 4,4′-diphenyl-2,2′-bipyridine, 1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, and 2,2′-biquinoline. Synthetic methods were developed by a sequential ligand-replacement, which occurred in the reaction vessel using a microwave oven. All complexes showed that LUMOs are based on the π-system contribution of the polypyridine ligand for [IrCl2(bpy)2]+, [IrCl2(dmbpy)2]+, [IrCl2(dpbpy)2]+, [IrCl2(phen)2]+, [IrCl2(dpphen)2]+ and [IrCl2(bqn)2]+. The HOMOs are also localized on the polypyridine ligand in the iridium complexes. It was found that [IrCl2L2]+ emits intense phosphorescence at room temperature. In particular, the use of dpbpy as ancillary ligands extends the lifetime (660 ns) of the 3(π-π*) excited states of Ir(III) polypyridine complexes. The complex [IrCl2(bqn)2]+ with electron acceptor substituents shows a large red-shift to 622 nm. It is noticed that iridium polypyridine complexes show intense emissions at various colors, such as yellow for [IrCl2(dmbpy)2]+ and red for [IrCl2(bqn)2]+, which can be applied to photosensitizers. The spectroscopic and electrochemical details are also reported herein.
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  • Taiming ZHANG, Yizeng LIANG, Boyan LI, Hui CUI, Fan GONG
    2004 Volume 20 Issue 4 Pages 717-724
    Published: 2004
    Released: October 08, 2004
    JOURNALS FREE ACCESS
    A method is described for the systemic identification and quantitative analysis of nitrogen-containing compounds and other non-hydrocarbons in crude oils. The pre-fractionation of a crude oil sample into 7 fractions was performed by diadsorption column chromatography using neutral aluminum oxide and silica gel. A subsequent high-resolution separation of individual components was achieved by using capillary column gas chromatography, and compound types were detected by a mass spectrometer. In conjunction with a chemometric method, the compounds in the fractions were further resolved or separated, which made it possible to identify some nitrogen-containing compounds and other non-hydrocarbons in crude oils. To a certain extent, this method could relieve the difficulty of classical analysis in identifying those species with very low contents or incompletely separation, particularly in the cases where authentic standards were not available for addition into the unknown samples in order to reveal what indeed existed in them. The structures and contents of 168 nitrogen-containing compounds in one crude sample and 60 non-nitrogen-containing compounds in one of non-hydrocarbon fractions of this oil sample were determined, and the addition-recovery examination of some standard compounds showed that the analytical veracity was satisfactory.
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  • Mohammad Reza GANJALI, Leila HAJIAGHA BABAEI, Alireza BADIEI, Ghodsi M ...
    2004 Volume 20 Issue 4 Pages 725-729
    Published: 2004
    Released: October 08, 2004
    JOURNALS FREE ACCESS
    A novel method for the rapid extraction and determination of a ppt level of Pb2+ and Cu2+ ions using partial silylated MCM-41 modified by a new salophen and inductively coupled plasma atomic emission spectrometry (ICP-AES) is introduced. The preconcentration factor of the method is 500, and the detection limits of Pb2+and Cu2+ are 335 and 34 ng L-1, respectively. The time and efficiency of extraction, the pH and flow rate, the type and minimum amount of acid for stripping of Pb2+ and Cu2+ from modified MCM-41 and the break-through volume were investigated. The maximum capacity of 4 mg of silylated MCM-41 modified by salophen used was found to be 150 ± 4 and 117 ± 3 µg of Pb2+ and Cu2+, respectively.
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