Vol. 4 8, No. 7
July, 1999
Fumio Nakadai, Keigo Ootagaki, Masayuki Itagaki and Kunihiro Watanabe*
*Department of Industrial Chemistry, Faculty of Science and Technology, Science University of Tokyo, 2641, Yamazaki, Noda-shi, Chiba 278-8510
(Received 10 December 1998, Accepted 10 March 1999)The catalytic kinetic determination of cobalt(II) with Eriochrome Black T (EBT) in the presence of hydrogen peroxide was investigated. Co(II) was determined by the reaction rate constant obtained from the decomposition of EBT with the hydroxyl radical due to the catalytic reaction of Co (II) in the presence of hydorogen peroxide. The change in the concentration of EBT was measured by a spectrophotometer. The effect of the concentration of EBT as an indicator reagent was greater than that estimated on the basis of the decomposition reaction with respect to the reaction rate constant. The cause of this phenomenon was the formation of an inert complex {Co(II):EBT=1:2}, which suppressed the formation of the hydroxyl radical produced in the presence of hydrogen peroxide and Co(II). A high sensitivity on the determination of Co(II) was obtained owing to the low concentration of EBT, because of the suppression of the inert complex formation. Therefore, indicator concentration used for the determination of Co(II) was decreased to be as low as possible by using a 5 cm cell. Farthermore, the effect of the addition of calcium(II) was examined in order to decrease the effective concentration of EBT. As a result, the addition of calcium ion increased the sensitivity of Co(II) determination as a ligand buffer reagent.
Keywords : catalytic kinetic analysis; determination of cobalt(II); Eriochrome Black T; effect of reagent concentration; ligand buffer reagent.
Kazuki Nanameki, Hideki Ushijima, Shinichiro Akase, Takehiro Matsumoto* and Satsuo Kamata**
*Scientific Investigation Research Laboratory, Kagoshima Prefecture Police HQ, 10-1, Kamoike-Shinmachi, Kagoshima 890-8566
**Department of Applied Chemistry and Chemical Engneering, Faculty of Engineering, Kagoshima University, 1-21-40, Korimoto, Kagoshima 890-0065
A surface plasmon resonance(SPR) sensor is an instrument that can respond to an immunoreaction. The sensor chip of SPR was prepared by immobilizing a monoclonal antibody (anti-A or B) on a gold thin layer for inspection of the ABO blood type. When a phosphate-buffered saline solution (pH 7.2) containing saliva or bloodstain was flowed into the cell, the following reactions were observed for each sample: 1) The A-type sample responded to the sensor-chip immobilizing anti-A monoclonal antibody (anti-A chip), but did not respond to the anti-B chip. On the other hand, 2) the B-type responded to the anti-B chip, but did not respond to the anti-A chip. 3) The O-type sample did not respond to either the anti-A chip or anti-B chip. 4) The AB-type sample responded to both the anti-A and anti-B chips. Thus, this method was rapid, sensitive and simple for inspecting the ABO blood type for saliva and blood samples.
Keywords : surface-plasmon resonance sensor; ABO blood type; monoclonal antibody; saliva; bloodstain.
Osamu Kiguchi*, Yuji Suzuki** and Katsumi Saitoh*
*Akita Prefectural Institute of Environmental Science, 191-18, Shimo-yabase, Yabase, Akita 010-0975
**Akita Prefectural Odate Health Office, 2-1-60, Nakamichi, Odate-shi, Akita 017-0878
We have developed a method for the simultaneous determination of 16 kinds of pesticides, including triclopyr and triclopyr butoxyethyl, in drain-water samples from golf courses by solid-phase extraction/HPLC. Using a polymethacrylate column (Golf-Pak HR 150×46 mm i.d.), 16 kinds of pesticides could be separated by changing from 50 mM phosphate buffer (pH 3.3)/acetonitrile=70/30→50/50 (0→8 min)-42/58 (8→15 min)-42/58→30/70 (15→25 min) as the mobile phase by a gradient program. The time required for the analysis was about 30 minutes, including the time for initializing. The linearities of the responses (peak area) versus the concentration of 16 kinds of pesticides were examined over the range from 0.06~0.4 mg/l to 10 mg/l. The mean recovery of 16 kinds of pesticides from pure water at a concentration of 0.008 mg/l was 75~107%, and the mean relative standard deviation was 1.6~5.7%. Using two solid-phase extraction cartridges connected in series, the mean recovery for 16 kinds of pesticides from river-water samples at a concentration of 0.008 mg/l was 73~119%, and the mean relative standard deviation was 0.2~8.4%. This analytical method could be successfully applied to the determination of 16 kinds of pesticides in drain-water samples from a golf course.
Keywords : simultaneous determination; HPLC; pesticide; solid-phase extraction; drain-water.
Kenji Fujiwara, Yoko Toumori, Hiroshi Mitsumata, Masanori Inada* and Taketoshi Nakahara**
*Electronics Research Laboratory, Corporate Technology Center, Matsushita Electronics Corporation, 1-1, Saiwai-cho, Takatsuki-shi, Osaka 569-1193
**Department of Applied Chemistry, Osaka Prefecture University, 1-1, Gakuen-cho, Sakai-shi, Osaka 599-8531
Silicon/germanium (SiGe) compound semiconductor devices have attracted much attention as high-frequency devices. However, there is some possibility that germanium (Ge) contaminates silicon (Si) devices, because both SiGe and Si devices can be made on the same Si wafer, using the same process. We therefore need a technique to determine an ultra-trace amount of Ge on a Si wafer. We have adopted a conventional hydrofluoric acid (HF) vapor-decomposition method as a pretreatment technique. The recovery was more than 95% when using oxidizer, such as a nitric acid, as a recovery solution. On the other hand, we used a microconcentric nebulizer (MCN)-ICP-MS as a measurement technique to enhance the analytical sensitivity and precision, because the sample volume required for the analysis should be minimized to determine trace elements on a Si wafer. The detection limit (3σ) was 13 pg ml-1 for a 0.5 ml recovery solution and 3×108 atoms cm-2 for a 6-inch wafer, RSD(%) was less than 3% for a 5 ng ml-1 Ge standard solution. We confirmed that this technique made it possible to determine ultra-trace Ge with high sensitivity and precision.
Keywords : silicon/germanium compound semiconductor; hydrofluoric acid vapor decomposition; microconcentric nebulizer-ICP-MS.
Mamoru Hamura and Teruo Tanabe*
*Department of Materials Science and Engineering, Kyoto University, Honmachi, Yoshida, Sakyou-ku, Kyoto 606-8501
(Received 13 July 1998, Accepted 29 March 1999)We tried to establish a new method involving the simultaneous analysis of Sb, Bi and As in copper concentrates by an atomic absorption method. To examine the effect of coexistent elements on the analysis, the main elements of Cu, Fe and/or S in the concentrates were added in the standard solutions. Sample pretreatment was very simple: the concentrate samples were heated mildly with HNO3, HCl and HBr to decompose, and the analysis was carried out for the obtained aqueous solutions after a filtration and cleaning process. Although the effect of coexistent elements of Cu, Fe and/or S was very large, their variations were minimized by adding LaCl3 to the sample solutions. The results obtained by the new method were in a fairly good agreement with those obtained by the traditional JIS atomic absorption and ICP methods.
Keywords : antimony; bismuth; arsenic; atomic absorption method; inductively coupled plasma method.
Yoshikatsu Takazawa, Hideyuki Itabashi and Hiroshi Kawamoto*
*Department of Applied Chemistry, Faculty of Engineering, Gunma University, Kiryu-shi, Gunma 376-8515
(Received 17 February 1999, Accepted 6 April 1999)The chelate extraction constants for the extraction of copper(II), zinc(II) and cadmium(II) with diphenylthiocarbazone (dithizone) and monothiothenoyltrifluoroacetone (STTA) were measured at various temperatures, and the thermodynamic quantities {enthalpy change (ΔH) and entropy change (ΔS)} were estimated by van't Hoff plot. In the case of dithizone extraction, ΔH for zinc(II) was positive, whereas that for cadmium(II) was negative, and ΔS for zinc(II) was much larger than that for cadmium(II). The extraction for copper(II) gave a negative ΔH and a large positive ΔS. From a comparison of these values, it was indicated that the larger extraction constant for copper(II) than that for zinc(II) can be attributable to a difference in ΔH, and than that for cadmium(II) is due to a difference in ΔS. On the other hand, STTA extractions for zinc(II) and cadmium(II) gave large positive ΔH and small positive ΔS, whereas that for copper(II) gave large negative ΔH and positive ΔS. For this reason, the extraction constant for copper(II) became much larger than that for zinc(II) and cadmium(II).
Keywords : chelate extraction; diphenylthiocarbazone; monothiothenoyltrifluoroacetone; enthalpy change; entropy change.
Susumu Muguruma*, Naoki Oguri, Naoto Harashima, Shigeki Uchino** and Jitsuo Kiji***
*Osaka Laboratory, Japan Analytical Industry Co., Ltd., Unilife 303, 5-13-8, Higashimikuni, Yodogawa-ku, Osaka 532-0002
**Laboratory, Japan Analytical Industry Co., Ltd., 208 Musashi, Mizuho, Nishitama, Tokyo 190-1213
***Department of Materials Science, Tottori University, 4-101, Koyama-minami, Tottori 680-0945
A polymer sample was cryogenically crushed in a sample vessel by a ball located in the vessel through repeated vertical movements of the vessel in liquid nitrogen. The composition of the ball, pre-cooling period before crushing and the crushing period were investigated in relation to the optimum condition for polymer crushing. As a result, the best method found is to use a tungsten carbide ball, 10 min of pre-cooling and 10 min of crushing. Under these conditions, each 3 g polymer sample was crushed into particles with an average size of 100~150 µm. Cryogenical crushing increased the efficiency of solvent extraction for the additives from the polymer (HDPE) by 3.5 times compared to the case of extraction from an HDPE pellet. Also, the amount of the volatile organic compounds from the crushed HDPE increased by 2.6 times compared to that from an HDPE pellet. We clarified that the IR transmission spectrum of vulcanized NR-SBR can be measured after cryogenic crushing of the rubber together with KBr.
Keywords : cryogenic sample crusher for polymer; polymer additive; IR transmission spectrum of vulcanized NR-SBR.
Kunihiro Watanabe, Hideki Miyamoto and Masayuki Itagaki*
*Department of Industrial Chemistry, Faculty of Science and Technology, Science University of Tokyo, 2641, Yamazaki, Noda-shi, Chiba 278-8510
(Received 18 February 1999, Accepted 30 March 1999)A flow-injection analysis technique along with chemiluminescence detection was investigated to determine small amounts of zinc ions by means of the 1,10-phenanthroline-hydrogen peroxide-sodium hydroxide system containing trimethylstearylammonium chloride (TSAC). This chemiluminescence method was based on the following chemical reaction: the superoxide ion (anion radical) reacts with 1,10-phenanthroline to form a 1,2-dioxetane derivative intermediate, which emits chemiluminescence by way of a excited 3,3'-diformyl-2,2'-dipyridyl. Among the examined cationic surfactants, TSAC provided the highest enhancement of the CL intensity, approximately 90- times higher than that in the absence of surfactants. The limit of the determination for Zn(II) was 2.3×10-8 mol/l (200×10-6 l sample injection) under the optimum conditions. Furthermore, in the presence of 2,2'-bipyridine, the CL intensity was enhanced nearly 5- times higher than that under the conditions without 2,2-bipyridine. The authors investigated the mechanism of CL enhancement by spectro-photometry. The role of 2,2'-bipyridine was revealed through the 3-dimensional spectra of Zn(II)-1,10-phenthroline complex formation; that is, 2,2'-bipyridine enhanced the rate of chelate formation on the Zn(II)-1,10-phenanthroline complex , which was needed to produce the super oxide ion (anion radical). As a result, 2,2'-bipyridine increased the amount of super oxide ion (anion radical) and the chemiluminesence was enhanced.
Keywords : chemiluminescence; 1,10-phenanthroline; zinc(II); surfactant; 2,2'-bipyridine.
Hiromasa Katoh, Naoko Katayama and Toshio Kaneko*
*Mitsubishi Chemical Corporation, Yokohama Research Center, Analytical Sciences Laboratory, 1000, Kamoshida-cho, Aoba-ku, Yokohama 227-8502
(Received 27 January 1999, Accepted 7 April 1999)The authors investigated Karl Fischer coulometric titration using a diaphragmless cell. Many samples, such as hydrocarbons, alcohols and polymers, were analyzed by the present method and the conventional method using a cell with a diaphragm. The relationship between both methods showed good agreement (relation coefficient, r=0.99996). Compounds containing a nitro group showed higher analytical values, because the products electrolyzed at the cathode reacted with the iodine produced at the anode. Present method is suitable for the coulometric titration/the moisture vaporization method in which the moisture in samples is introduced into the electrolyzing cell by heating and purging.
Keywords : Karl Fischer titration; moisture; coulometric titration; diaphragmless cell.
K. Imamura, M. Eguchi, S. Ohira, T. Tashiro, S. Tachibana, M. Tanaka, K. Hirai, Y. Fujikata, G. Fujise, Y. Maeda, Y. Yasaka and M. Warashina**
**Section of the 23rd Cooperative Test, Association for Environmental Analysis in Osaka, 1-8-4, Utsubohonmachi, Nishi-ku, Osaka 550-0004
(Received 3 February 1999, Accepted 16 March 1999)Round-robin tests were conducted in order to investigate a canister method for determining standard gas mixtures of volatile organic hazardous air pollutants by 14 members of the Association for Environmental Analysis in Osaka. A first standard gas containing seven analytes (acrylonitrile, dichloromethane, chloroform, 1,2-dichloroethane, benzene, trichloroethylene, and tetrachloroethylene at ca. 300 ppm each) was prepared in a glass vessel from their mixed solution according to our previous paper. An aliquot of this gas was transferred into a canister (61) using a syringe, and diluted (ca. 10 ppb each). The resulting standard gas mixture was evaluated by GC/MS after concentration. The obtained results prove this method to be both accurate and precise for the preparation of a standard gas mixture at low ppb levels. Another gas mixture containing nine analytes (vinyl chloride and 1,3-butadiene in addition to the above-mentioned seven compounds at 3 ppb each) was also prepared in a canister, and similarly treated by GC/MS. It was found that the canister method is remarkably accurate and precise. However, the acrylonitrile values had in large standard deviations.
Keywords : round-robin test; canister method; volatile organic hazardous air pollutants; gas chromatography/mass spectrometry.
Makoto Torigai, Satoshi Okita, Sun-Ja Yun, Tsuneo Hashiba and Kiyoshi Iwashima*
*The Institute of Basic Environmental Research, Environmental Control Center Co., Ltd. 323-1, Shimoongata-machi, Hachioji-shi, Tokyo 192-0154
(Received 6 May 1999, Accepted 4 June 1999)Three deuterated beta-estradiol compounds (2,4-d2, 16,16,17-d3, 2,4,16,16-d4) were investigated for use as internal standard substances in the determination of beta-estradiol. The mass spectrum of two of the deuterated compounds (2,4-d2, 2,4,16,16-d4) showed structural changes due to hydrolysis (1 M-HCl/methanol, 80°C, 20 min), which was required for the decomposition of conjugates in the sample pretreatment. On the other hand, the mass spectrum of the 16,16,17-deuterated compound was not changed. Therefore, we advise that beta-estradiol-16,16,17-d3 should be used as the internal standard. In case where beta-estradiol-2,4,16,16-d4 must be used, it should be spiked after hydrolysis.
Keywords : beta-estradiol; deuterated compound; internal standard substance; GC/MS; river water.
Tsuyoshi Murahashi
Division of Pharmaceutical Sciences, Graduate School, Kyushu University 3-1-1, Maidashi, Higashi-ku, Fukuoka 812-8582
(Awarded by Kanazawa University dated March 25, 1998)Two HPLC methods for the determination of nitroarenes were developed. One allows the simultaneous determinations of four nitroarenes (1,3-, 1,6- and 1,8-dinitropyrenes and 1-nitropyrene) and ten polycyclic aromatic hydrocarbons (PAHs; fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a,h]anthracene, benzo[ghi]perylene and indeno[1,2,3-cd]pyrene). The other can handle small amounts of nitroarenes, such as 2-nitrofluoranthene, 2- and 4-nitropyrenes and 6-nitrochrysene. The Atmospheric behaviors of nitroarenes were analyzed by these analytical methods. The atmospheric concentrations of 1,3-, 1,6- and 1,8-dinitropyrenes and 1-nitropyrene in the downtown area of Kanazawa were higher between 6:00 and 20:00 and lower between 0:00 and 6:00. Large correlation coefficients (>0.8) between the nitroarene concentrations and traffic volume suggest that the main source of nitroarenes was vehicles. 4-Nitropyrene and 6-nitrochrysene were detected in diesel exhaust particulates, and their concentrations were higher from 10:00 to 18:00 and lower from 0:00 to 6:00. On the other hand, the concentrations of 2-nitrofluoranthene and 2-nitropyrene were highest from 16:00 to 18:00, suggesting that the two nitroarenes were formed in the atmosphere. Most of each nitroarene (>67%) existed as fine particulates (diameters<1.1 µm) which could reach pulmonary alveoli more easily. The sum of the mutagenic contributions of the above eight nitroarenes was estimated to be 6.0%.
(Received February 26, 1999)Keywords : nitroarene; airborne particulate; HPLC; polycyclic aromatic hydrocarbon; diesel exhaust particulate; mutagenicity.
Nariaki Takayama
Forensic Science Laboratory, Ishikawa Prefectural Police Headquarters: 2-1-1 Hirosaka, Kanazawa 920-8553
(Awarded by Kanazawa University dated September 30, 1998)An HPLC/chemiluminescence detection method of analyzing methamphetamine (MA), which is the most frequently abused illegal drug, and its metabolites, was developed. Analyses were performed using urine and hair samples from MA addicts. The following results were obtained. First, MA and its metabolites, including glucuronide conjugates, were detected in 2 ml of urine; also, this method could reveal the present ratio of MA and its metabolites in the urine of MA addicts. Second, this method allowed the detection of MA and its major metabolite, amphetamine (AP), using only a single hair, and was shown to be an excellent analytical method when the collection of a large quantity of hair is difficult. Third, hair was shown to be an excellent sample for proving drug use based on considerations of the results of the analysis of hair and urine samples together with the situation of MA use. Fourth, since this analysis can be performed using only a single hair, the black hair and white hair of addicts could be separately analyzed; it was found that the MA and AP contents of white hair are lower than that of black hair, suggesting the affinity of these compounds with melanin. Fifth, it was demonstrated that the contents of MA and AP decrease after permanent wave, dye and decolorant treatments of natural black hair of addicts containing these compounds.
(Received March 3, 1999)Keywords : HPLC/chemiluminescence detection method; dansyl chloride; naphthalene-2,3-dicarboxaldehyde; methamphetamine; metabolites; urine; hair.
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