Vol. 52 No. 3
March, 2003
Takahiro Iijima1,2, Motohiro Mizuno1, Masahiko Suhara1 and Kazunaka Endo1
1 Department of Chemistry, Faculty of Science, Kanazawa University, Kakuma-machi, Kanazawa-shi, Ishikawa 920-1192
2 Present address, Nanomaterials Laboratory, National Institute for Materials Science (NIMS), 3-13, Sakuraˇ¤Tsukuba-shi, Ibaraki 305-0003
(Received 28 August 2002, Accepted 18 December 2002)A method using the 2H-NMR spectra was shown to be useful to study the solid state physics in diamagnetic and paramagnetic compounds and in crystals having a modulated structure. The spectra and T1 of NMR in solids were measured for [M(H2O)6][AB6] crystals to investigate the static and dynamic structure of H2O and [M(H2O)6]2+ as well as the dynamics of the electron spin in the paramagnetic M2+ ion. The physical properties of [M(H2O)6][AB6] were found to be as follows: (1) The spin-lattice relaxations of the electron spin of M2+ in [M(H2O)6][SiF6] (M2+=Fe2+, Co2+, Ni2+) are dominated by the Orbach process, the Orbach process, and the Raman process, respectively. The spin-lattice relaxation of the electron spin of Cu2+ in [Cu(H2O)6][PtCl6] is caused by jumping between the Jahn-Teller configurations. (2) In [Cu(H2O)6][PtCl6], H2O and [Cu(H2O)6]2+ undergo 180° flips and jumping between the different Jahn-Teller configurations, respectively. A weakening of the hydrogen bond O-H…Cl upon deuteration results in a lowering of the transition temperature. (3) In [M(H2O)6][SiF6], H2O and [M(H2O)6]2+ undergo 180° flips and reorientation about the C3 axis, respectively. The order-disorder transition is closely related to a freezing of this reorientation. (4) By elongation of [M(H2O)6]2+ along the C3 axis, the mobility becomes higher. (5) The disorder of [Fe(H2O)6]2+ in the high-temperature phase of [Fe(H2O)6][SiF6] is dynamic. Rotational modulation of [Mg(H2O)6]2+ along the C3 axis exists in the incommensurate phase of [Mg(H2O)6][SiF6].
Keywords : solid state NMR; molecular dynamics; electron spin dynamics; phase transition; numerical simulation.
Yoshinori Kato1, Akinori Maekawa1 and Toshiaki Nomura1
1 Department of Chemistry, Faculty of Science, Shinshu University, 3-1-1, Asahi, Matsumoto-shi, Nagano 390-8621
(Received 8 November 2002, Accepted 20 December 2002)Copper(II) could be determined indirectly by adding excess chelating agent to a sample solution and passing it through an electrode-separated piezoelectric quartz crystal (electrode-separated PQC) to be adsorbed on a quartz plate as an associated ion pair with a surfactant. 2-(5-Nitro-2-pyridylazo)-5-[N-proryl-N-(3-sulfopropyl)amino]-phenol (Nitro-PAPS) and Eriochrome Black T (BT) were used as water-soluble and water-insoluble chelating reagents, respectively. The surfactants used as counter ions were hexadecyltrimethylammonium chloride (CTAC) for the former and zephiramine for the latter. The frequency shifts of the electrode-separated PQC, resulting from adsorption of the associated ion pair, depended on the concentration of the counter ion, flow rate, mixing tube length, and so on. The concentrations of copper(II) over the range of 1.0~40 µM for Nitro-PAPS and 0.2~5.0 µM for BT could be determined with good reversibility.
Keywords : indirect determination of copper(II); electrode-separated piezoelectric quartz crystal; associated ion pair; Nitro-PAPS; BT.
Gu Jin1,2, Arkin Iburaim1,3, Masayuki Itagaki1 and Kunihiro Watanabe1
1 Department of Pure and Applied Chemistry, Faculty of Science and Technology, Tokyo University of Science, 2641, Yamazaki, Noda-shi, Chiba 278-8510
(Received 19 November 2002, Accepted 15 January 2003)The spectrophotometric determination of trace amounts of phenols was investigated for flow-injection analysis. Phenols reacted with 4-aminoantipyrine(4-AAP) to form stable antipyrine dyes, which were concentrated on a Teflon(PTFE) filter tube. The antipyrine dyes collected on the filter tube were eluted with 99% ethanol. The conditions for the antipyrine dye synthesis used in this study were remarkably different from that for the conventional batch method. Because a large excess of 4-AAP interferes with the adsorption of antipyrine dyes on a Teflon filter tube, 4-AAP was used at a lower concentration than that of the batch method. As a result, the reaction of antipyrin dye synthesis consumed a long time. Concerning the pH for the synthesis of antipyrine dyes, 7.3 was selected from the standpoint of the collection efficiency for the antipyrine dyes. The sensitivity of the determination of phenols by the present method was enhanced by 18 times compared to other concentration methods using Amberlite XAD resin. The detection limits was 0.04 µg l-1 for phenols for a concentration time of 15 min. The optimum procedure for the determination of phenols by the present method was as follows: a sample solution containing less than 5 µg of phenols was adjusted with a KH2PO4-K2HPO4 buffer solution to pH 7.3. Then, 0.5 ml of 0.04% 4-AAP and 1.0 ml of 0.16%KFe(CN)6 were added to the solution. The sample solution was left standing for 15 min to produce antipyrine dye. The obtained dye solution(100 ml) was transported to a Teflon filter tube at a flow rate of 1.6 ml/min for 15 min. The absorbance of the dyes eluted with ethanol (1.6 ml/min) was measured at 510 nm. The phenols were determined over the range of 0.5~40 µg l-1. The RSD was 2.1% for 0.5 µg l-1 phenols (n=7). Aniline and its derivative interfered with the determination of phenols at more than 10 times the amount of phenols. Inorganic ions did not interfere with the determination of phenols except for sodium sulfite.
Keywords : determination of phenols; Teflon filter tube; 4-aminoantipyrin; on-line concentration; flow-injection analysis.
Masashi Nojima1, Yusuke Kanda1,2, Masayuki Toi1,2, Bunbunoshin Tomiyasu3, Tetsuo Sakamoto1,3, Masanori Owari1,3 and Yoshimasa Nihei1,2
1 Institute of Industrial Science, University of Tokyo, 4-6-1, Komaba, Meguro-ku, Tokyo 153-8505
2 Faculty of Industrial Science and Technology, Tokyo University of Science, 2641, Yamazaki, Noda-shi, Chiba 278-8510
3 Environmental Science Center, University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-0033
(Received 5 December 2002, Accepted 23 January 2003)Recent electronic devices with fine and complex structures have been actively advancing. Therefore, it is necessary to develop a new analytical method for these devices. Because of this motivation, we developed a nano-beam secondary mass spectrometry (SIMS) method which can realize a high spatial resolution and a high efficiency of secondary ion detection. The edge resolution, which almost indicates lateral resolution, was estimated to be 22 nm by the standard deviation. We discussed the useful yield of a nano-beam SIMS apparatus; the value indicated that the method is applicable for some 10 nm depth dimensions. Elemental mapping of Al wires on a DRAM was performed with an especially high resolution and a high efficiency of secondary ion detection.
Keywords : nano-beam; SIMS; lateral resolution; elemental mapping.
Shoji Kurata1, Naoyuki Aizawa1, Haruo Hirano1 and Masatoshi Nagai2
1 Criminal Investigation Laboratory, Metropolitan Police Department, 2-1-1, Kasumigaseki, Chiyoda-ku, Tokyo 100-8929
2 Graduate School of Bio-applications and Systems Engineering, Tokyo University of Agriculture and Technology, 2-24, Nakamachi, Koganei-shi, Tokyo 184-8588
(Received 18 September 2002, Accepted 20 December 2002)Three-layer extraction followed by fluorescence spectrometry has been developed for the rapid discrimination of oils containing coumarin. The proposed method provides facilities, such as rapidity, convenience, and down-sizing. The procedure of the method is as follows: 0.25 ml of oil samples was used for quantification. After shaking a mixture of the sample with 1.5 ml of dodecane, two ml of butanol-ethanol (4:3; v/v) solution, and 1.25 ml of alkaline aqueous solution (2.5 M NaOH) for three min, non-fluorescing o-coumarinate ions produced from coumarin by hydrolysis were extracted in an alkaline aqueous solution. Fluorescent compounds in oils were extracted together with the o-coumarinate ions in the alkaline aqueous solution, and interfered with the quantification of the o-coumarate ions using fluorescence spectrophotometry. The addition of inorganic salts to the alkaline aqueous solution was very effective to quench the fluorescent interference of the co-extracted substances from oils. The addition of sodium nitrate which was the most effective quencher, suppressed any unfavorable fluorescent interferences. After the o-coumarinate ions were converted into isomeric o-coumarate ions by the irradiation of ultraviolet light for five min, fluorescence intensities at 500 nm were measured. The fluorescence intensity showed a good linear relationship with the gas-oil content in the range of 5~100% of fuel oil A in the gas-oil mixtures. A statistical analysis of the calibration curve gave an excellent relation with a correlation coefficient of 0.996~0.999. The proposed method could successfully discriminate illegal diesel fuels containing coumarin.
Keywords : coumarin; fuel oil A and gas oil; fluorescence; o-coumarate; inorganic salt as quencher.
Xiu-Feng Gao1, Yong-Sheng Li2 and Isao Karube3
1 Department of Medical Test, College of Medicine, University of Beihua, No.1, Beijin road, Jilin city, 132011, Jilin province, China
2 Department of Applied Chemistry, Northeast China Institute of Electrical Power Engineering, No.169, Chang chun road, Jilin city, 132012, Jilin province, China
3 Research Center for Advanced Science and Technology, University of Tokyo, 4-6-1, Komaba, Meguro-ku, Tokyo 153-8904
(Received 1 November 2002, Accepted 14 January 2003)A simple assay of sulfated bile acid (SBA) in urine using flow-injection(FI)-spectrophotometry with immobilized enzyme reactors is proposed. The system consists of an injection valve, a switch valve, two immobilized enzymes reactors and a UV-VIS detector with a flow cell. The multi-step enzymatic reactions occur when an injected sample containing SBA passes through the immobilized enzyme reactors. First, SBA will desulfate under the catalysis of immobilized bile acid sulphate sulfatase (BSS) to form 3β-hydroxyl bile acids; the produced 3β-hydroxyl bile acid reacts with nicotinamide adenine dinucleotide (NAD+) under the catalysis of co-immobilized 3β-hydroxylsteroid dehydrogenase (3β-HSD), and is converted to the 3-ketosteroid. Meanwhile, β-NAD+ is converted to reduced nicotinamide adenine dinucleotide (NADH). Then, by the catalysis of immobilized diaphorase, NADH reacts with a novel reagent, called “water soluble tetrazolium blue” (WST-5), to generate a blue diformazan dye, which is detected at 550 nm. By using FI-spectrophotometry manifold and optimized conditions, we obtained a linear response for 1~75 µM glycolithocholate sulfate (GLCA-S) with a correlation coefficient of 0.999 and an analytical rate of 15 samples per hour. The RSD was less than 1%. The recoveries (91~108%) of GLCA-S added into urine were satisfactory and the assay correlativity well with the manual UBASTEC kit. Therefore, it will be applicable for urine tests on patients suffering from hepatobiliary disease.
Keywords : sulfated bile acid; water soluble tetrazolium blue-5; flow injection analysis; spectrophotometry; immobilized enzyme.
Michio Zenki1, Hiroaki Itoh1, Shinsuke Himeno1 and Takashi Yokoyama1
1 Department of Chemistry, Faculty of Science, Okayama University of Science, 1-1, Ridai-cho, Okayama-shi, Okayma 700-0005
(Received 20 November 2002, Accepted 17 January 2003)A simple solid-phase colorimetry using polyurethane foam (PUF) for the determination of iron(II) has been proposed. The 1,10-phenanthroline (phen) method is selective and sensitive, and is widely used for the determination of Fe(II) in aqueous solution. It is worthwhile to develop this method, which is suitable for visual colorimetry. An iron(II)-phen complex and its ion-associates, such as Br-, SCN- and ClO4-, were not extracted onto PUF at all. In the presence of sodium dodecyl sulfate (SDS), we found iron(II)-phen complex was adsorbed onto PUF and the iron concentration was visually measured from the resulting color onto PUF. The recommended procedure is as follows. Five ml of a 1 M acetate buffer solution (pH 4.7), 1 ml of 10 w/v% ascorbic acid, 3 ml of 0.1 w/v% phen, and 4 ml of 5×10-3 M SDS were added to a 200 ml sample solution containing less than 200 ppb of Fe(II). A chip of PUF (2×2×2 cm) was put into the solution and stirred with a magnetic stirrer for 20 minutes. The chip taken up from the solution was rinsed with distilled water and squeezed to remove any water. The color intensity of the PUF was then visually compared by a standard series method.
Keywords : visual colorimetry; Fe(II)-1,10-phenanthroline; polyurethane foam.
Jun Onodera1, Yoshihisa Ueda1, Jae-Won Choi2, Shunji Hashimoto2, Noriyuki Suzuki2, Masatoshi Morita2 and Hisakuni Sato3
1 Application & Reseach Center, JEOL Ltd., 3-1-2, Musashino, Akisima-shi, Tokyo 196-8558
2 National Institute for Environmental Studies, 16-2, Onogawa, Tsukuba-shi, Ibaraki 305-8506
3 Laboratory of Analytical Chemistry, Faculty of Engineering, Yokohama Nationl University, 79-5, Tokiwadai, Hodogaya-ku, Yokohama 240-8501
(Received 18 October 2002, Accepted 10 January 2003)In the near future, poly-brominated dibenzo-p-dioxins(PBDDs) and poly-brominated dibenzofurans(PBDFs) will produce a big environ mental problem, as in the case of poly-chlorinated dibenzo-p-dioxins(PCDDs) and poly-chlorinated dibenzofurans(PCDFs). Therefore, the establishment of an analysis method for PBDDs and PBDFs is very important and urgently necessary. However, the necessary information is insufficient. We studied the interfering influence of polybrominated-diphenyl ethers (PBDEs), which are generally used as brominated frame retardants, upon PBDFs by HRGC/HRMS analysis. As a result, we ascertained that PBDEs disturb PBDFs on a SIM chromatograph due to a similar structural formula. Therefore, PBDEs should be removed from the sample during sample clean-up and simultaneously detected with PBDD and PBDFs by an HRGC/HRMS analysis.
Keywords : PBDDs; PBDFs; PBDEs; HRGC/HRMS; BFRs.
Hideyuki Yoshida
Faculty of Pharmaceutical Sciences, Fukuoka University, 8-19-1, Nanakuma, Johnan-ku, Fukuoka 814-0180
(Awarded by Fukuoka University dated October 9, 2001)Studies on liquid chromatography (LC) with novel luminol-type chemiluminescence derivatization reagents and with chemiluminescence detection using a ruthenium complex have been carried out. In the first study, 6-[N-(3-propionohydrazino)thioureido]benzo[g]phthalazine-1,4(2H,3H)-dione (PROB), a selective luminol-type chemiluminescence-labeling reagent for carboxylic acids, was developed. PROB reacted with fatty acids under mild conditions, and the derivatives were detected chemiluminometrically by a reaction with hydrogen peroxide in the presence of alkaline potassium hexacyanoferrate(III). This method has sufficient selectivity and sensitivity for the determination of free fatty acids in human plasma. In a second study, 7-amino-6-sulfanylphthalazine-1,4(2H,3H)-dione (ASP), an ultra-sensitive luminol-type chemiluminescence-generating reagent for aromatic aldehydes, was developed. Aromatic aldehydes were converted with ASP to highly fluorescent and chemiluminescent products. From this study, a novel structure was found which chemiluminesced more intensely than luminol. Based on the finding, 4-(6,7-dihydro-5,8-dioxothiazolo[4,5-g]phthalazin-2-yl)benzoic acid N-hydroxysuccinimide ester (TPB-Suc), a sensitive luminol-type chemiluminescence-labeling reagent for primary and secondary amines, was developed. TPB-Suc could make amines labeled under mild conditions and detected by chemiluminescence generation. This TPB-Suc method was successfully applied to the determination of amantadine in human plasma. In the last study, a determination method of tricyclic antidepressants was developed using LC with tris(bipyridyl)ruthenium(III) chemiluminescence detection. This method was successfully applied to the determination of imipramine, amitriptyline and their metabolites in human plasma. All of these methods should be useful for analyses of biological, pharmaceutical and environmental samples.
Keywords : liquid chromatography; chemiluminescence detection; derivatization reagent; luminol; 6-[N-(3-propionohydrazino)thioureido]benzo[g]phthalazine-1,4(2H,3H)-dione; 7-amino-6-sulfanylphthalazine-1,4(2H,3H)-dione; 4-(6,7-dihydro-5,8-dioxothiazolo[4,5-g]phthalazin-2-yl)benzoic acid N-hydroxysuccinimide ester; tris(bipyridyl)ruthenium(II).
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