1995 Fiscal Year Final Research Report Summary
Study of Dynamic Process of Reactions in Solution and its Application to Analytical Chemistry
| Project/Area Number |
06303005
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| Research Category |
Grant-in-Aid for Co-operative Research (A)
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| Allocation Type | Single-year Grants |
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| Research Field |
分離・精製・検出法
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| Research Institution | University of Tsukuba |
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Principal Investigator |
KAWASHIMA Takuji Univ.of Tsukuba, Inst.Chem.Prof., 化学系, 教授 (50041760)
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| Co-Investigator(Kenkyū-buntansha) |
TABATA Masaki Saga Univ., Fac.Sxi.& Eng.Prof., 理工学部, 教授 (40039285)
MOTOMIZU Shoji Okayama Univ., Fac.Sci.Prof., 理学部, 教授 (50032826)
FUNAHASHI Shigenobu Nagoya Univ., Fac.Sci.Prof., 理学部, 教授 (30022700)
OHASHI Kousaburo Ibaraki Univ., Fac.Sci.Prof., 理学部, 教授 (60007763)
WATANABE Hiroto Hokkaido Univ., Fac.Eng.Prof., 工学部, 教授 (80002856)
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| Project Period (FY) |
1994 – 1995
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| Keywords | Reaction in Solution / Dynamic Process / Chemiluminescence / Caaalytic Effect / Solvent Extraction / Flow-injection Analysis / Ion Association Reaction / Structure of Metal Complexes in Solution |
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| Research Abstract |
The peroxidase (POD) -catalyzed luminol chemiluminescence (CL) was used for the detection of H_2O_2 formed during the catalytic oxidation of glutation (GSH) by Cu (II). The maximum light emission was obtained by using arthromices romosus POD (ARP) and was found to be dependent on the concentration of GSH : thus a minute amount of GSH can easily be determined. A CL emission mechanism in metal-catalyzed oxidation of luminol in reverse micelles and its application to analytical chemistry was studied : it has bee pointed out the water pool plays an important role in the CL process. Kinetics and mechanistic studies on induced electron-transfer reactions involving superoxide radicals were carried out and new methods for traces of Cu (II) and nitrous acid were developed. The rates of metalloporphyrin formation are several orders of magnitude slower than that of the complex formation of open-chain ligands. The great difference in the reaction rate is due to a less flexible porpyirin ring and a
… More
less accessible lone-pair electrone on the porphyrin for the incoming metal ions. The dynamic mechanism of metal ion into deformed porphyirins were studied spectrophotometrically and the intermediate of the so-called sitting-atop complex was directly observed by X-ray, NMR and laser photolysis etc. Flow injection method was developed for the determination of traces of Cr (III) based on its catalytic effect on the oxidative coupling of 3-methyl-2-benzothiazolinone hydrazon (MBTH) with N-ethyl-N- (2-hydroxy-3-sulfopropyr)-3-methylaniline (ADOS). MBTH reacts with ADOS to form an intense colored dye in the presence of Cr (III) and H_2O_2 EDTA and phen showed large activating effect on the catalysis of Cr (III). By using this reaction a sensitive catalytic method for Cr (III) was developed and the methods was successfully applied to the determination of Cr in Vehicle Exhaust Particulates and reference river water. Catalytic oxidation reaction of protocatechuic acid by H_2O_2 in an alkaline medium was used for the sensitive post column detection of trace amounts of Mn. Stopped-flow FIA system and the simultaneous determination of Ni and Fe was successfully developed by ligand-substitution reaction of metal Nitros-PAPS somplexes with EDTA.Dynamic aspects of ligand-substitution reaction of a metal-chromgenic ligand complex with a polycarboxilic ligand and the catalytic effect of an additional ligand were also studied. The extraction of Ga (III) with newly prepared 8-qinolinol derivatives has been studies to obtain detailed informations concerning the steric effect of the alkyl substiuents in the hydrophobic 8-quinolinol moiety. Cationic triphenylmethane dyes have been used for the separation and determination of ions coupled with solvent extraction, precipitation, adsorption at liquid-liquid interface, and membrane filtration. Equilibria and kinetic studies on the cationic dyes have been performed. Three cationic dyes were desighnd and synthesized from the experimental res Less
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