| Project/Area Number |
16550067
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Analytical chemistry
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| Research Institution | Ibaraki University |
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Principal Investigator |
IMURA Hisanori Ibaraki University, College of Science, Professor, 理学部, 教授 (60142923)
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| Co-Investigator(Kenkyū-buntansha) |
OHASHI Kousaburo Ibaraki University, College of Science, Professor, 理学部, 教授 (60007763)
OHASHI Akira Ibaraki University, College of Science, Lecturer, 理学部, 講師 (50344833)
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| Project Period (FY) |
2004 – 2005
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| Project Status |
Completed (Fiscal Year 2005)
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| Budget Amount *help |
¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 2005: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2004: ¥2,500,000 (Direct Cost: ¥2,500,000)
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| Keywords | absolute determination / capillary electrophoresis / NMR / enantiomeric isomer / isotope dilution / substoichiometry / phosphorus-containing amino acid / lithium / 同位体希釈法 / アミノ酸 / 絶対定量 / 光学異性体 / シクロデキストリン / 協同効果抽出 |
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| Research Abstract |
1. A novel absolute determination method using chirality without any calibration curves or comparison standards has been proposed for phosphorus-containing amino acid-type herbicides, glufosinate (D,L-GLUF). This method is based on a change in the enantiomeric ratio after the spiking of a known amount of the enantiomers with different enantiomeric ratios to a sample. D,L-GLUF was determined by adding a known amount of L-GLUF to the sample, derivatizing them with dansyl chloride, and measuring the ratio of the peak area of the D-isomer to that of the L-isomer by means of γ-cyclodextrin modified capillary zone electrophoresis with UV detection. The accuracy and precision of the method were evaluated using a synthetic sample. The mean values obtained for D- and L-GLUF agreed with the values taken within 1.6% ; also the reproducibility was as good as less than 2.8%. Furthermore, fluorescence detection and large-volume sample stacking for the capillary electrophoresis were studied to resolve and detect trace D,L-GLUF in femto-mole levels.
2. A novel analytical method, substoichiometric isotope dilution nuclear magnetic resonance analysis (SID-NMR), has been proposed. The present method consists of the complexation of Li^+ with a substoichiometric amount of cryptand [2.1.1] (C211) and the subsequent signal intensity measurement of an isotope of ^7Li by ^7Li-NMR. The resonance signal (chemical shift) of the Li(C211)^+ complex was completely separated from that of free Li^+ in the NMR spectrum and the integrated area of the signal from a constant amount of the Li(C211)^+ complex was substoichiometrically measured. The reproducibility of the integrated area was 2.1% as relative standard deviation for (4.1-8.2) × 10^<-3> mol dm^<-3> Li when a Li-β-diketone complex was used as an external standard. The validity and the usefulness of SID-NMR were demonstrated by the determination of Li in a synthetic solution.
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