Development of Novel Absolute Determination Methods for Chiral Organic Compounds and Lithium

手性有机化合物和锂的绝对测定新方法的开发

• 批准号: 16550067
• 负责人: IMURA Hisanori
• 金额: $ 2.05万
• 依托单位: Ibaraki University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16550067/
• 关键词: 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

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.

1.提出了一种基于手性的含磷氨基酸型除草剂草甘膦(D，L-GLUF)的手性绝对测定方法。这种方法是基于将已知数量的具有不同对映体比例的对映体添加到样品中后对映体比例的变化。D，L-GLUF的测定是在样品中加入已知量的L-GLUF，用丹磺酰氯进行衍生化，并用γ-环糊精修饰毛细管区带电泳法测定D-异构体与L-异构体的峰面积之比。用合成样品对该方法的准确度和精密度进行了评价。D-和L-GLUF测定值的平均值与1.6%以内的测定值吻合，重复性好，重复性好，小于2.8%。在此基础上，研究了毛细管电泳法的荧光检测和大体积样品堆积，实现了对飞摩尔水平上痕量D，L-GLUF的拆分和检测。提出了一种新的分析方法--亚化学计量同位素稀释核磁共振分析(SID-NMR)。本方法包括Li~(++)与亚化学计量比密码[2.1.1](C211)的络合以及随后用^7Li-核磁共振测量~7Li同位素的信号强度。在核磁共振谱中，Li(C211)~+与游离Li~(2+)的共振信号(化学位移)完全分离，并用亚化学计量学方法测量了恒量Li(C~(211))~+的信号积分面积。以Li-β-二酮络合物为外标时，积分面积的重现性为2.1%，相对标准偏差为(4.1-8.2x10^&lt；-3&gt；moldm^&lt；-3&gt；Li)。通过对合成溶液中锂的测定，验证了SID-核磁共振的有效性和实用性。

项目成果

Absolute Determination Method Using Chirality for Glufosinate and Bialaphos by γ-Cyclodextrin Modified Capillary Zone Electrophoresis

• DOI: 10.2116/analsci.21.31
• 发表时间: 2005-01
• 期刊: Analytical Sciences
• 影响因子: 1.6
• 作者: T. Asami;H. Imura;A. Ohashi;K. Ohashi;T. Ishiwata

Equilibrium and Mass Spectrometric Studies on the Ion-pair Extraction of Antimony(III) and Antimony(V) with Pyrogallol and Tetraphenylarsonium Chloride

连苯三酚和氯化四苯砷离子对萃取锑(III)和锑(V)的平衡和质谱研究

• 发表时间: 2005
• 期刊: Solvent Extraction for Sustainable Development (ed by ISEC 2005 Organizing Commitee, Beijing)
• 作者: Hashi;T.;Hata;N.;Kuramitu;H.;Taguchi;S.;H.Imura;H.Imura;T.Asami;H.Imura
• 通讯作者: H.Imura

Synergistic Cloud Point Extraction Behavior of Aluminum(III) with 2-Methyl-8-quinolinol and 3,5-Dichlorophenol

2-甲基-8-羟基喹啉和 3,5-二氯苯酚对铝(III)的协同浊点萃取行为

• 发表时间: 2004
• 期刊: Anal. Sci. 20
• 作者: T.Asami;H.Imura;A.Ohashi;K.Ohashi;T.Ishiwata;A.Ohashi
• 通讯作者: A.Ohashi

Direct Determination of Chromium(III) Complexed with Humic Acid by Energy Dispersive X-ray Fluorescence Spectrometry

能量色散X射线荧光光谱法直接测定与腐殖酸络合的铬(III)

• 发表时间: 2005
• 期刊: BUNSEKI KAGAKU 54
• 作者: Hashi;T.;Hata;N.;Kuramitu;H.;Taguchi;S.;H.Imura;H.Imura;T.Asami;H.Imura;大橋弘三郎;H.Imura;T.Asami;H.Imura;K.Ohashi
• 通讯作者: K.Ohashi

基本分析化学(日本分析化学会編)

基础分析化学（日本分析化学会编）

• 发表时间: 2004
• 作者: A.Ohashi;A.Tsuguchi;H.Imura;K.Ohashi;井村久則(分担執筆)
• 通讯作者: 井村久則(分担執筆)