Study of Organic derivatizing Reagents in Ultratrace Metal Analysis by HPLC-spectrophotometric/fluorimetric System.

本研究的目的是开发反相高效液相色谱-分光光度/荧光法联用分析超痕量金属的有机衍生试剂。(1)苯甲酰腙衍生物的某些金属螯合物具有很好的高效液相色谱分离和测定性能。使用化合物1开发了<Al^（3+）>离子在亚ppb范围内的高灵敏度荧光检测。通过分光光度法检测，化合物2对<V^（5+）>离子的检测限为0.1 ppb，而不受摩尔过量100倍的<Fe^（3+）>离子的干扰。通过使用化合物3成功地构建了镍特异性测定体系。系统的合理化研究的螯合物的结构和洗脱曲线表明，<alpha>-二亚胺框架的配体可能是至关重要的镍特异性。(2)建立了一种高灵敏度、高选择性的测定雨水和大气颗粒物中钒的高效液相色谱方法。在0.005吸光度单位满量程下达到0.08 ppb的检测限，这比原子光谱技术低至少一个数量级。该方法成功地应用于仙台市市区获得的真实的样品。

The aim of this research is the exploitation of organic derivatizing reagents for ultratrace metal analysis by coupled use of reversed-phase HPLC with spectrophotometry/fluorometry.(1) Some metal chelates of benzoylhydrazone derivatives are highly amenable to the HPLC separation and determination. The highly sensitive fluorometric detection of <Al^(3+)> ion in the sub-ppb range was devepoled using Compound 1. The detection limit of 0.1 ppb for <V^(5+)> ion was attained with Compound 2 by spectrophotometric detection without interference from <Fe^(3+)> ion in a 100-fold molar excess. The nickel-specific determination system was successfully constructed by the use of Compound 3. Systematic rationalization study on the chelate structure and the elution profiles showed that the <alpha> -diimine framework in the ligands is likely to be vital for the nickel-specificity.(2) A highly sensitive and selective HPLC method for monitoring of vanadium in rain water and air-borne particulates was developed with Compound 4 (QADAP). The detection limit of 0.08 ppb was reached at 0.005 absorbance unit full-scale, which is at least an order of magnitude lower than those of the atomic spectroscopic techniques. The method was successfully applied for the real samples obtained in the urban area of Sendai city.