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/荧光联用分析超痕量金属的有机衍生化试剂。(1)苯甲酰肼类化合物的某些金属络合物对高效液相色谱分离测定具有很强的适应性。用化合物1建立了~lt；Al^(3+)&Gt；离子在亚ppb范围内的高灵敏荧光检测。用化合物2测定~lt；V^(5+)&Gt；离子的检出限为0.1 ppb，而不受~lt；Fe^(3+)&Gt；离子的干扰，摩尔过量为100倍。利用化合物3成功地构建了镍的专一性测定体系。对络合结构和洗脱图谱的系统合理化研究表明，配体中的α-二亚胺骨架可能是镍专一性的关键。(2)以化合物4(QADAP)为底物，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吸光度单位满刻度时，检测下限达到0.08ppb，比原子光谱分析技术低至少一个数量级。该方法已成功地应用于仙台市城区的实际样品。

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.