Development of New Reagents for Spectrophotometric Determination of Fluoride Based on Mixed Ligand Complex Formation

基于混合配体络合物形成的分光光度测定氟化物新试剂的研制

• 批准号: 02640444
• 负责人: YUCHI Akio
• 金额: $ 1.22万
• 依托单位: Nagoya Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02640444/
• 关键词: Fluoride Ion; Spectrophotometry; Mixed Ligand Complex; Chelating Reagent; Zirconium; Flow Injection Analysis; 吸光光度分析

Semi-xylenol Orange was, as its zirconium(IV) complex, a promising reagent for spectrophotometric determination of fluoride. Experimental conditions were optimized for practical use. The sensitivity is almost the same as La-Alizarin Complexon method, but a reagent blank is low and the reaction concludes within a minute. Flow injection analysis was successfully applied to this reaction system.The equilibrium relevant to this color change was studied using a fluoride ion-selective electrode. A partly hydrolyzed parent complex reacts with fluoride to form mixed ligand complexes. The phenolic oxygen atom made free by the partial hydrolysis again coordinates to zirconium upon mixed ligand complex formation. This finding helps the design of new organic reagents.Effect of a side-arm on formation of the mixed ligand complex was studied using simpler ligands (L) ; aminopolycarboxylates. DTPA and DPTA complexes do not react with fluoride. In the case of potentially decadentate TTHA, a protonated complex ZrHL has fairly high affinity to fluoride, whereas a complex ZrL does not. In the case of HEDTA, a complex ZrL has a higher stability constant for fluoride than EDTA or CDTA complex. The complex ZrH-_1L formed by deprotonation from alcoholic OH group, on the other hand, has much lower affinity to fluoride.

半二甲酚橙子与锆（IV）形成络合物，是一种很有前途的光度法测定氟化物的试剂。实验条件进行了优化，实际应用。该方法的灵敏度与茜素络合剂法基本相同，但试剂空白低，反应在1分钟内结束。用氟离子选择性电极研究了该反应体系的色变平衡。部分水解的母体络合物与氟化物反应形成混合配体络合物。通过部分水解而游离的酚氧原子在混合配体络合物形成时再次与锆配位。这一发现有助于新的有机试剂的设计。侧臂对混合配体络合物形成的影响进行了研究，使用更简单的配体（L）;氨基多羧酸酯。DTPA和DPTA络合物不与氟化物反应。在潜在的decadentate TTHA的情况下，质子化的络合物ZrHL具有相当高的亲和力，氟化物，而复杂的ZrL没有。在HEDTA的情况下，络合物ZrL具有比EDTA或CDTA络合物更高的氟化物稳定常数。而醇羟基去质子化形成的配合物ZrH-1 L对氟离子的亲合力则低得多。

项目成果

湯地 昭夫,帆刈 典久,和田 弘子: "Zirconium(IV) Semiーxylenol Orange as a New Spectrophotometric Reagent for Fluoride"

Akio Yuchi、Norihisa Hogari、Hiroko Wada：“锆 (IV) 半二甲酚橙作为氟化物的新型分光光度试剂”

"Masking of Zirconium (IV) in the Determination of Fluoride with an Ion-selective Electrode : Application to Zirconium (IV) Fluoride-based Glasses" Analyst. 116. 45-48 (1991)"Zirconium (IV) Semi-xylenol Orange as a few Spectrophotometric Reagent for Fluor

“用离子选择性电极测定氟化物时掩蔽锆 (IV)：在氟化锆 (IV) 玻璃中的应用”分析师。

湯地 昭夫,帆刈 典久,和田 弘子: "Zirconium(IV)Semiーxylenol Orange as a New Spectrophotometric Reagent for Fluoride"

Akio Yuchi、Norihisa Hogari、Hiroko Wada：“锆 (IV) 半二甲酚橙作为新型氟化物分光光度试剂”