Meso-四（磺酸丁氧基）苯基卟啉与金属离子的络合反应

Study on the Complexation Reactions of Meso-tetrakis[4-(4-sulfobutyloxyl)-phenyl]porphyrin with Metal Ions

摘要

本文合成了水溶性Meso-四（磺酸丁氧基）苯基卟啉，研究了该卟啉在甲醇、水介质中与金属离子的络合反应。通过其与铜、锌、钴、铅及锰的乙酸盐在甲醇介质中反应制备了相应的金属卟啉，使用¹H NMR、¹³C NMR、紫外吸收光谱、荧光光谱及质谱对卟啉化合物的结构进行了表征，紫外吸收光谱和¹H NMR对金属卟啉的结构进行了表征。研究了其与铜、铅、镁、铝、镍、钴、锌、二价铁、三价铁等金属离子在水介质中的络合反应。实验结果表明：在水介质中，该卟啉能与铜离子迅速形成金属卟啉，利用这一特性通过紫外-可见光分光光度法建立了一种简便、快速的铜离子测量方法，铜离子的浓度在2.67×10^-7～11.0×10^-7 mol·L^-1内符合Lambert-Beer定律。实测了含铜不锈钢材料中多种金属离子共存状态下铜离子的含量，回收率达93.10%～98.60%。

Abstract

This paper describes the synthesis of hitherto water-soluble meso-tetrakis-[4- (4-sulfobutyloxy) phenyl]porphyrin and its complexation reaction with metal ions in methanol and water. Metalloporphyrins were synthesized by reacting with Cu²⁺, Zn²⁺, Co²⁺, Pb²⁺ and Mn²⁺ acetates in methanol. The structure of the porphyrin was characterized by ¹H NMR, ¹³C NMR, UV and fluorescence spectroscopy, and mass spectrometry. The corresponding metalloporphyrins were characterized by UV spectroscopy and ¹H NMR. The complexation reactions of meso-tetrakis-[4-(4-sulfobutyloxy) phenyl]porphyrin with various metals ions, including Cu(II), Pb(II), Mg(II), Al(III), Ni(II), Co(II), Zn(II), Fe(II) and Fe(III), in aqueous media were also investigated. Copper ions were found to be able to rapidly form a copper-porphyrin complex in water. Based on this observation, a quick and straightforward UV-Vis spectrophotometric determination method for copper ions was established, Beer's law is obeyed in the range of 2.67×10^-7—11.0×10^-7 mol·L^-1 for Cu(II). The copper content in copper containing stainless steel samples was determined in the presence of other metals and the recoveries was found to be between 93.10% and 98.60%.

Graphical abstract

关键词

Meso-四(磺酸丁氧基)苯基卟啉 / 金属卟啉 / 络合反应 / 紫外-可见光分光光度法 / 铜离子测定

Key words

5,10,15,20-tetrakis[4- (4-sulfobutyloxyl) phenyl]porphyrin / metalloporphyrins / complexation reaction / UV-Vis spectrophotometry / copper ion determination

基金资助

山西省重点研发计划项目(201803D31010)