A Ruthenium(II) complex based long lifetime phosphorescent probe for copper ions and pH detection

Yan Chen, Xufeng Mai, Jiecheng Zhao, Cuiqin Huang, Jun Li, Zhuopeng Ruan, Huijuan Yu
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Abstract

Objective

Transition metal ruthenium(II) complex was used to prepare a dual-functional phosphorescent probe for the detection of Cu2+ ion and pH.

Methods

The ligand (E)-6-((thiazol-2-yl methylene)amino)-1,10-phenanthrolin-5-amine (tmpa) was prepared by condensation of 5,6-diamine-1, 10-phenanthroline with 2-formylthiazole, and then ruthenium(II) complex [Ru(bpy)2tmpa](PF6) (Ru-tmpa, bpy ​= ​2,2′-bipyridine) was synthesized by the coordination of tmpa with cis-Ru(bpy)2Cl2. Phosphorescence spectra were measured to investigate its response to metal ions (Li+, Na+, K+, Mg2+, Ca2+, Mn2+, Pb2+, Cr2+, Co2+, Ni2+, Cu+, Cu2+, Fe3+, Fe2+ and Zn2+). The binding affinity and detecting limit of Ru-tmpa to copper ions were tested by titration experiment. The ability of the probe to monitor copper ion levels inside cells was tested by confocal microscopy imaging.

Results

Ru-tmpa can rapidly, sensitively and selectively detect Cu2+ in water and biological sample, and shows a sensitive phosphorescence response to pH. Ru-tmpa can penetrate cell membrane, enter the cell, and monitor the level of copper ions inside cell.

Conclusion

A novel fluorescent probe Ru-tmpa was synthesized to provide a powerful tool for the detection of Cu2+ and pH in biological and environmental systems.

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基于钌(II)配合物的长寿命磷光探针,用于铜离子和 pH 值检测
目的利用过渡金属钌(II)配合物制备一种用于检测 Cu2+ 离子和 pH 值的双功能磷光探针。方法 配体(E)-6-((噻唑-2-基亚甲基)氨基)-1,10-菲罗啉-5-胺(tmpa)由 5,6-二氨基-1,10-菲罗啉与 2-甲酰基噻唑缩合制备而成、然后通过 tmpa 与顺式-Ru(bpy)2Cl2 配位合成了钌(II)配合物 [Ru(bpy)2tmpa](PF6)(Ru-tmpa,bpy = 2,2′-联吡啶)。测量了磷光光谱以研究其对金属离子(Li+、Na+、K+、Mg2+、Ca2+、Mn2+、Pb2+、Cr2+、Co2+、Ni2+、Cu+、Cu2+、Fe3+、Fe2+ 和 Zn2+)的反应。通过滴定实验测试了 Ru-tmpa 与铜离子的结合亲和力和检测限。结果 Ru-tmpa 能快速、灵敏、选择性地探测水和生物样品中的 Cu2+,并对 pH 值显示出灵敏的磷光响应。结论 新型荧光探针 Ru-tmpa 的合成为检测生物和环境系统中的 Cu2+ 和 pH 值提供了一种强有力的工具。
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