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基于香豆素的荧光化学传感器对铜(II)离子的“开-关”型荧光传感性能研究:实验研究、理论计算、矿物和饮用水分析。

Fluorescence "Turn On-Off" Sensing of Copper (II) Ions Utilizing Coumarin-Based Chemosensor: Experimental Study, Theoretical Calculation, Mineral and Drinking Water Analysis.

机构信息

Department of Chemistry, Kamil Ozdag Science Faculty, Karamanoglu Mehmetbey University, 70100, Karaman, Turkey.

Van't Hoff Institute for Molecular Sciences, Analytical-Chemistry Group, University of Amsterdam, Amsterdam, Netherlands.

出版信息

J Fluoresc. 2020 Mar;30(2):317-327. doi: 10.1007/s10895-020-02503-4. Epub 2020 Feb 3.

Abstract

Herein, we report the preparation of a fluorescent sensor based on coumarin derivative for copper (II) ion sensing in CHCN/HEPES media. 6,7-dihydroxy-3-(4-(trifluoro)methylphenyl)coumarin (HMAC) sensor was fabricated and analyzed by spectroscopic techniques. The sensor demonstrates "turn on-off" fluorescence quenching in the presence of copper (II) ions at 458 nm. A clear complex between the chemosensor HMAC and copper (II) ions was characterized by ESI-MS as well as the Job's method. Also, the limit of detection (LOD, 3σ/k) value was determined as 24.5 nM in CHCN/HEPES (95/5, v/v) buffer media (pH = 7.0). This value is lower than the admissible level of copper (II) ions in drinking water (maximum 31.5 μM) reported by EU Water Framework Directive (WFD) and World Health Organization (WHO) guidelines. The theoretical calculations (density functional theory, DFT) have been performed for the geometric optimized structures. As a final stage, real sample analyses have successfully been performed by using HMAC, as well as ICP-OES method. The relative standard deviation for copper (II) in mineral and drinking water samples has been determined to be below 0.15% and recovery values are in the range of 95.48-109.20%.

摘要

本文报道了一种基于香豆素衍生物的荧光传感器在 CHCN/HEPES 介质中用于铜(II)离子传感的制备。通过光谱技术制备和分析了 6,7-二羟基-3-(4-(三氟甲基)苯基)香豆素(HMAC)传感器。该传感器在存在铜(II)离子时在 458nm 处表现出“开-关”荧光猝灭。通过 ESI-MS 以及 Job 法也证实了化学传感器 HMAC 与铜(II)离子之间存在明显的配合物。此外,在 CHCN/HEPES(95/5,v/v)缓冲介质(pH=7.0)中,检测限(LOD,3σ/k)值确定为 24.5nM。这个值低于欧盟水框架指令(WFD)和世界卫生组织(WHO)指南规定的饮用水中铜(II)离子的允许水平(最大 31.5μM)。还进行了理论计算(密度泛函理论,DFT)以获得几何优化结构。最后,成功地使用 HMAC 和 ICP-OES 方法对实际样品进行了分析。在矿泉和饮用水样品中,铜(II)的相对标准偏差确定为低于 0.15%,回收率值在 95.48-109.20%范围内。

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