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一种基于铁(II)螯合物对氧的催化活化作用来测定溶解氧的简单荧光探针。

A simple fluorescent probe for the determination of dissolved oxygen based on the catalytic activation of oxygen by iron(II) chelates.

作者信息

Luo Wei, Abbas M E, Zhu Lihua, Zhou Wenyi, Li Kejing, Tang Heqing, Liu Shushen, Li Weiying

机构信息

College of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, 1037 Luo-Yu Road, Hong-Shan Qu, Wuhan 430074, PR China.

出版信息

Anal Chim Acta. 2009 Apr 27;640(1-2):63-7. doi: 10.1016/j.aca.2009.03.024. Epub 2009 Mar 24.

Abstract

This work aims at establishing a simple fluorescent probe for the determination of dissolved oxygen. It is found that iron(II) ions activate oxygen to produce reactive species being capable of oxidizing non-fluorescent coumarin to fluorescent 7-hydroxycoumarin. However, this process is not effective because the yield of the reactive species is very low in the presence of simple iron(II) salts alone. The addition of organic ligands such as oxalate results in the formation of complexes between iron(II) ions, which leads to considerable increase in the yield of reactive species (such as hydroxyl radicals) and then increase in the fluorescence intensity of 7-hydroxycoumarin to a significant level. It has been observed that in the mixture solution of iron(II) ions, ligand, coumarin, and dissolved oxygen, there is an excellent linear response between the fluorescence and dissolved oxygen. Therefore, a new spectrofluorimetric method has been proposed for the determination of dissolved oxygen by using catalytic activation of O(2) by iron(II) chelates. Under optimized conditions, a linear correlation (r=0.995) has been observed between the fluorescence intensity of 7-hydroxycoumarin at 456 nm and the concentration of dissolved oxygen over the range of 0.96-9.22 mg L(-1). The limit of detection for dissolved oxygen at a signal-to-noise ratio of 3 has been estimated to be 0.35 mg L(-1). The proposed method has been applied to determine the concentration of dissolved oxygen in practical water samples with results as satisfactory as that obtained by the standard iodometric method.

摘要

本工作旨在建立一种用于测定溶解氧的简单荧光探针。研究发现,亚铁离子可激活氧气生成能够将非荧光香豆素氧化为荧光7-羟基香豆素的活性物种。然而,该过程并不高效,因为仅在简单亚铁盐存在的情况下活性物种的产率很低。添加草酸盐等有机配体可导致亚铁离子之间形成配合物,这使得活性物种(如羟基自由基)的产率大幅增加,进而使7-羟基香豆素的荧光强度显著提高。据观察,在亚铁离子、配体、香豆素和溶解氧的混合溶液中,荧光与溶解氧之间存在良好的线性响应。因此,提出了一种利用亚铁螯合物对O(2)的催化活化作用来测定溶解氧的新荧光光谱法。在优化条件下,观察到456 nm处7-羟基香豆素的荧光强度与0.96 - 9.22 mg L(-1)范围内溶解氧浓度之间存在线性相关性(r = 0.995)。在信噪比为3时,溶解氧的检测限估计为0.35 mg L(-1)。所提出的方法已应用于实际水样中溶解氧浓度的测定,结果与标准碘量法获得的结果一样令人满意。

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