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基于同时引入香豆素衍生物作为绿色荧光团和壳聚糖诱导的金/银合金纳米颗粒作为催化剂用于灵敏测定葡萄糖的鲁米诺化学发光评估。

Evaluation of luminol chemiluminescence based on simultaneous introducing of coumarin derivatives as green fluorophores and chitosan-induced Au/Ag alloy nanoparticle as catalyst for the sensitive determination of glucose.

作者信息

Chaichi M J, Alijanpour S O, Asghari S, Shadlou S

机构信息

Department of Chemistry, University of Mazandaran, Babolsar, Iran,

出版信息

J Fluoresc. 2015 Mar;25(2):263-75. doi: 10.1007/s10895-015-1502-8. Epub 2015 Feb 3.

Abstract

We report herein the development of a novel chemiluminescence system based on simultaneous introducing of synthetic coumarin derivatives and chitosan-induced Au/Ag alloy NPs on the luminol CL system and suggest how it may be useful for determination of glucose. Chitosan-induced Au/Ag nanoalloys in the coumarin derivatives intensified-luminol CL system, in addition to catalyze CL reaction can make a change in the process of coumarin derivatives effect as fluorophore on the luminol CL system. This phenomenon is caused by interaction between active functional groups of coumarin derivatives and chitosan. The interaction strength depends on the coumarin derivatives' structure and their substituents. Considering the inevitable trend luminol radical and superoxide anion radical to absorption on the surface of the embedded Au/Ag nanoalloy in the chitosan matrix, it can be concluded that chitosan acts as a platform for all reagents involved in the CL reaction including coumarin derivatives, Au/Ag nanoalloy and luminol, and electron-transfer taking place on it; Placing all chemiluminescent reagents together on the chitosan network can lead to a powerful CL due to increasing rigidity of CL system. The most efficient coumarin derivative on the Au/Ag nanoalloy-fluorophore-luminol-H2O2 CL system, in relation to interaction capability with chitosan' functional groups, was selected and the CL condition in presence of it was optimized. Whereas the glucose oxidase-mediated oxidation of glucose yields gluconic acid and H2O2, under optimum condition the most efficient CL system was applied to detection of glucose due to enzymatically production of hydrogen peroxide. The linear response range of 1.5 × 10(-6)-5.0 × 10(-3) M and the detection limit (defined as the concentration that could be detected at the signal-to-noise ratio of 3) of 7.5 × 10(-7) M was found for the glucose standards. Also, the developed method was successfully applied to determination of glucose in real serum and urine samples of diabetic patients and validated against colorimetric spectroscopy method.

摘要

我们在此报告一种新型化学发光系统的开发,该系统基于在鲁米诺化学发光体系中同时引入合成香豆素衍生物和壳聚糖诱导的金/银合金纳米粒子,并说明了其在葡萄糖测定中的应用。壳聚糖诱导的金/银纳米合金存在于香豆素衍生物增强的鲁米诺化学发光体系中,除了催化化学发光反应外,还能改变香豆素衍生物作为荧光团对鲁米诺化学发光体系的作用过程。这种现象是由香豆素衍生物的活性官能团与壳聚糖之间的相互作用引起的。相互作用强度取决于香豆素衍生物的结构及其取代基。考虑到鲁米诺自由基和超氧阴离子自由基不可避免地会吸附在壳聚糖基质中嵌入的金/银纳米合金表面,可以得出结论,壳聚糖作为化学发光反应中所有试剂(包括香豆素衍生物、金/银纳米合金和鲁米诺)的平台,电子转移在其表面发生;由于化学发光体系刚性增加,将所有化学发光试剂一起置于壳聚糖网络上可导致强烈的化学发光。基于与壳聚糖官能团的相互作用能力,在金/银纳米合金-荧光团-鲁米诺-H₂O₂化学发光体系中选择了最有效的香豆素衍生物,并优化了其存在下的化学发光条件。而葡萄糖氧化酶介导的葡萄糖氧化产生葡萄糖酸和H₂O₂,在最佳条件下,由于酶促产生过氧化氢,最有效的化学发光体系被应用于葡萄糖检测。葡萄糖标准品的线性响应范围为1.5×10⁻⁶ - 5.0×10⁻³ M,检测限(定义为在信噪比为3时可检测到的浓度)为7.5×10⁻⁷ M。此外,所开发的方法成功应用于糖尿病患者实际血清和尿液样本中葡萄糖的测定,并与比色光谱法进行了验证。

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