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基于还原性有机笼的氧化降解对羟基自由基和葡萄糖进行灵敏的荧光开启传感。

Sensitive fluorescence turn-on sensing of hydroxyl radical and glucose based on the oxidative degradation of reductive organic cage.

作者信息

Xu Ying, Dai Cong, Xu Zhifeng

机构信息

College of Chemistry and Materials Science, Hunan Engineering Research Center for Monitoring and Treatment of Heavy Metals Pollution in the Upper Reaches of Xiangjiang River, Hengyang Normal University, Hengyang, 421001, China.

College of Chemistry and Materials Science, Hunan Engineering Research Center for Monitoring and Treatment of Heavy Metals Pollution in the Upper Reaches of Xiangjiang River, Hengyang Normal University, Hengyang, 421001, China.

出版信息

Talanta. 2025 May 1;286:127518. doi: 10.1016/j.talanta.2025.127518. Epub 2025 Jan 2.

DOI:10.1016/j.talanta.2025.127518
PMID:39755078
Abstract

The accurate and sensitive quantification of hydroxyl radical (·OH) and glucose is necessary for disease diagnosis and health guidance, but still challenging owing to the low concentration of ·OH and poor water solubility of fluorescent probes. In addition, fluorescent probes may cause secondary pollution to the environment. Here an organic cage was reported as a sensitive fluorescent probe for ·OH and glucose in aqueous solution without serious secondary pollution. The prepared organic cage with good water solubility showed specific redox affinity to ·OH in acidic condition, resulting in two oxidation stages of mild oxidation and subsequent oxidative degradation. Fluorescence around 485 nm enhanced remarkably in the first stage, and benzene ring in organic cage was degraded in the second stage. Based on the significant fluorescence enhancement, a sensitive fluorescence turn-on sensing method for ·OH was established within 90 s with the limit of detection (3s/k, where s and k are the standard deviation for 10 replicate detections of blank and the slope of calibration function) of 5 nM. The recoveries of spiked ·OH in human serum and water samples ranged from 95.2 % to 102.7 %. After the glucose oxidase enzyme-Fenton reaction was involved, the ·OH detection was also applied to sensitive sensing of glucose with the limit of detection (3s/k) of 6 nM. The recoveries of spiked glucose in sugary drinks ranged from 96.2 % to 102.6 %. Furthermore, the proposed method would also be suitable for other hazardous substances and biomarkers which can produce hydrogen peroxide and further form ·OH via Fenton reaction.

摘要

准确灵敏地定量检测羟基自由基(·OH)和葡萄糖对于疾病诊断和健康指导至关重要,但由于·OH浓度低且荧光探针水溶性差,这一检测仍具有挑战性。此外,荧光探针可能会对环境造成二次污染。在此,报道了一种有机笼状化合物作为水溶液中·OH和葡萄糖的灵敏荧光探针,且不会造成严重的二次污染。所制备的具有良好水溶性的有机笼状化合物在酸性条件下对·OH表现出特定的氧化还原亲和力,导致两个氧化阶段,即轻度氧化和随后的氧化降解。在第一阶段,485 nm左右的荧光显著增强,在第二阶段有机笼状化合物中的苯环被降解。基于显著的荧光增强,建立了一种90 s内检测·OH的灵敏荧光开启传感方法,检测限(3s/k,其中s和k分别为空白10次重复检测的标准偏差和校准函数的斜率)为5 nM。加标·OH在人血清和水样中的回收率在95.2%至102.7%之间。在引入葡萄糖氧化酶-芬顿反应后,·OH检测也可用于灵敏检测葡萄糖,检测限(3s/k)为6 nM。加标葡萄糖在含糖饮料中的回收率在96.2%至102.6%之间。此外,所提出的方法也适用于其他能够产生过氧化氢并通过芬顿反应进一步形成·OH的有害物质和生物标志物。

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