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一种基于四磺酸基苯基卟啉-儿茶酚的用于快速灵敏检测组氨酸的新型荧光和比色双传感系统。

A novel fluorescence and colorimetric dual sensing system for rapid and sensitive detection of histidine based on TSPP-CA.

作者信息

Zou Dajie, Lu Chenyan, Jia Yanyan, Wang Huan, Wang Jiuli

机构信息

Modern Tibetan Medicine Creation Engineering Technology Research Center of Qinghai Province, China; Phytochemistry Key Laboratory of Tibetan Plateau of Qinghai Province, China; College of Pharmacy, Qinghai Minzu University, Xining 810007, China.

QingHai Higher Vocational and Technical Institute, China.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2025 Sep 5;337:126145. doi: 10.1016/j.saa.2025.126145. Epub 2025 Mar 31.

Abstract

Histidine (His) plays an important role in human health and life activities. It will harm human health when His intake is insufficient or excessive. Its residue also will pollute the natural environment. Therefore, establishing a reliable and sensitive method for detecting histidine is particularly important. However, most of the existing detection methods of His rely on the single change of single signal, which are susceptible to interference from testing environmental factors and prone to generating false positive results. In contrast, the fluorescence and colorimetric dual-signal sensing system can not only effectively improve the reliability of detection, but also significantly reduce the risk of false positives. Therefore, the dual-signal sensing system has gradually become the research hotspot. Based on this, 5,10,15,20-tetra-(4-sulfophenyl) porphyrin (TSPP) was selected as the fluorescence and colorimetry dual-signal probe for the rapid detection of His in this study. Since TSPP could interact with many substances due to the specificity of molecular structure, it is the best choice to build an "ON-OFF-ON" sensing system in order to improve the specificity of the sensing system. Therefore, citric acid (CA) as an intermediate based on TSPP probe was successfully developed fluorescence and colorimetric dual-sensing system for the quantitative detection of histidine in real samples. The signal of the dual sensing system was "turned on" when the red TSPP solution obtained the fluorescence emission wavelength of 642 nm at the 514 nm optimal excitation wavelength and the UV-Vis absorption at 413 nm, respectively. The fluorescence intensity and absorbance of TSPP gradually decreased with the introduction of CA. At this time, the signal of the dual-sensing system became "turned off", and the color of the solution changed from light pink to light green. The quenched fluorescence intensity and absorbance, however, was restored upon the introduction of histidine into the system. Simultaneously, the color of the solution changed from light green to light pink, and the dual-sensing system became "turned on". Therefore, a novel fluorescence and colorimetric dual-signal sensing system based on TSPP was proposed for histidine detection. The results indicated that the linear ranges of the fluorescence sensing system were 8.34 × 10 M - 1.51 × 10 M and 1.85 × 10 M - 1.4 × 10 M with detection limits of 0.282 μM and 10.91 μM (LOD, S/N = 3), respectively. The linear range of the colorimetric sensing system was 2.04 × 10 M-4.35 × 10 M with a detection limit of 11.97 μM (LOD, S/N = 3). Meanwhile, the dual-sensing system provided a promising platform for practical samples sensing applications.

摘要

组氨酸(His)在人类健康和生命活动中发挥着重要作用。当组氨酸摄入不足或过量时,会对人体健康造成危害。其残留也会污染自然环境。因此,建立一种可靠且灵敏的组氨酸检测方法尤为重要。然而,现有的大多数组氨酸检测方法依赖于单一信号的单一变化,易受测试环境因素干扰,且容易产生假阳性结果。相比之下,荧光和比色双信号传感系统不仅能有效提高检测的可靠性,还能显著降低假阳性风险。因此,双信号传感系统逐渐成为研究热点。基于此,本研究选择5,10,15,20-四(4-磺酸苯基)卟啉(TSPP)作为荧光和比色双信号探针用于快速检测组氨酸。由于TSPP分子结构的特殊性,它能与多种物质相互作用,为提高传感系统的特异性,构建“开-关-开”传感系统是最佳选择。因此,成功开发了一种基于TSPP探针并以柠檬酸(CA)为中间体的荧光和比色双传感系统,用于实际样品中组氨酸的定量检测。当红色的TSPP溶液在514nm最佳激发波长下分别获得642nm的荧光发射波长和413nm的紫外可见吸收时,双传感系统的信号“开启”。随着CA的引入,TSPP的荧光强度和吸光度逐渐降低。此时,双传感系统的信号“关闭”,溶液颜色从浅粉色变为浅绿色。然而,当向系统中引入组氨酸时,猝灭的荧光强度和吸光度得以恢复。同时,溶液颜色从浅绿色变回浅粉色,双传感系统“开启”。因此,提出了一种基于TSPP的新型荧光和比色双信号传感系统用于组氨酸检测。结果表明,荧光传感系统的线性范围分别为8.34×10⁻⁶M - 1.51×10⁻⁵M和1.85×10⁻⁵M - 1.4×10⁻⁴M,检测限分别为0.282μM和10.91μM(LOD,S/N = 3)。比色传感系统的线性范围为2.04×10⁻⁵M - 4.35×10⁻⁴M,检测限为11.97μM(LOD,S/N = 3)。同时,该双传感系统为实际样品传感应用提供了一个有前景的平台。

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