基于四苯基乙烯-罗丹明的HClO/ClO^(-)可视化荧光探针的合成及性质研究

Synthesis and Properties of HClO/ClO^(-) Visual Fluorescent Probe Based on Tetraphenylethylene-Rhodamine

次氯酸(HOCl)/次氯酸盐(ClO^(-))作为一种强氧化剂应用广泛,在机体免疫防御中也起着至关重要的作用,过量HOCl/ClO^(-)对环境及人体造成潜在威胁。因此,建立可靠、精准检测HOCl/ClO^(-)的分析方法具有重要意义。通过缩合、还原两步合成得到具有聚集诱导性质的四苯基乙烯-罗丹明类衍生物TPE-RhB2,探针TPE-RhB2在乙醇/水溶液中实现了对ClO^(-)的可视化荧光识别,在505 nm处荧光发生猝灭,猝灭比为90.2%,同时在572 nm处出现新的荧光发射峰。该探针在pH 1~12内荧光响应稳定,并具有较强的抗干扰能力和灵敏度,检出限低至5.32×10^(-7) mol/L,Stokes位移高达155 nm,有望在复杂环境中实现对ClO^(-)的检测。通过ESI-MS谱初步确定ClO^(-)通过氧化水解机制引起了荧光信号和探针溶液颜色变化,根据所建分析方法实现了实际水样中ClO^(-)的检测。

Hypochlorous acid(HOCl)/hypochlorite(ClO^(-)) as a strong oxidant is widely used in life and plays a crucial role in the body′s immune defense.Excessive HOCl/ClO^(-) may pose a potential threat to the environment and human body.Therefore,it is of great significance to establish a reliable and accurate analysis method for HOCl/ClO^(-) detection.In this paper,tetraphenylene-rhodamine derivatives TPE-RhB2 with aggregation induced fluorescence effect was synthesized by condensation and reduction.The probe TPE-RhB2 realized the visual fluorescence recognition of ClO^(-) in ethanol/water.The fluorescence quenching occurred at 505 nm with a quenching ratio of 90.2%,and a new fluorescence emission peak appeared at 572 nm.The fluorescence response of the probe is stable in pH 1~12,and it has strong anti-interference ability and sensitivity.The detection limit is as low as 5.32×10^(-7) mol/L,and the Stokes shift is as high as 155 nm.It is expected to realize the detection of ClO^(-) in complex environment.The fluorescence signal and the color change of the probe solution caused by the oxidation hydrolysis mechanism of ClO^(-) were preliminarily determined by ESI-MS spectrum,and the detection of ClO^(-) in actual water samples was realized according to the established analytical method.