基于氟硼二吡咯衍生物比率型荧光探针检测氰根离子

Detection of cyanide ion by ratiometric fluorescent probe based on BODIPY derivative

合成了一种可在含水介质中单一性识别CN^-的比率型荧光探针BODIPY 1.通过荧光光谱和紫外吸收光谱来研究BODIPY 1检测CN^-的能力.结果表明,在四氢呋喃和水(V/V=9/1)的混合溶液中,BODIPY 1的最大吸收波长和荧光最大发射波长分别为515 nm和534 nm(激发波长为515 nm),所测阴离子中,包括CN^-、F^-、Cl^-、Br^-、I^-、ClO_4^-、Ac_O^-、NO_3^-、H_2PO_4^-和HSO_4^-,仅CN^-可与BODIPY 1发生加成反应从而引起其吸收峰蓝移18 nm,并且荧光最大发射波长蓝移20 nm,并伴随着强度降低40%.BODIPY 1检测CN^-的检测限可以达到0.98μmol·L^(-1),低于世界卫生组织规定饮用水中的CN^-的最大含量不能超过1.9μmol·L^(-1).将其应用到实际水样,发现和纯水样的响应基本一致,表明BODIPY 1可用于实际水样的检测.

In this paper,a novel ratiometric fluorescent sensor BODIPY 1 for cyanide（CN^-）detection was developed. Sensing behavior of the probe 1 towards anions was monitored by UVvisible and fluorescence spectroscopies. Results show that the absorption band and fluorescene emission band of BODIPY 1 in a mixture of tetrahydrofuran and water（V/V = 9/1） centered around515 nm and 534 nm（the excitation wavelength is 515 nm）,respectively. Among the tested anions,including CN-,F-,Cl-,Br-,I-,Cl O4-,Ac O-,NO3-,H2PO_4-and HSO4-,only CN-reacted with the dicyanovinyl moiety of BODIPY 1 by nucleophilic addition,leading to a blue shift（18 nm） in the absorption band and a blue shift（20 nm） in the emission band. A concomitant 40% fluorescence intensity decrease from its initial level was also observed. The detection limit of BODIPY 1 was calculated to be 0.98 μmol·L-1,which is lower than the maximum allowed concentration in drinking water（1.9 μmol·L-1） set by the World Health Organization（WHO）. The detection of cyanide in real samples was essentially the same as in pure water,showing that BODIPY 1 can be used to detect real water samples.