芘-邻香兰素类Cu(Ⅱ)荧光传感器的制备及其性能

Preparation and properties of pyrene-o-vanillin Cu(Ⅱ) fluorescence sensor

采用芘为荧光基团、肼为连接臂,根据席夫碱反应,制备芘-邻香兰素类Cu(Ⅱ)荧光传感器(TM),其结构经熔点、1HNMR、13CNMR、IR、MS和元素分析表征。TM在乙腈体系中对Cu(Ⅱ)有很好的紫外、荧光和比色响应,响应时间为12 min,不受其他金属离子干扰且对Cu(Ⅱ)的识别可视、可逆。通过荧光滴定法计算出TM对Cu(Ⅱ)的检出限为0.48μmol/L。TM具有桔黄色的固体荧光,但其乙腈溶液荧光很弱,通过对比加水或Cu(Ⅱ)的荧光强度,结合紫外和荧光滴定光谱以及量子化学计算,探讨了TM的聚集诱导发光(AIE)识别机理。TM可用于自来水中Cu(Ⅱ)的检测,回收率为91.2%~107.3%,相对误差为6.3%~8.8%。高选择性和对Cu(Ⅱ)的快速响应使TM有望成为AIE型荧光传感器,用于实际样品中Cu(Ⅱ)的检测。

A novel pyrene-o-vanillin Cu(Ⅱ) fluorescence sensor TM was prepared with pyrene as fluorophore and hydrazine as linker by Schiff base reaction. Its structure was characterized by melting point, 1 HNMR, 13 CNMR, IR, MS and elemental analysis. Sensor TM had good UV, fluorescence and colorimetric response to Cu(Ⅱ) in acetonitrile system with response time of 12 min. Moreover, sensor TM was not interfered by other metal ions and could recognize Cu(Ⅱ) visually and reversibly. The detection limit of TM to Cu(Ⅱ) was calculated to be 0.48 μmol/L by fluorescence titration method. Sensor TM had orange solid fluorescence. However, it showed a very weak fluorescence in acetonitrile solution. By comparing the fluorescence intensity after adding water or Cu(Ⅱ), the aggregation-induced emission(AIE) recognition mechanism of TM was discussed under the aid of UV and fluorescence titration spectra as well as quantum chemical calculation. Sensor TM could be used for the detection of Cu(Ⅱ) in tap water with a recovery of 91.2%~107.3%, and relative error of 6.3%~8.8%. High selectivity and rapid response of TM to Cu(Ⅱ) make it as a new AIE-type fluorescence sensor for the detection of Cu(Ⅱ) in actual samples.