一种同时分辨识别Zn^(2+)和F^-离子的双功能探针（英文）

A Readily Accessible Difunctional Probe: Simultaneous Recognition of Cation Zn^(2+) and Anion F^- via Distinguishable Wavelengths

由8-甲酰基-7-羟基香豆素与碳酰肼经一步缩合反应可制得探针1。研究发现,探针1对Zn^(2+)和F-离子均呈现荧光增强和比率比色的高灵敏和高选择性响应,检出限低至10-8 mol·L^(-1)。通过光谱、ITC、1H NMR滴定及质谱分析,详细地研究了探针与离子形成的配合物性质。在不同的介质中,探针不仅同时表现出对金属阳离子Zn^(2+)和对阴离子F-的识别,而且吸收和发射波长均有显著的差异:1-Zn^(2+)配合物的最大吸收波长为360 nm,而1-F-配合物为400 nm;1-Zn^(2+)配合物的荧光激发和发射波长分别为360和454 nm,而1-F-配合物分别为400和475 nm。此外,探针1还能应用于活体PC3细胞中Zn^(2+)的荧光成像。

The probe 1 was readily prepared via condensation of 8-formyl-7-hydroxy-coumarin and carbonic dihydrazide in a one-step procedure. Probe 1 exhibited high sensitivity and selectivity towards Zn2＋ and F- through a ＂turn-on＂ fluorescence response and/or ratiometric eolorimetric response with low detection limits of the order of 10-8 mol.L-1. The complex behaviour was fully investigated by spectral titration, isothermal titration calorimetry, 1H NMR spectroscopic titration and mass spectrometry. Interestingly, probe 1 not only recognizes the cation Zn2＋ and the anion F-, but can also distinguish between these two ions via the max wavelength in their UV- Vis spectra （360 nm for 1-Zn2＋ vs 400 nm for I-F- complex） or their fluorescent spectra （Aex, kern=360, 454 nm for 1-Zn2＋ vs An, Aem=400, 475 nm for I-F- complex） due to their differing red-shifts. Additionally, probe 1 has been further explored in the detection of Zn2＋ in living cells.