1. 贵州省大环化学及超分子化学实验室，贵州大学化学与化工学院，贵州 贵阳 550025 2. Department of Applied Chemistry, Faculty of Science and Engineering, Saga University, Honjo-machi 1, Saga 840-8502, Japan
The Thiacalix[4]arene-Coumarin Fluorescence Probe Recognition for Fe3+ and Bovine Hemoglobin
LI Yan-qin1, MU Lan1, ZENG Xi1*, LI Jun1, Takehiko Yamato2
1. Key Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province, Guizhou University, Guiyang 550025, China 2. Department of Applied Chemistry, Faculty of Science and Engineering, Saga University, Honjo-machi 1, Saga 840-8502, Japan
Abstract：1,3-alternate coumarin substituted thiacalix[4]arene fluorescent probe 1 was synthesised from 1,3-alternate diethyl thiacalix[4]arene and 7-hydroxycoumarin by-step reactions. In DMSO/H2O (φ, 3/7, pH 7) solution, the strong fluorescence emission and UV absorption of probe 1 can be selectively quenched or significantly enhanced by Fe3+ ion. The probe 1 showed high Fe3+ selective fluorescence quenching or absorption enhancement over commonly coexistent metal ions in neutral aqueous media, and the limit of detections were obtained as low as 10-8 mol·L-1 of Fe3+ by fluorescence and absorption spectrometry. Spectral titration, isothermal titration calorimetry and mass spectrometry were showed that probe and Fe3+ form 1∶1 complexes, the constant up to 105 L·mol-1 and coordinate process was spontaneous by the mole binding free energy and entropy of probe with Fe3+. In addition, the probe can identification bovine hemoglobin (BHb) over other proteins through quenched its fluorescence in DMSO/H2O (φ，1/9，Tris-HCl，pH 7，0.1 mol·L-1 NaCl) media. The limit of detection was obtained as 0.12 μg·mL-1 of BHb, as well as a linearity of 0.2～3.0 μg·mL-1, indicating the probe of high sensitivity and quantitation range. It can be used as a selective recognition Fe3+ and BHb of thiacalix[4] arene fluorescent probe.
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