State Key Laboratory of Environment-friendly Energy Materials, School of Materials and Chemistry, Southwest University of Science and Technology, Mianyang 621010, PR China.
State Key Laboratory of Environment-friendly Energy Materials, School of Materials and Chemistry, Southwest University of Science and Technology, Mianyang 621010, PR China.
Spectrochim Acta A Mol Biomol Spectrosc. 2023 May 15;293:122501. doi: 10.1016/j.saa.2023.122501. Epub 2023 Feb 15.
Thorium, as a radioactive element, is always associated with rare earth in nature. So it is an exacting challenge to recognize thorium ion (Th) in the presence of lanthanide ions because of their overlapping ionic radii. Here three simple acylhydrazones (AF, AH and ABr, with the functional group fluorine, hydrogen and bromine, respectively) are explored for Th detection. They all exhibit excellent "turn-on" fluorescence selectivity toward Th among f-block ions in aqueous medium with outstanding anti-interference abilities, where the coexistence of lanthanide and uranyl ions in addition with other ordinary metal ions have negligible effects during Th detection. Interestingly, pH variation from 2 to 11 has no significant influence on the detection. Among the three sensors, AF displays the highest sensitivity to Th and ABr the lowest with the emission wavelengths in the order of λ < λ < λ. The detection limit of AF to Th can reach 29 nM (pH = 2) with a binding constant of 6.64 × 10 M. Response mechanism for AF toward Th is proposed based on the results of HR-MS, H NMR and FT-IR spectroscopies together with DFT calculations. This work provides important implications on the development of related series of ligands in nuclide ions detection and future separation from lanthanide ions.
钍作为一种放射性元素，在自然界中总是与稀土元素共存。因此，由于它们的离子半径重叠，在存在镧系元素离子的情况下识别钍离子（Th）是一项艰巨的挑战。在这里，研究了三种简单的酰腙（AF、AH 和 ABr，分别具有氟、氢和溴官能团）用于 Th 检测。它们都在水相中对 f 区离子表现出出色的“开启”荧光选择性和出色的抗干扰能力，其中在 Th 检测过程中，镧系元素和铀酰离子以及其他普通金属离子的共存几乎没有影响。有趣的是，pH 值从 2 到 11 的变化对检测没有明显影响。在这三种传感器中，AF 对 Th 的灵敏度最高，而 ABr 最低，发射波长的顺序为 λ<λ<λ。AF 对 Th 的检测限可达 29 nM（pH = 2），结合常数为 6.64×10 M。基于高分辨率质谱、1H NMR 和傅里叶变换红外光谱以及密度泛函理论计算的结果，提出了 AF 对 Th 的响应机制。这项工作对发展相关系列配体在核素离子检测和未来与镧系元素离子分离方面具有重要意义。
