Xu Tang,Juan Han,Yun Wang,Xu Bao,Liang Ni,Lei Wang,Longhua Li
A fluorescence probe has been designed and synthesized, and applied with a combined theoretical and experimental study. Research suggests that the probe can be used to sense Zn 2 + and Hg 2 + through selective turn-on fluorescence responses in the aqueous HEPES buffer (0.05M, pH = 7.4). The limit of detection (LOD) were determined as 1.46 × 10 − 7 M (Zn 2 + ) and 2.50 × 10 − 7 M (Hg 2 + ). Moreover, based on DFT, the geometry optimizations of probe 1, [1-Hg 2 + ] complex and [1-Zn 2 + ] complex were carried out using the Gaussian 09 program, in which the B3LYP function was used. The electronic properties of free probe 1 and the metal complexes were studied based on the Natural Bond Orbital (NBO) analyses. The probe 1 has also been successfully applied to detection of Zn 2 + and Hg 2 + in living cells.
In this work, the solvent extraction and complexation behaviors of U(VI) by two novel asymmetrical tetra-alkylcarbamides, N,N’-butyl-N,N’-hexylurea ( L1 : SBHU ) and N,N’-butyl-N,N’-pentylurea ( L2 : SBPU ) in HNO 3 media were systematically investigated. Both two ligands extract U(VI) more effectively than other metals such as Pu(IV), Np(IV), and Th(IV) in a wide range of acidity. Under 5 mol/L HNO 3 , D U reached 5.25, while D Pu = 1.08, D Np = 0.11, D Th = 0.13.. Additionally, no third-phase was present by the extraction of highly uranium concentration solution with SBHU even under 7 mol/L HNO 3 after four cycles demonstrating good acid resistance and resistance to the formation of the third phase. Slope analyses and FT-IR indicate that the U(VI) complexes are a form of UO 2 (NO 3 ) 2 ·2 L for the two ligands during the extraction. Additionally, based on the DFT calculations, the NBO analysis, and topological analysis were analyzed in detail. The results demonstrate that the interactions between ligands and U(VI) are shown mainly as ionic characteristics, and the ligand-to-metal charge transfer was also observed. This study enriches the coordination chemistry of actinides: Th(IV), U(VI), Np(IV), Am(III), and Pu(IV) by tetra-alkylcarbamides, which may shed light on the design and synthesis of novel U(VI) selective ligands.
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