Theoretical Insights into the Selective Separation of Am(III)/Eu(III) Using Hydrophilic Triazolyl-Based Ligands.

Designing ligands with efficient actinide (An(III))/lanthanide (Ln(III)) separation performance is still one of the key issues for the disposal of accumulated radioactive waste and the recovery of minor actinides. Recently, the hydrophilic ligands as promising extractants in the innovative Selective ActiNide Extraction (i-SANEX) process show excellent selectivity for Am(III) over Eu(III), such as hydroxylated-based ligands. In this work, we investigated the selective back-extraction toward Am(III) over Eu(III) with three hydrophilic hydroxylated triazolyl-based ligands (the skeleton of pyridine La, bipyridine Lb, and phenanthroline Lc) using scalar-relativistic density functional theory. The properties of three hydrophilic hydroxylated ligands and the coordination structures, bonding nature, and thermodynamic properties of the Am(III) and Eu(III) complexes with three ligands have been evaluated using multiple theoretical methods. The results of molecular orbitals (MOs), quantum theory of atoms in molecules (QTAIMs), and natural bond orbital (NBO) reveal that Am-N bonds possess more covalent character compared to Eu-N bonds. The thermodynamic results indicate that the complexing ability of Lb and Lc with metal ions is almost the same, which is stronger than that of La. However, La has the best Am(III)/Eu(III) selectivity among three ligands, which is attributed to the largest difference in covalency between Am-Ntrzl and Eu-Ntrzl bonds in MLa(NO3)3. This work provides an in-depth understanding of the preferential selectivity of the hydrophilic hydroxylated ligands with An(III) over Ln(III) and also provides theoretical support for designing potential hydrophilic ligands with excellent separation performance of Am(III)/Eu(III).

Theoretical Insights into the Separation of Am(III)/Eu(III) by Hydrophilic Sulfonated Ligands.

In this work, we focused on the separation of Am(III)/Eu(III) with four hydrophilic sulfonated ligands (L) based on the framework of phenanthroline and bipyridine through scalar relativistic density functional theory. We studied the electronic structures of [ML(NO3)3] (M = Am, Eu) complexes and the bonding nature between metal and ligands as well as evaluated the separation selectivity of Am(III)/Eu(III). The tetrasulfonated ligand L2 with a bipyridine framework has the strongest complexing ability for metal ions probably because of the better solubility and flexible skeleton. The disulfonated ligand L1 has the highest Am(III)/Eu(III) selectivity, which is attributed to the covalent difference between the Am-N and Eu-N bonds based on the quantum theory of atoms in the molecule analysis. Thermodynamic analysis shows that the four hydrophilic sulfonated ligands are more selective toward Am(III) over Eu(III). In addition, these hydrophilic sulfonated ligands show better complexing ability and Am(III)/Eu(III) selectivity compared to the corresponding hydrophobic nonsulfonated ones. This work provides theoretical support for the separation of Am(III)/Eu(III) using hydrophilic sulfonated ligands.

[Analysis of apoptosis-related gene expression in different serum level of insulin-like growth factor-1 in mice breast cancer tissue].

OBJECTIVE: A stable primary breast cancer model in liver-specific insulin-like growth factor 1 (IGF-1) deficient (LID) mice and control mice was established. To screen apoptosis related genes expression in different serum IGF-1 levels by gene chip and flow cytometry. METHODS: The LID mice and control mice were used. Induction of breast cancer was achieved by using the 7,12-dimethylbenz(a) anthracene. Ginsenoside Rg3 was used to interfering therapy treatment. The incidence of breast cancer in every group was compared, and expression of apoptosis associated genes was detected by gene chip and flow cytometry. RESULTS: The incidence of tumor in none ginsenoside Rg3 injected control mice was 66.7%. The incidence of tumor in ginsenoside Rg3 injected LID mice was 12.0% which was significantly lower than any other group (P < 0.05). The apoptosis percentage in none ginsenoside Rg3 injected control mice was (2.7 +/- 0.7)%. The apoptosis percentage in ginsenoside Rg3 injected LID mice was (14.0 +/- 1.7)%. The results of gene chip indicated that in contrast to LID mice, LTA, LTB, TNF-alpha, TRAIL, TRANCE, BLK, BOK, CASP8, TRAF5, and APAF1 genes were down-regulated, and LTBR, TRAF4 genes were up-regulated in the breast cancer tissues of control mice. Application of ginsenoside Rg3 therapy could change the expression of these genes. CONCLUSIONS: Circulating IGF-1 levels play a role in the onset and development of breast cancer. Degrade serum IGF-1 level is able to promote apoptosis by affecting the expression of a series of apoptosis related genes consequently inhibit the growth of breast cancer. There was a synergistic effect with the application of ginsenoside Rg3.