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With the fast development of nuclear energy, the issue related to spent nuclear fuel reprocessing has been regarded as an imperative task, especially for the separation of minor actinides. In fact, it still remains a worldwide challenge to separate trivalent An(iii) from Ln(iii) because of their similar chemical properties. Therefore, understanding the origin of extractant selectivity for the separation of An(iii)/Ln(iii) by using theoretical methods is quite necessary. In this work, three ligands with similar structures but different bridging frameworks, Et-Tol-DAPhen (La), Et-Tol-BPyDA (Lb) and Et-Tol-PyDA (Lc), have been investigated and compared using relativistic density functional theory. The electrostatic potential and molecular orbitals of the ligands indicate that ligand La is a better electron donor compared to ligands Lb and Lc. The results of QTAIM, NOCV and NBO suggest that the Am-N bonds in the studied complexes have more covalent character compared to the Eu-N bonds. Based on the thermodynamic analysis, [M(NO)(HO)] + L + 2NO = [ML(NO)] + 8HO should be the most probable reaction in the solvent extraction system. Our results clearly verify that the relatively harder oxygen atoms offer these ligands higher coordination affinities toward both of the An(iii) and Ln(iii) ions compared to the relatively softer nitrogen atoms. However, the latter possess stronger affinities toward An(iii) over Ln(iii), which partly results in the selectivity of these ligands. This work can afford useful information on achieving efficient An(iii)/Ln(iii) separation through tuning the structural rigidity and hardness or softness of the functional moieties of the ligands.

Low frequency ultrasound (<1 MHz) has been demonstrated to be a promising approach for non-invasive neuro-stimulation. However, the focal width is limited to be half centimeter scale. Minimizing the stimulation region with higher frequency ultrasound will provide a great opportunity to expand its application. This study first time examines the feasibility of using high frequency (5 MHz) ultrasound to achieve neuro-stimulation in brain, and verifies the anatomical specificity of neuro-stimulation in vivo. 1 MHz and 5 MHz ultrasound stimulation were evaluated in the same group of mice. Electromyography (EMG) collected from tail muscles together with the motion response videos were analyzed for evaluating the stimulation effects. Our results indicate that 5 MHz ultrasound can successfully achieve neuro-stimulation. The equivalent diameter (ED) of the stimulation region with 5 MHz ultrasound (0.29 ± 0.08 mm) is significantly smaller than that with 1 MHz (0.83 ± 0.11 mm). The response latency of 5 MHz ultrasound (45 ± 31 ms) is also shorter than that of 1 MHz ultrasound (208 ± 111 ms). Consequently, high frequency (5 MHz) ultrasound can successfully activate the brain circuits in mice. It provides a smaller stimulation region, which offers improved anatomical specificity for neuro-stimulation in a non-invasive manner.

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The stability of many MOFs is not satisfactory, which severely limits the exploration of their potential applications. Given this, we have proposed a strategy to improve the stability of MOFs by introducing alkali metal K+ capable of coordinating with metal nodes, which finally induces the interpenetrating uranyl-porphyrin framework to connect as a whole (IHEP-9). The stability experiments reveal that the IHEP-9 has good thermal stability up to 400 °C and can maintain its crystalline state in the aqueous solution with pH ranging from 2 to 11. The catalytic activity of IHEP-9 as a heterogeneous photocatalyst for CO2 cycloaddition under the driving of visible light at room temperature is also demonstrated. This induced interpenetration and fixation method may be promising for the fabrication of more functional MOFs with improved structural stability.

At present, designing novel ligands for efficient actinide extraction in spent nuclear fuel reprocessing is extremely challenging due to the complicated chemical behaviors of actinides, the similar chemical properties of minor actinides (MA) and lanthanides, and the vulnerability of organic ligands in acidic radioactive solutions. In this work, a quantum chemical study on Am(III), Cm(III) and Eu(III) complexes with N,N,N',N'-tetraoctyl diglycolamide (TODGA) and N,N'-dimethyl-N,N'-diheptyl-3-oxapentanediamide (DMDHOPDA) has been carried out to explore the extraction behaviors of trivalent actinides (An) and lanthanides (Ln) with diglycolamides from acidic media. It has been found that in the 1 : 1 (ligand : metal) and 2 : 1 stoichiometric complexes, the carbonyl oxygen atoms have stronger coordination ability than the ether oxygen atoms, and the interactions between metal cations and organic ligands are substantially ionic. The neutral ML(NO3)3 (M = Am, Cm, Eu) complexes seem to be the most favorable species in the extraction process, and the predicted relative selectivities are in agreement with experimental results, i.e., the diglycolamide ligands have slightly higher selectivity for Am(III) over Eu(III). Such a thermodynamical priority is probably caused by the higher stabilities of Eu(III) hydration species and Eu(III)-L complexes in aqueous solution compared to their analogues. In addition, our thermodynamic analysis from water to organic medium confirms that DMDHOPDA has higher extraction ability for the trivalent actinides and lanthanides than TODGA, which may be due to the steric hindrance of the bulky alkyl groups of TODGA ligands. This work might provide an insight into understanding the origin of the actinide selectivity and a theoretical basis for designing highly efficient extractants for actinide separation.

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Separation of trivalent actinides An­(III) from lanthanides Ln­(III) is a worldwide challenge owing to their very similar chemical behaviors. It is highly desirable to understand the nature of selectivity for the An­(III)/Ln­(III) separation with various ligands through theoretical calculations because of their radiotoxicity and experimental difficulties. In this work, we have investigated three dithioamide-based ligands and their extraction behaviors with Am­(III) and Eu­(III) ions using the scalar-relativistic density functional theory. The results show that the dithioamide-based ligands have stronger electron donating ability than do the corresponding diamide-based ones. All analyses including geometry, Mulliken population, QTAIM (quantum theory of atoms in molecules), and NBO (natural bond orbital) suggest that the Am–S/N bonds possess more covalency compared to the Eu–S/N bonds, and the M–S bonds have more covalent character than the M–N bonds. Thermodynamic results reveal that N 2,N 9-diethyl-N 2,N 9-di-p-tolyl-1,10-phenanthroline-2,9-bis­(carbothioamide) (L 1 ) has a stronger complexing ability with metal ions owing to its rigid structure and that N 6,N 6′-diethyl-N 6,N 6′-di-p-tolyl-[2,2′-bipyridine]-6,6′-bis­(carbothioamide) (L 2 ) shows a higher selectivity for the Am­(III)/Eu­(III) separation. In addition, these dithioamide-based ligands possess Am­(III)/Eu­(III) selectivity higher than those of the corresponding diamide-based ones, although the former have weaker complexing ability with metal ions, probably due to the greater covalency of the M–S bonds. This theoretical evaluation provides valuable insights into the nature of the selectivity for the Am­(III)/Eu­(III) separation and information on designing of efficient An­(III)/Ln­(III) separation with dithioamide-based ligands.