Extraction chromatographic method for the separation of actinides and lanthanides using EDHBA grafted AXAD-16 polymer

A new extraction chromatographic method has been developed by grafting chloromethylated polymer support with 4-ethoxy-N,N-dihexylbutanamide (EDHBA), for the selective extraction of U(VI), Th(IV), La(III) and Nd(III) from highly acidic matrices. The developed grafted polymer has been characterized using ¹³C-CPMAS NMR spectroscopy, FT-NIR spectroscopy and also by CHN elemental analysis. The water regaining capacity of the grafted polymer is studied by TGA measurements and the active participation of the amide moiety towards metal ion complexation has been confirmed by Far IR spectroscopy. For the quantitative extraction of metal ions to the resin phase, various physio-chemical parameters are optimized by both static and dynamic methods. The developed amide grafted polymeric matrix shows good distribution ratio values even at high acidities, with the maximum metal sorption capacity values being 0.36, 0.69, 0.32 and 0.42 mmol g⁻¹ for U(VI), Th(IV), La(III) and Nd(III), respectively, at 6 M HNO₃ medium. The kinetics of metal ion phase equilibration is found to be moderately fast, with t_1/2 values of <6 min, for all the analytes of interest. The limits of analyte quantification (LOQ) using the developed method are in the range of 15-30 μg L⁻¹. Moreover, the sequential separation of the sorbed actinides and lanthanides could be achieved by first eluting with 100 mL of distilled water (for actinides) followed by elution with 20 mL of 0.1 M EDTA (for lanthanides). The selectivity behavior and the practical applicability of the developed resin are tested using synthetic low level nuclear reprocessing mixtures and also with monazite sand. The analytical data are within 3.8% relative standard deviation, reflecting the reproducibility and reliability of the developed method.     

A facile solvent-free three-component domino synthesis of novel 2,4-diaryl-5,6-dihydrobenzo[j][1,7]phenanthrolines

Molecular Diversity - A simple, efficient and green procedure for the synthesis of novel 2,4-diaryl-5,6-dihydrobenzo[j][1,7]phenanthrolines has been developed via a Krohnke-type one-pot...     

Crystallographic evidence of nitrate-pi interactions involving the electron-deficient 1,3,5-triazine ring

The reaction of Zn(NO3)2.6H2O or Cu(NO3)2.3H2O with the star-shaped ligand 2,4,6-tris(di-2-picolylamino)[1,3,5]triazine (dipicatriz) in acetonitrile results in the formation of the mono- or trinuclear coordination compounds [Zn(dipicatriz)(NO3)2] (1), [Zn3(dipicatriz)(NO3)6](CH3CN)3 (2), and [Cu3(dipicatriz)(NO3)2(H2O)6](NO3)4 (3), depending on the metal-to-ligand ratios used during the crystallization process. Their crystal structures exhibit unique supramolecular interactions. Compounds 1 and 2 show anion-pi interactions between coordinated nitrate ions and the s-triazine ring. Compound 3 exhibits remarkable interactions between two noncoordinated nitrate anions and the two faces of the electron-deficient heteroaromatic ring, corroborating earlier theoretical investigations in this area. New theoretical investigations have been carried out on nitrate-pi interactions, taking into account the particular position of the anion toward the aromatic ring observed in the crystal structures.