Band 104, Heft 10

An extraction of Th(IV) was performed using 1- methylimidazole (1-MIM) or 2-methylimidazole (2-MIM) as the extractant in imidazolium type ionic liquids (ILs) or n -pentanol. The extractability for Th 4+ in ILs was by far higher than that obtained in n -pentanol. The extraction mechanism was determined by slope analysis and ESI-MS. The transfer of Th 4+ with MIM into ILs proceeded through both a cationic exchange and a neutral solvation mechanism, whereas the partitioning of Th 4+ with MIM into n -pentanol only underwent a neutral solvation mechanism. The thermodynamic parameters values (Δ H , Δ S and Δ G ) for extraction of Th 4+ with 1-MIM in IL were calculated and the results indicated the extraction reaction was spontaneous and went through endothermic process. Separation of Th 4+ from the solution of lanthanides (III) and uranium was also carried out by 1-MIM in ILs and n -pentanol.

Thorium oxide is poorly soluble: unlike uranium oxide, concentrated nitric acid medium is not sufficient to get quantitative dissolution. Addition of small amounts of fluoride is required to achieve thorium oxide total dissolution. The effect of several parameters on thorium oxide dissolution in order to optimize the dissolution conditions is reported in this paper. Thus the influence of solid characteristics, dissolution method, temperature and composition of dissolution medium on ThO 2 dissolution rate has been studied. No complexing agents tested other than fluoride allows total dissolution. Beyond a given HF concentration a decrease of the dissolution rate is observed due to the formation of a precipitate at the solid/solution interface. It was demonstrated by XPS measurements that this precipitate is constituted of thorium fluoride (ThF 4 ) formed during the ThO 2 dissolution. The low concentration of HF required to achieve a total dissolution and the activation energy value measured tends to show a catalytic effect of HF on the dissolution process.

Hydrazine nitrate is being used as a stabilizer for U(IV) as well as Pu(III) during partitioning of Pu in PUREX process by scavenging the nitrous acid present along with nitric acid. As hydrazine hydrate as well as its salts have been successfully used for scrubbing of degradation products of TBP to aqueous phase, experiments were conducted to evaluate the consequence of hydrazine content during Pu partitioning. It was observed that higher amount of hydrazine nitrate along with uranous nitrate in the partitioning stream of PUREX process leads to build up of DBP in aqueous phase and resulted in precipitation of Pu.

Electrochemical pre-concentration has been shown to effectively increase sample sensitivity and decrease processing time; however, the basic mechanism and optimal conditions of the technique remain unknown, specifically for lanthanides. To gain a better understanding of the mechanism of action, the aqueous solution conditions required to maximize the electrochemical pre-concentration of lanthanum (La) were studied. Parameters investigated included pH, applied potential, and ionic strength. To further optimize and elucidate the mechanism of lanthanide pre-concentration, specific interactions of lanthanum with the mercury film electrode were studied. Three possible mechanisms were proposed based on preliminary observations, including ligand bridging, hydroxide formation, and amalgamation.

In this study, the MOF concept contributed to the preparation of a novel, bone-ablating agent composed of Cu(II) using the in vivo generator 166 Dy/ 166 Ho and 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetramethylene phosphonic acid (DOTMP). The product was characterized (IR, elemental analysis: CHN, ICM-MS, PIXE, DLS, XRD) and quality-controlled (radio-thin layer chromatography (RTLC)). The stability and in vitro hydroxyapatite binding was checked up to one week at 37°C in human serum. Radio-MOF crystals and colloidal radio-MOF particles were obtained by varying the synthesizing conditions (including pH and temperature), and they had similar IR patterns and similar elemental analysis results. The estimated chemical formula was [1Lu-1Cu-1Cl-1DOTMP] for both. The final product was synthesized at pH = 8 while stirring at room temperature using 166 Dy/ 166 Ho-nitrate, CuCl 2 , and DOTMP (yield > 99%, RTLC). Dynamic light scattering (DLS) measurements showed particles in the size range of 60 to 100 nm for the resultant radio-MOF particles (RMP). In vitro binding experiments showed acceptable bone-seeking affinity of the prepared formula even after one week of storage in human serum at 37°C. Importantly, this is the first study of the use of the MOF concept to provide a highly-stable organometallic compound containing 166 Dy/ 166 Ho in vivo generator for bone marrow ablation.

Nowadays, the bone-seeking radiopharmaceuticals play an important role in the treatment of the bone-related pathologies. Whereas various phosphonate ligands have already been identified, a DOTA-based bisphosphonate, 4-{[(bis(phosphonomethyl))carbamoyl]methyl}- 7,10-bis(carboxymethyl)-1,4,7,10-tetraazacyclododec- 1-yl (BPAMD) with better characteristics has recently been synthesized. In this study, 90 Y-BPAMD was developed with radiochemical purity >98% and the specific activity of 3.52 TBq/mmol in the optimized conditions as a new bone-seeking therapeutic agent. The complex demonstrated significant stability at room temperature and in human serum even after 48 h. At even low amount of hydroxyapatite (5 mg), more than 90% binding to hydroxyapatite was observed. Biodistribution studies after injection of the complex into the Syrian rats showed major accumulation of the labelled compound in the bone tissue and an insignificant uptake in the other organs all the times after injection. Generally, 90 Y-BPAMD demonstrated interesting characteristics compared to the other 90 Y bone-seeking agents and even 166 Ho-BPAMD, and can be considered as a new bone-seeking candidate for therapeutic applications.

Using radioisotope markers the distribution coefficients (K d ) of the following elements In, Sn, Sb, Te, Bi, Co, Fe, Nb, Sr, Ba, Ag, Cd, Zr, Hf and Ti were determined with different concentrations of HCl, H 2 SO 4 and HNO 3 for the extraction chromatographic resin Uranium and TEtraValent Actinides (UTEVA). This data can be used for separation of elements in complex mixtures, as well as for correct assessment of the elements chemistry with higher valences such as 3, 4, 5 or 6.

As a major contribution to modern web-based education and training in nuclear chemistry we have built and operated a remote-controlled experiment – IonLab – as part of the integrated EUFP7 project CINCHII. The setup is suitable for teaching basics on extraction chromatography and ion exchange using radionuclides. We describe separation of the beta emitting nuclides Sr-90 and Y-90 followed by radiometric detection, but the experiment is easily adapted to other separation schemes. This approach is aimed at institutions in academic or vocational education who need to convey the skills of handling radioactive (or otherwise dangerous, e.g. biotoxic) substances without appropriately licensed laboratory space for teaching. This camera-monitored remote controlled lab experiment has proved to be much closer to a real hands-on training and superior to a mere computer simulation.