Recovery of 177Lu from Irradiated HfO2 Targets for Nuclear Medicine Purposes.

A new method of production of one of the most widely used isotopes in nuclear medicine, 177Lu, with high chemical purity was developed; this method includes irradiation of the HfO2 target with bremsstrahlung photons. The irradiated target was dissolved in HF and then diluted and placed onto a column filled with LN resin. Quantitative sorption of 177Lu could be observed during this process. The column later was rinsed with the mixture of 0.1 M HF and 1 M HNO3 and then 2 M HNO3 to remove impurities. Quantitative desorption of 177Lu was achieved by using 6 M HNO3. The developed method of 177Lu production ensures high purification of this isotope from macroquantities of hafnium and zirconium and radioactive impurities of carrier-free yttrium. The content of 177mLu in 177Lu in photonuclear production was determined. Due to high chemical and radionuclide purity, 177Lu obtained by the developed method can be used in nuclear medicine.

Yields of Photo-Proton Reactions on Nuclei of Nickel and Separation of Cobalt Isotopes from Irradiated Targets.

Nowadays, cobalt isotopes 55Co, 57Co, and 58mCo are considered to be promising radionuclides in nuclear medicine, with 55Co receiving the most attention as an isotope for diagnostics by positron emission tomography. One of the current research directions is dedicated to its production using electron accelerators (via photonuclear method). In our work, the yields of nuclear reactions occurring during the irradiation of natNi and 60Ni by bremsstrahlung photons with energy up to 55 MeV were determined. A method of fast and simple cobalt isotopes separation from irradiated targets using extraction chromatography was developed.

Carbon Nanomaterials for Sorption of 68Ga for Potential Using in Positron Emission Tomography.

In present work, carbon nanomaterials (CNMs) are investigated as potential carriers of 68Ga, which is widely used in positron emission tomography (PET) in nuclear medicine. Sorption behavior of 68Ga was studied onto CNMs of various structures and chemical compositions: nanodiamonds (ND), reduced graphite oxide (rGiO) and multi-walled carbon nanotubes (MWCNT), as well as their oxidized (ND-COOH) or reduced (rGiO-H, MWCNT-H) forms. The physicochemical properties of the nanoparticles were determined by high resolution transmission electron microscopy, x-ray photoelectron spectroscopy, dynamic light scattering and potentiometric titration. The content of 68Ga in the solutions during the study of sorption was determined by gamma-ray spectrometry. The highest degree of 68Ga sorption was observed on ND and ND-COOH samples, and the optimal sorption conditions were determined: an aqueous solution with a pH of 5-7, m/V ratio of 50 µg/mL and a room temperature (25 °C). The 68Ga@ND and 68Ga@ND-COOH conjugates were found to be stable in a model blood solution-phosphate-buffered saline with a pH of 7.3, containing 40 g/L of bovine serum albumin: 68Ga desorption from these samples in 90 minutes was no more than 20% at 25 °Ð¡ and up to 30% at 37 °Ð¡. Such a quantity of desorbed 68Ga does not harm the body and does not interfere with the PET imaging process. Thus, ND and ND-COOH are promising CNMs for using as carriers of 68Ga for PET diagnostics.

Magnesium Potassium Phosphate Compound for Immobilization of Radioactive Waste Containing Actinide and Rare Earth Elements.

The problem of effective immobilization of liquid radioactive waste (LRW) is key to the successful development of nuclear energy. The possibility of using the magnesium potassium phosphate (MKP) compound for LRW immobilization on the example of nitric acid solutions containing actinides and rare earth elements (REE), including high level waste (HLW) surrogate solution, is considered in the research work. Under the study of phase composition and structure of the MKP compounds that is obtained by the XRD and SEM methods, it was established that the compounds are composed of crystalline phases—analogues of natural phosphate minerals (struvite, metaankoleite). The hydrolytic stability of the compounds was determined according to the semi-dynamic test GOST R 52126-2003. Low leaching rates of radionuclides from the compound are established, including a differential leaching rate of 239Pu and 241Am—3.5 × 10−7 and 5.3 × 10−7 g/(cm²âˆ™day). As a result of the research work, it was concluded that the MKP compound is promising for LRW immobilization and can become an alternative material combining the advantages of easy implementation of the technology, like cementation and the high physical and chemical stability corresponding to a glass-like compound.

Hard-and-soft phosphinoxide receptors for f-element binding: structure and photophysical properties of europium(iii) complexes.

New phosphinoyl-containing tetradentate heterocycles preorganised for metal ion binding were designed and prepared in high yields. The X-ray structures of two allied phosphinoyl-bearing 2,2'-bipyridyl and phenanthroline ligands, as well as closely related structures of 2,6-bis(diphenylphosphinoyl)pyridine and 9-(diphenylphosphinoyl)-1,10-phenanthroline-2-one, are reported. Complexes of nitrates of several lanthanides and trifluoroacetate of Eu(iii) with two phosphinoyl-bearing 2,2'-bipyridyl and phenanthroline ligands were isolated and characterised. The first structures of lanthanide complexes with phosphinoyl-bearing 2,2'-bipyridyl and phenanthroline ligands are reported. The nature of the counter-ion is crucial for the coordination environment of the metal ion. The photophysical properties of the complexes differring in both the nature of the ligand and counter-ion were investigated. The photophysical properties of the complexes are strongly ligand- and counter-ion-dependent. Absorbance and luminescence excitation spectra of complexes showed main peaks in the UV range which correspond to the absorption of light by the ligand and these are ligand-dependent. Luminescence spectra of complexes show typical europium emission in the red region with a high quantum yield, which corresponds to the transitions 5D0 → 7FJ (J = 0-6). The value of deviation of the components of 5D0 → 7F2 and 5D0 → 7F1 transitions from the inversion centre shows a larger dependence on the counter-ion than on the nature of the ligand. The value of the luminescence quantum yield is larger for europium complexes with 2,2'-bipyridyl-based ligands and NO3 counter-ions than for complexes with phenanthroline-based ligands and NO3 counter-ions. A low dependence of the luminescence lifetime of Eu complexes on the nature of the ligand has been demonstrated: values in the solid state were in the range 1.1-2.0 ms.

Multiscale Speciation of U and Pu at Chernobyl, Hanford, Los Alamos, McGuire AFB, Mayak, and Rocky Flats.

The speciation of U and Pu in soil and concrete from Rocky Flats and in particles from soils from Chernobyl, Hanford, Los Alamos, and McGuire Air Force Base and bottom sediments from Mayak was determined by a combination of X-ray absorption fine structure (XAFS) spectroscopy and X-ray fluorescence (XRF) element maps. These experiments identify four types of speciation that sometimes may and other times do not exhibit an association with the source terms and histories of these samples: relatively well ordered PuO2+x and UO2+x that had equilibrated with O2 and H2O under both ambient conditions and in fires or explosions; instances of small, isolated particles of U as UO2+x, U3O8, and U(VI) species coexisting in close proximity after decades in the environment; alteration phases of uranyl with other elements including ones that would not have come from soils; and mononuclear Pu-O species and novel PuO2+x-type compounds incorporating additional elements that may have occurred because the Pu was exposed to extreme chemical conditions such as acidic solutions released directly into soil or concrete. Our results therefore directly demonstrate instances of novel complexity in the Å and µm-scale chemical speciation and reactivity of U and Pu in their initial formation and after environmental exposure as well as occasions of unexpected behavior in the reaction pathways over short geological but significant sociological times. They also show that incorporating the actual disposal and site conditions and resultant novel materials such as those reported here may be necessary to develop the most accurate predictive models for Pu and U in the environment.

Interaction of transuranium elements with biologically important ligands: structural and spectroscopic evidence for nucleotide coordination to plutonium.

The first complex of a transuranium element (tetravalent plutonium) with nucleotide (deoxycytidinemonophosphate, dCMP) was synthesized and structurally characterized. The crystal structure of [Pu(4)(NO(3))(8)(HdCMP)(4)(H(2)O)(8)](NO(3))(4).2H(2)O consists of complex cations [Pu(4)(NO(3))(8)(HdCMP)(4)(H(2)O)(8)](4+), NO(3)(-) anions, and water molecules. There are two crystallographically independent Pu atoms in the structure, both having similar surroundings. Each of the Pu atoms is coordinated by three O atoms of phosphate groups belonging to three different (HdCMP)(-) anions, two bidentate nitrate anions, and two water molecules. The crystal structure is confirmed by IR and UV/vis/near-IR spectroscopic data.

Interaction of transuranium elements with biologically important molecules: structural and spectroscopic study of NP(V) complexes with imidazole.

New Np(V) complexes with imidazole, [NpO(2)(CH(3)COO)(Im)(2)(H(2)O)], [(NpO(2))(2)(C(2)O(4))(Im)(6)] x 5 Im x H(2)O, and [NpO(2)(NO(2))(Im)(4)], were synthesized. Their crystal structures were determined using X-ray single-crystal diffractometry. The crystal structures are confirmed by IR and UV-vis spectroscopic data. In all three complexes, neptunium coordinates the imidazole molecule through the nitrogen atom. These complexes are the first example of direct bonding of the imidazole molecule to the actinide atom. These results suggest that coordination of histidine residue in proteins or other imidazole-containing biologically important molecules could occur under usual biological conditions.

Application of ionic liquids for solid-phase extraction of trace elements.

That phosphonium-type ionic liquids (ILs) can be used for preparation of novel solid-phase extractants has been shown. The conditions of IL immobilization on the different matrices (polyacrilonitrile, Amberlite XAD-7, hyper cross-linked polystyrene, and multi-walled carbon nanotubes) were determined. The solid-phase extraction of Pt(IV) from 1-2 M HCl and Pu(IV) from 3 M HNO(3) has been investigated. The possibility of retaining ligands on the solid phases by means of ILs to prepare the complexing solid-phase extractants has been demonstrated.

First structural evidence of actinide-nitrite coordination.

The first nitrite complex of actinide metal, {C(NH 2)3}2[NpO 2(NO 2)(Pic)2], was synthesized, and its crystal structure was determined using X-ray diffractometry and confirmed by NIR and IR spectroscopies. Main crystallographic data: space group P1, triclinic, a = 8.9329(1) A, b = 11.6669(2) A, c = 11.6698(2) A, alpha = 68.080(1) degrees, beta = 88.213(1) degrees, gamma = 73.254(1) degrees, V = 1076.45(3) A (3), and Z = 2.

Colloid transport of plutonium in the far-field of the Mayak Production Association, Russia.

Sorption of actinides, particularly plutonium, onto submicrometer-sized colloids increases their mobility, but these plutonium colloids are difficult to detect in the far-field. We identified actinides on colloids in the groundwater from the Mayak Production Association, Urals, Russia; at the source, the plutonium activity is approximately 1000 becquerels per liter. Plutonium activities are still 0.16 becquerels per liter at a distance of 3 kilometers, where 70 to 90 mole percent of the plutonium is sorbed onto colloids, confirming that colloids are responsible for the long-distance transport of plutonium. Nano-secondary ion mass spectrometry elemental maps reveal that amorphous iron oxide colloids adsorb Pu(IV) hydroxides or carbonates along with uranium carbonates.

Highly porous uranyl selenate nanotubules.

A first amine-templated uranyl selenate based upon highly porous uranyl selenate nanotubules, (C4H12N)14[(UO2)10(SeO4)17(H2O)], has been prepared in the room-temperature reaction of uranyl nitrate, butylamine, and H2SeO4 in aqueous solution. The structure consists of nanometer-scale tubular [(UO2)10(SeO4)17(H2O)]14- units packed in a hexagonal-type fashion. The tubules have elliptical cross section with outer dimensions of 25 x 23 A = 2.5 x 2.3 nm. The internal free crystallographic diameter of the tubules is 12.6 A = 1.26 nm, which is comparable to the effective pore size in large-pore zeolites. This finding demonstrates the possibility of nanostructures for actinides in higher oxidation states and opens up a new area of research and exploration.