Radiochemical separation and quality assessment for the <Superscript>68</Superscript>Zn target based <Superscript>64</Superscript>Cu radioisotope production

The radiochemical separation of the different radionuclides (⁶⁴Cu, ⁶⁷Cu, ⁶⁷Ga, ⁶⁶Ga, ⁵⁶Ni, ⁵⁷Ni, ⁵⁵Co, ⁵⁶Co, ⁵⁷Co, ⁶⁵Zn, ¹⁹⁶Au) induced in the Ni supported Cu substrate — ⁶⁸Zn target system, which was bombarded with the 29.0 MeV proton beam, was performed by ion-exchange chromatography using successive isocratic and/or concentration gradient elution techniques. The overlapped gamma-ray spectrum analysis method was developed to assess the ⁶⁷Ga and ⁶⁷Cu content in the ⁶⁴Cu product and even in the post-⁶⁷Ga production ⁶⁸Zn target solution without the support of radiochemical separation. This method was used for the assessment of ⁶⁴⁺⁶⁷Cu radioisotope separation from ⁶⁷Ga, the quality control of ⁶⁴Cu product and the determination of the ⁶⁸Zn (p,2p)⁶⁷Cu reaction yield. The improvement in the targetry and the optimization of proton beam energy for the ⁶⁸Zn target based ⁶⁴Cu and ⁶⁷Ga production were proposed based on the stopping power and range of the incident proton and on the excitation functions, reaction yields and different radionuclides induced in the target system.     

Influence of biological activity on <Superscript>65</Superscript>Zn and <Superscript>109</Superscript>Cd removal from tidal water by chronically-polluted mangrove sediments

The biological activity influence on the mangrove sediment capacity to remove ⁶⁵Zn and ¹⁰⁹Cd from tidal water was evaluated in a site chronically polluted. Benthic Activity Indexes (BAI), corresponding to relative estimates of biological impact on radiotracer accumulation, were higher for ¹⁰⁹Cd (~?38%) than for ⁶⁵Zn (~?10%) in the top centimetre of sediment. However, BAI exceeded 96% for deeper sediment layers. This apparent decrease in radiotracer diffusion into deep sediments through biological activity inhibition is stronger than reported for much less polluted mangrove nearby, suggesting that benthic organisms tolerant of chronic metal pollution may affect metal sorption mechanisms.     

Synthesis,crystal structures,and antibacterial activities of Schiff base zinc(II) complexes [Zn(L<Superscript>1</Superscript>)<Subscript>2</Subscript>] and [Zn(L<Superscript>2</Superscript>)<Subscript>2</Subscript>]

The reaction of cyclopentylamine with 2-hydroxy-1-naphthaldehyde and 5-nitrosalicylaldehyde, respectively, in methanol affords two new Schiff bases, 1-(cyclopentyliminomethyl)naphthalen-2-ol (HL¹) and 4-nitro-2-(cyclopentyliminomethyl)phenol (HL²). Two new zinc(II) complexes, [Zn(L¹)₂] (I) and [Zn(L²)₂] (II), derived from the Schiff bases, have been prepared and characterized by single-crystal X-ray diffraction, FT-IR, and elemental analysis. Complex I crystallizes in the monoclinic space group P2₁/c with a = 17.834(4), b = 14.738(3), c = 9.868(2) Å, β = 91.20(3)°, V = 2593.1(9) ų, Z = 4. Complex II crystallizes in the triclinic space group P \(\bar 1\) with a = 10.206(1), b = 10.502(1), c = 12.554(1) Å, α = 66.771(2)°, β = 78.133(2)°, γ = 76.292(2)°, V = 1191.8(1) ų, Z = 2. The Zn atom in each complex is coordinated by two N and two O atoms from two Schiff base ligands, forming a tetrahedral geometry. The Schiff bases and the complexes were assayed for antibacterial activities.     

Radiochemical separation of <Superscript>67</Superscript>Ga from Zn and Cu using the adsorbent resin Amberlite XAD-7

Summary A column chromatography was developed using a nonionic, polar adsorbent resin Amberlite XAD-7 for routine radiochemical separation of ⁶⁷Ga from Zn and Cu. 7M HCl was found to be the optimum concentration for adsorption of ⁶⁷Ga and elution of both Zn and Cu. Distilled water was used for elution of ⁶⁷Ga from the column. The optimum flow rate of the solutions on to the column was 5 ml/min. The concentrations of Zn and Cu in the final product (30 ml), measured by a polarography method, were 2.0 and 0.5 ppm, respectively. A solvent extraction method, using diisopropyl ether/7M HCl system was also tested to perform the same separation and a comparison between the two methods was made. The radiochemical chromatographic separation system is simple in design and easy to operate for separations in a hot cell.     

Recovery of <Superscript>65</Superscript>Zn from waste solutions from gallium targets at Brookhaven Linac Isotope Producer

A procedure for recovery of ⁶⁵Zn from acidic Ga-rich solutions generated in ⁶⁸Ge production process was developed and implemented in a “hot cell” environment. A one step simple separation was carried out on anion exchange column filled with Biorad AG1-X8 resin. With ⁶⁵Zn recovery yields of more than 95% this procedure is currently routinely used at Brookhaven Linac Isotope Producer.     

Adducts of zinc and copper(II) dialkyldithiocarbamate complexes with dialkylamines: Synthesis,EPR, and <Superscript>13</Superscript>C and <Superscript>15</Superscript>N CP/MAS NMR

Crystalline adducts of zinc and copper(II) dithiocarbamate (Dtc) complexes with dialkylamines [M(NHR′₂)(S₂CNR₂)₂] (M = Zn, ⁶³Cu, ⁶⁵Cu; R = CH₃, C₂H₅, or R₂ = (CH₂)₄O; R′ = C₂H₅, C₃H₇) have been preparatively isolated. The structures and spectral properties of the adducts have been studied by EPR and ¹³C and ¹⁵N MAS NMR. Chemisorption of bases on powders of dinuclear dithiocarbamates leads to their dissociation into monomeric adducts. Computer simulation demonstrates that the experimental EPR spectra of isotope-substituted copper(II) adducts have an individual character. The geometry of the copper polyhedra is intermediate between a trigonal bipyramid (TBP) and a tetragonal pyramid (TP). The TBP and TP contributions have been quantified based on EPR data. ¹³C and ¹⁵N MAS NMR data show that the Dtc ligands incorporated into the zinc adduct molecule are structurally nonequivalent. The dependence of the isotropic ¹⁵N chemical shifts of the Dtc groups on the alkyl substituents at the nitrogen atom is interpreted based on the concept of joint manifestation of the (+)inductive effect of the alkyl substituents and the mesomeric effect of the Dtc groups.     

Changes in structural and conducting characteristics of zinc nanotubes by bombardment with Xe<Superscript>+22</Superscript> heavy ions

Results of targeted modification of the structure and properties of ordered arrays of zinc nanotubes (Zn NTs) by accelerated Xe⁺²² heavy ions with a fluence of 1 × 10⁹ to 5 × 10¹¹ cm^–2 in the energy range of 1.0–1.75 MeV/nucleon are reported. Dynamics of changes in the crystallite shape and orientation of Zn NTs before and after irradiation has been studied by X-ray diffraction. It has been shown that irradiation with accelerated ions has a significant effect on the texture coefficients of Zn NTs. In addition, at a fluence of 1 × 10¹¹ m^–2 or higher, the formation of loose areas in the structure of Zn NTs as a result of partial degradation of the crystal structure and, consequently, a decline in conductivity are observed.     

Zinc(II) complexes of 4-aminoantipyrine (AAP). Crystal structure of [Zn(AAP)<Subscript>2</Subscript>Cl<Subscript>2</Subscript>]

Zinc(II) complexes of 4-aminoantipyrine (AAP), [Zn(AAP)₂X₂] (X = Cl^–, I^–) and [Zn(AAP)(CN)₂] · 2H₂O were prepared and characterized by elemental analysis, IR and NMR (¹H & ¹³C) spectroscopy. The crystal structure of [Zn(AAP)₂Cl₂] (1) was determined by X-ray crystallography. The structural analysis of 1 shows that the complex exists as a monomeric nonionic molecule with zinc atom bound to two AAP ligands and two chloride ions adopting a distorted tetrahedral geometry. In [Zn(AAP)₂(CN)₂] · 2H₂O, the appearance of a band at 2162 cm^–1 in IR and resonances around 142 ppm in the ¹³C NMR spectra indicated the binding of cyanide to zinc(II).     

Two novel four-coordinated zinc(II) complexes [Zn(dmatrz)<Subscript>2</Subscript>Cl<Subscript>2</Subscript>] and [Zn(dmatrz)<Subscript>2</Subscript>(SCN)<Subscript>2</Subscript>] exhibiting strong blue fluorescent properties

Two novel complexes, [Zn(dmatrz)₂]Cl₂ (1) and [Zn(dmatrz)₂(SCN)₂] (2), have been prepared and characterized by X-ray crystallography, absorption and luminescence spectrometries (dmatrz=3,5-dimethy-4-amino-1,2,4-triazole). The coordination environment of the zinc(II) ions in (1) and (2) has a distorted tetrahedral geometry completed via two independent nitrogen atoms of two triazole ligands and two anions, respectively. Both (1) and (2) show strong blue luminescence properties. Furthermore, (1) displays stronger blue photoluminescence than (2) as the result of different anions (Cl^- and SCN^-) coordinated to the zinc(II) ions.     

Relationships among <Superscript>137</Superscript>Cs, <Superscript>133</Superscript>Cs,and K in plant uptake observed in Japanese agricultural fields

Plant uptake of radiocesium (¹³⁷Cs) was investigated in consideration of the relationships with naturally existing ¹³³Cs and potassium (K). We first determined plant-unavailable fraction of ¹³⁷Cs in soil by batch sorption and sequential extraction methods with a radiotracer. Then, using the data obtained from the batch sorption and extraction methods, we clarified the relationships of plant-available and plant-unavailable fractions between ¹³⁷Cs, ¹³³Cs, and K in soil. Additionally, ¹³⁷Cs concentrations in crop were estimated using ¹³⁷Cs in soil and several factors, i.e. fixation ratio of ¹³⁷Cs in soil, cation exchange capacity, and K concentration in crop. The results implied that the fixation ratio of ¹³⁷Cs in soil was a very important key to understanding ¹³⁷Cs plant uptake.     

Preparation of <Superscript>26</Superscript>Al, <Superscript>59</Superscript>Ni, <Superscript>44</Superscript>Ti, <Superscript>53</Superscript>Mn and <Superscript>60</Superscript>Fe from a proton irradiated copper beam dump

The station for pions cancer therapy was operated at PSI from 1980 to 1992. After a cooling time of 12 years it’s made of copper beam dump was cut and samples were taken for analytical purposes. The sampling collected about 500 g of high active copper chips that can be used for separation of exotic radionuclides. The analyses by gamma spectrometry, LSC and AMS showed main nuclides present to be ⁶⁰Co, ⁵⁴Mn, ²²Na, ⁶⁵Zn, ²⁶Al, ⁵³Mn, ⁵⁹Ni, ⁶³Ni, ⁵⁵Fe and ⁶⁰Fe and ⁴⁴Ti with a daughter nuclide ⁴⁴Sc. In the frame of ERAWAST project a procedure combining selective precipitation and ion exchange for the separation of the rare radionuclides from the copper beam dump was developed. The proposed separation procedure is easy for remote controlled implementation in a hot cell. The ion exchange separation of Ni, Al, Mg, Ti and Fe was complete and high decontamination factors for copper and cobalt were achieved. Based on the developed procedure a remotely controlled system for separation of exotic radionuclides from the copper chips was set up. The full scale system was installed in a hot cell where high activity levels can be handled. In order to evaluate the reliability and functionality of the system extensive tests have been done. During the test period 13.86 g in total of the proton irradiated copper beam dump were processed for separation of ²⁶Al, ⁵⁹Ni, ⁵³Mn, ⁴⁴Ti and ⁶⁰Fe. The results showed that the system was operational and the radionuclide separation was selective with high chemical yield. The procedure manages as well the generated liquid wastes containing high level of ⁶⁰Co activity.     

Facile one-pot synthesis of nano-zinc hydroxide by electro-dissolution of zinc as a sacrificial anode and the application for adsorption of Th<Superscript>4+</Superscript>, U<Superscript>4+</Superscript>, and Ce<Superscript>4+</Superscript> from aqueous solution

Facilely synthesized zinc hydroxide nanoparticles by electro-dissolution of zinc sacrificial anodes were investigated for the adsorption of thorium (Th⁴⁺), uranium (U⁴⁺) and cerium (Ce⁴⁺) from aqueous solution. Various operating parameters such as effect of pH, current density, temperature, electrode configuration, and electrode spacing on the adsorption efficiency of Th⁴⁺, U⁴⁺ and Ce⁴⁺ were studied. The results showed that the maximum removal efficiency was achieved for Th⁴⁺, U⁴⁺ and Ce⁴⁺ with zinc as anode and stainless steel as cathode at a current density of 0.2 A/dm² and pH of 7.0. First- and second-order rate equations were applied to study the adsorption kinetics. The adsorption process follows second order kinetics model with good correlation. The Langmuir, Freundlich adsorption models were applied to describe the equilibrium isotherms and the isotherm constants were determined. The experimental adsorption data were fitted to the Langmuir adsorption model. Thermodynamic parameters such as free energy (ΔG°), enthalpy (ΔH°), and entropy changes (ΔS°) for the adsorption of Th⁴⁺, U⁴⁺ and Ce⁴⁺ were computed to predict the nature of adsorption process. Temperature studies showed that the adsorption was endothermic and spontaneous in nature.     

Study of <Superscript>239</Superscript>Pu, <Superscript>144</Superscript>Ce,and <Superscript>90</Superscript>Sr Behavior During Radioactive Wastes Treatment by Thermal Plasma Technology

A computer model is used to study the volatility of some radioelements (Cerium, Plutonium and Strontium) during radioactive wastes treatment by thermal plasma technology. This model is based on the calculation of system composition using the free enthalpy minimization method, coupled with the equation of mass transfer at the reactional interface. The model enables the determination of the effects of various parameters (e.g., temperature, plasma current, and presence of oxygen in the carrier gas) on the radioelement volatility. The obtained results indicate that any increase in molten bath temperature causes an increase in the radioelement volatility. It is also found that the oxygen flux in the carrier gas strengthens the radioelement incorporation in the containment matrix. For electrolyses effects, an increase in the plasma current increases both the vaporization speed and the vaporized quantities of ²³⁹Pu, ¹⁴⁴Ce, and ⁹⁰Sr.     

Preparation and preliminary evaluation of <Superscript>211</Superscript>At-labeled amidobisphophonates

In this paper, 3-amino-1-hydroxypropylidene-1,1-bisphosphonate(APB), a amidobisphophonate was synthesized and labeled with the α-emitter ²¹¹At by an indirect method using N-succinimidyl 5-(tributylstannyl)-3-pyridinecarboxylate (SPC) as a bi-functional linker, and the conjugated amidobisphophonate (²¹¹At-SAPC-APB) was preliminarily evaluated in vitro and in vivo by comparison with free astatide (²¹¹At⁻) and ^99mTc-MDP. 3-amino-1-hydroxypropylidene-1,1-bisphosphonate(APB) was prepared using β-alanine as the starting material. With SPC bi-functional linker, APB was conjugated with ²¹¹At in a labeling yield of 80–90% with radiochemical purity of more than 99%. The conjugated amidobisphophonate (²¹¹At-SAPC-APB) exhibited considerable stability in vitro, in that the radiochemical purity of ²¹¹At-SAPC-APB was still more than 98% in 0.1 mol/L PBS (pH 7.6) or in fetal calf serum, even stayed for 24 h at room temperature (RT). Biodistribution of ²¹¹At-SAPC-APB was investigated in NIH strain mice by I.V injection. The results showed that ²¹¹At-SAPC-APB could rapidly locate in shank, with the maximum uptake of 23.70 ± 2.29% I.D/g at 6 h, earlier than that of ^99mTc-MDP at 12 h, and stayed in the bone for long time. Moreover, ²¹¹At-SAPC-APB uptake in some key organs or tissues, especially in thyriod, stomach, lung and spleen, was much less than that of free astatide (²¹¹At⁻), implying that ²¹¹At-SAPC-APB was constantly stable in vivo as well as in vitro. These results indicated that ²¹¹At-SAPC-APB will be a suitable candidate for the targeted radiotherapy of bone metastases and should be further investigated.     

Synthesis,Structure, and Keto-Enol Tautomerism of 3-R<Superscript>1</Superscript>-5,5-R<Superscript>2</Superscript>,R<Superscript>2</Superscript>-6-R<Superscript>3</Superscript>-2,3,5,6-Tetrahydropyran-2,4-diones

Ethyl esters of 2,4-dibromo-2-R¹-4-R²-3-oxopentanoic and -hexanoic acids react with zinc and aliphatic or aromatic aldehydes under the conditions of the Reformatskii reaction to give 3-R¹-5,5-R², R²-6-R³-2,3,5,6-tetrahydropyran-2,4-diones, which are obtained in three forms: keto, enol with enolization of the keto group, and enol with enolization of the ester group. The keto form is isolated by crystallization from a mixture of CCl₄ and petroleum ether; the first enol form, from MeOH, EtOH, and polar aprotic solvents; and the second enol form, from CHCl₃. The second enol form is oxidized in DMSO to form a keto compound containing a hydroxy group at the 3-position of the heteroring.     

Electrocarboxylation of CCI<Subscript>4</Subscript> in MeCN during electrolysis with the sacrificial Zn anode

The regularities of galvanostatic electrocarboxylation of CCl₄ in Alk₄NBr/MeCN in an undivided cell with sacrificial Zn anode were studied. The major product of the electrolysis is zinc trichloroacetate, which is formed as a result of the reaction of the cathode-generated CCl₃- anion with CO₂. The further trichloroacetate reduction is prevented by cathode passivation. Therefore, small amounts of zinc dichloro- and monochloroacetates are formed due to the chemical reduction of zinc trichloroacetate with Zn⁰ rather than the cathodic reduction. Zero-valence zinc is formed in minor amounts when Zn²⁺ ions are discharged at the cathode surface because of the low solubility of ZnBr₂ in MeCN. The treatment of (Cl₃CCOO)₂Zn with H₂SO₄ in MeOH gives Cl₃CCO₂Me in 11% yield based on the starting CCl₄.     

Preparation of [<Superscript>66</Superscript>Ga]bleomycin complex as a possible PET radiopharmaceutical

Summary Gallium-66 (T_1/2 = 9.49 h) is an interesting radionuclide that has potential use for positron emission tomography (PET) imaging of biological processes in intermediate to slow target tissue uptake. ⁶⁶Ga was produced in the NRCAM cyclotron as a result of 15 MeV proton bombardment of ⁶⁶Zn with current intensity of 180 μA (yield 11.2 mCi/μAh). Bleomycin (BLM) was labeled with [⁶⁶Ga]GaCl₃     

Determination of <Superscript>241</Superscript>Am/<Superscript>243</Superscript>Am ratios

Determination of ²⁴¹Am/²⁴³Am ratios is required for vanous purposes including assay of Am by isotope dilution techniques. Alpha-spectrometry on electrodeposited sources is a preferred technique for this determination. However, there is an inherent problem of tail contribution which necessitates the use of suitable algorithms to account for the same. Recently, in the frame of a Coordinated Research Program (CRP) of the International Atomic Energy Agency (IAEA), WinALPHA software has been developed which is a combination of an asymmetrical Gaussian for the main part of the peak and a low energy function. Therefore, it was of interest to compare the use of this algorithm with the routinely used method, in our laboratory, based on geometric progression (G. P.) decrease. Since, there are no reference materials available commercially for ²⁴¹Am/²⁴³Am ratios, synthetic mixtures covening a wide range (0.3 to 2.0) of ²⁴¹Am/²⁴³Am α-activity ratios were used and un-ignited electrodeposited sources were prepared for α-spectrometry. The α-spectra obtained using PIPS detector, were evaluated using the two algonthms The ²⁴¹Am/²⁴³Am α-activity ratios obtained were also compared with those determined by thermal ionization mass spectrometry (TIMS). An agreement of about 1% was obtained in the ²⁴¹Am/²⁴³Am ratios determined by the two methods and also by using the two algorithms for α-spectrum evaluation.     

Evaluation of <Superscript>137</Superscript>Cs soil-to-plant transfer: Natural and model experiments

Soil and meadow grass were sampled in the whole territory of Lithuania in 1992–2000. For the laboratory experiment, spring wheat Triticum aestivum L. “Nandu” was used because its root system type is similar to that of perennial meadow grass. The ¹³⁷Cs soil-to-plant transfer factor of spring wheat was determined and the results were compared with the predicted values using a compartment model of soil-to-plant transfer and with the results of the field experiment. The results of comparing the measured and calculated transfer factor using the model show rather good coincidence, however, the calculated values were overestimated. The reason for overestimation can be that the uptake rate is not influenced only by the soil-to-plant transfer. The results of the model experiment (from 0.005 m²·kg⁻¹ to 0.053 m²·kg⁻¹) are close to those of the field measurements for grass (from 0.013 m²·kg⁻¹ in 1992–1995 to 0.10 m²·kg⁻¹ in 1999–2000).