Adsorption of <Superscript>125</Superscript>Sb on alumina and titania surfaces

Adsorption of long-lived ¹²⁵Sb radioisotope (T _1/2 = 2.75 y) on alumina (Al₂O₃) and titania (TiO₂) has been studied at different pH. Both the oxides have good adsorption capability for the ¹²⁵Sb radioisotopes but the TiO₂ is much superior. Adsorption kinetics of ¹²⁵Sb radioisotopes on TiO₂ surface and desorption of ¹²⁵Sb radioisotopes from TiO₂ surface in acidic and alkaline media have also been studied. The ¹²⁵Sb-TiO₂ phase has been subjected to γ-irradiation and found to be radiation stable against antimony release.     

Modeling β-γ coincidence spectra of <Superscript>131m</Superscript>Xe, <Superscript>133</Superscript>Xe, <Superscript>133m</Superscript>Xe,and <Superscript>135</Superscript>Xe

In support of the Comprehensive Nuclear-Test-Ban Treaty (CTBT), improvements have been made to the model of the Automated Radioxenon Sampler/Analyzer (ARSA) β-γ coincidence detector for radioxenon monitoring. MCNPX is used to simulate the detector response for all the electrons and photons emitted from ^131mXe, ¹³³Xe, ^133mXe, ¹³⁵Xe, and ¹³⁷Cs signals. A MatLab code was written to incorporate the MCNPX results in the calculation of β-γ coincidence spectra. These will aid in the development of the Spectral Deconvolution Analysis Tool (SDAT)¹ and to calibrate β-γ coincidence systems. The models developed for this work include improvements over previous models in their ability to address Compton scattering in the β-cell, and the β-distribution offset in the 31 keV γ-ray region for ¹³³Xe.     

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).     

Novel methodology for the study of mercury methylation and reduction in sediments and water using <Superscript>197</Superscript>Hg radiotracer

Mercury tracers are powerful tools that can be used to study mercury transformations in environmental systems, particularly mercury methylation, demethylation and reduction in sediments and water. However, mercury transformation studies using tracers can be subject to error, especially when used to assess methylation potential. The organic mercury extracted can be as low as 0.01% of the endogenous labeled mercury, and artefacts and contamination present during methylmercury (MeHg) extraction processes can cause interference. Solvent extraction methods based on the use of either KBr/H₂SO₄ or HCl were evaluated in freshwater sediments using ¹⁹⁷Hg radiotracer. Values obtained for the ¹⁹⁷Hg tracer in the organic phase were up to 25-fold higher when HCl was used, which is due to the coextraction of ¹⁹⁷Hg²⁺ into the organic phase during MeHg extraction. Evaluations of the production of MeHg gave similar results with both MeHg extraction procedures, but due to the higher Hg²⁺ contamination of the controls, the uncertainty in the determination was higher when HCl was used. The Hg²⁺ contamination of controls in the HCl extraction method showed a nonlinear correlation with the humic acid content of sediment pore water. Therefore, use of the KBr/H₂SO₄ method is recommended, since it is free from these interferences. ¹⁹⁷Hg radiotracer (T _1/2 = 2.673 d) has a production rate that is about 50 times higher than that of ²⁰³Hg (T _1/2 = 46.595 d), the most frequently used mercury radiotracer. Hence it is possible to obtain a similar level of performance to ²⁰³Hg when it is used it in short-term experiments and produced by the irradiation of ¹⁹⁶Hg with thermal neutrons, using mercury targets with the natural isotopic composition. However, if the 0.15% natural abundance of the ¹⁹⁶Hg isotope is increased, the specific activity of the ¹⁹⁷Hg tracer can be significantly improved. In the present work, ¹⁹⁷Hg tracer was produced from mercury 51.58% enriched in the ¹⁹⁶Hg isotope, and a 340-fold increase in specific activity with respect to natural mercury targets was obtained. When this high specific activity tracer is employed, mercury methylation and reduction experiments with minimum mercury additions are feasible. Tracer recovery in methylation experiments (associated with Me¹⁹⁷Hg production from ¹⁹⁷Hg²⁺ spike, but also with Hg²⁺ contamination and Me¹⁹⁷Hg artefacts) with marine sediments was about 0.005% g⁻¹ WS (WS: wet sediment) after 20 h incubation with mercury additions of 0.05 ng g⁻¹ WS, which is far below natural mercury levels. In this case, the amount of Hg²⁺ reduced to Hg⁰ (expressed as the percent ¹⁹⁷Hg⁰ recovered with respect to the ¹⁹⁷Hg²⁺ added) varied from 0.13 to 1.6% g⁻¹ WS. Me¹⁹⁷Hg production from ¹⁹⁷Hg²⁺ spike after 20 h of incubation of freshwater sediment ranged from 0.02 to 0.13% g⁻¹ WS with mercury additions of 2.5 ng g⁻¹ WS, which is also far below natural levels. ¹⁹⁷Hg⁰ recoveries were low, 0.0058 ± 0.0013% g⁻¹ WS, but showed good reproducibility in five replicates. Me¹⁹⁷Hg production from ¹⁹⁷Hg²⁺ spiked in freshwater samples ranged from 0.1 to 0.3% over a period of three days with mercury additions of 10 ng L⁻¹. A detection limit of 0.05% for Me¹⁹⁷Hg production from ¹⁹⁷Hg²⁺ spike was obtained in seawater in a 25 h incubation experiment with mercury additions of 12 ng L⁻¹.     

Biosorptive behavior of mango (<Emphasis Type="Italic">Mangifera indica</Emphasis>) and neem (<Emphasis Type="Italic">Azadirachta indica</Emphasis>) barks for <Superscript>134</Superscript>Cs from aqueous solutions: A radiotracer study

The role of dead biomasses viz., mango (Mangifera indica) and neem (Azadirachta indica) bark samples are assessed in the removal behavior of, one of important fission fragments, Cs(I) from aqueous solutions employing a radiotracer technique. The batch type studies were carried out to obtain various physico-chemical data. It is to be noted that the increase in sorptive concentration (from 1.0·10⁻⁸ to 1.0·10⁻² mol·dm⁻³), temperature (from 298 to 328 K) and pH (2.6 to 10.3) apparently favor the uptake of Cs(I) by these two bark samples. The concentration dependence data obeyed Freundlich adsorption isotherm and the uptake follows first order rate law. Thermodynamic data evaluation and desorption experiments reveal the adsorption to be irreversible and endothermic in nature proceeding through ion-exchange and surface complexation for both dead biomasses. Both bark samples showed a fairly good radiation stability in respect of adsorption uptake of Cs(I) when irradiated with a 300 mCi (Ra-Be) neutron source having an integral neutron flux of ∼3.85·10⁶ n·cm⁻²·s⁻¹ and associated with a nominal γ-dose of ∼1.72 Gy·h⁻¹.     

Synthesis of pyridyl derivatives for the future functionalization of biomolecules labeled with the fac-[<Superscript>188</Superscript>Re(CO)<Subscript>3</Subscript>(H<Subscript>2</Subscript>O)<Subscript>3</Subscript>]<Superscript>+</Superscript> precursor

In this paper, we investigated three ligand systems, symmetric and asymmetric pyridyl-containing tridentate ligands (L¹NH₂ = (bis(2-pyridylmethyl)-amino)-ethylamine, L²H = (bis(2-pyridylmethyl)-amino)-acetic acid, L³NH₂ = [(6-amino-hexyl)-pyridyl-2-methyl-amino]-acetic acid) as bifunctional chelating agents for labeling biomolecules. These ligands reacted with the precursor fac-[¹⁸⁸Re(CO)₃(H₂O)₃]⁺ and yielded the radioactive complexes fac-[¹⁸⁸Re(CO)₃L] (L = three ligands), which were identified by RP-HPLC. The corresponding stable rhenium tricarbonyl complexes (1–3) were allowed for macroscopic identification of the radiochemical compounds. ¹⁸⁸Re tricarbonyl complexes, with log P _o/w values ranging from −1.36 to −0.32, were obtained with yields of ≥90% using ligand concentrations within the 10⁻⁶−10⁻⁴M range. Challenge studies with cysteine and histidine revealed the high stability properties of these radioactive complexes, and biodistribution studies in normal mice indicated a fast rate of blood clearance and high rate of total radioactivity excretion, primarily through the renal-urinary pathway. In summary, these asymmetric and symmetric pyridyl-containing tridentate ligands are potent bifunctional chelators for the future biomolecules labeling of fac-[¹⁸⁸Re(CO)₃(H₂O)₃]⁺.     

Targetry and specification of <Superscript>167</Superscript>Tm production parameters by different reactions

In recent years, there has been a rapid expansion in the use of radio nuclides for therapeutic purposes. Thulium–167 is an important radionuclide (T _1/2 = 9.25 d) due to it could be used for tumor and bone studies in nuclear medicine. ¹⁶⁷Tm complexed with hydroxy ethylene diamine tetra-acetic acid (HEDTA) could be used with the aim of bone imaging. ¹⁶⁷Tm emits a prominent γ ray of 208 keV energy and low energy electrons. This study describes calculations on the excitation functions of ¹⁶⁵Ho(α,2n)¹⁶⁷Tm, ¹⁶⁷Er(p,n)¹⁶⁷Tm, ^natEr(d,xn)¹⁶⁷Tm and ^natEr(p,xn)¹⁶⁷Tm reactions by ALICE/ASH (hybrid and GDH models) and TALYS-1.0 codes. In addition, calculated data by codes were compared to experimental data that earlier were published and TENDL-2010 database. Moreover, optimal thickness of the targets and physical yield were obtained by SRIM (stopping and range of ions in matter) code for each reaction. According to the results, the ¹⁶⁷Er(p,n)¹⁶⁷Tm and ¹⁶⁵Ho(α,2n)¹⁶⁷Tm reactions are suggested as the best method to produce ¹⁶⁷Tm owing to minimum impurities. The TALYS-1.0 code, predict the maximum cross-section of about 382 mb at 11 MeV and 849 mb at 26 MeV for ¹⁶⁷Er(p,n)¹⁶⁷Tm and ¹⁶⁵Ho(α,2n)¹⁶⁷Tm reactions, respectively. Finally, deposition of ^natEr₂O₃ on Cu substrate was carried out via the sedimentation method. The 516 mg of erbium(III)oxide with 103.2 mg of ethyl cellulose and 8 mL of acetone were used to prepare a ^natEr₂O₃ layer of 11.69 cm². ¹⁶⁷Tm was produced via the ^natEr(p,n)¹⁶⁷Tm nuclear process at 20 μA current and 15 → 7 MeV protons beam (1 h). Yield of about 3.2 MBq ¹⁶⁷Tm per μA h were experimentally obtained.     

Molecular modeling of hydration properties of hydrophobic ions Li<Superscript>+</Superscript>@C<Subscript>60</Subscript> and K<Superscript>+</Superscript>@C<Subscript>60</Subscript>

The Gibbs free energies of solvation (ΔG _s) and the electronic structures of endohedral metallofullerenes M⁺@C₆₀ (M⁺= Li⁺, K⁺) were calculated within the framework of the density functional theory and the polarizable continuum model. In water environment, the equilibrium position of K⁺ is at the center of the fullerene cavity whereas that of Li⁺ is shifted by 0.14 nm toward the fullerene cage. The Li⁺ cation is stabilized by interactions with both the fullerene and solvent. The equilibrium structures of both endohedral metallofullerenes are characterized by very close ΔG _s values. In particular, the calculated ΔG _s values for K⁺@C₆₀ are in the range from −124 to −149 kJ mol⁻¹ depending on the basis set and on the type of the density functional. Molecular dynamics simulations (TIP3P H₂O, OPLS force field, water sphere of radius 1.9 nm) showed that the radial distribution functions of water density around C₆₀ and M⁺@C₆₀ are very similar, whereas orientations of water dipoles around the endohedral metallofullerenes resemble the hydration pattern of isolated metal ions.     

<Superscript>234</Superscript>U/<Superscript>235</Superscript>U activity ratios as a probe for the <Superscript>238</Superscript>U/<Superscript>235</Superscript>U half-life ratio

High-resolution alpha-particle spectrometry was performed on three uranium materials enriched in ²³⁵U. Besides the ²³⁵U peaks, separate peaks belonging to impurity traces of ²³⁴U could be quantified. Relying on the isotopic composition of the uranium, as determined by mass spectrometry, the ratio of the half-lives of ²³⁸U and ²³⁵U was determined via the activity ratio of ²³⁴U and ²³⁵U in the materials. As an intermediate link, the ²³⁴U/²³⁸U half-life ratio was taken from published mass spectrometric analyses of ‘secular equilibrium’ uranium material. The resulting half-life ratio T _1/2(²³⁸U)/T _1/2(²³⁵U) = 6.351±0.031 is in agreement with the commonly adopted half-life values determined by Jaffey et al.     

Functionalization of one or two methyl groups in the [Cp*<Subscript>2</Subscript>RuBr]<Superscript>+</Superscript>Br<Superscript>−</Superscript> complex in the reaction with bromine

The reaction of [Cp*₂RuBr]⁺Br⁻ with bromine in CH₂Cl₂ (CD₂Cl₂) in an inert atmosphere at room temperature produces the complexes [Cp*Ru(Br)C₅Me₄CH₂Br]⁺Br₃ ⁻ (syn conformer), [Cp*Ru(Br)C₅Me₃(CH₂Br)₂]⁺ (syn and anti conformers), and [Ru(Br)(C₅Me₄CH₂Br)₂]⁺ (syn conformer). All complexes were characterized by ¹H and ¹³C NMR spectroscopy; the former complex, by elemental analysis. These complexes were also prepared by the reaction of [Cp*RuC₅Me₄CH₂]⁺BF₄ ⁻ with bromine in CH₂Cl₂. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2712–2718, December, 2005.     

Anomalously high activities of <Superscript>137</Superscript>Cs in soils and vegetation on and near a diabase outcrop in La Sierra de Lema,Venezuela

As a result of routine soil sampling to determine the ¹³⁷Cs background activities country-wide in Venezuela, it was decided to further investigate El Mirador (Lookout) area at the base of the Sierra de Lema mountain range. In April 2003 (A), soil samples were collected at eight sites on and around the edge of the diabase outcrop to confirm that this area had anomalously high ¹³⁷Cs activities. In July 2003 (B), not only soil samples were collected again, but also black mat, palm tree leaves and trunks, fruit bushes leaves and its fruit and fern leaves. The ¹³⁷Cs content was measured by high resolution gamma-ray spectroscopy by a comparative method with reference materials. The ¹³⁷Cs activity values range from 16.3 to 30.8 Bq·kg-1 in the soil samples collected in July 2003, 20.7–32.1 Bq·kg⁻¹ for the black mat, 26.3–38.4 Bq·kg⁻¹ for the palm leaves, 16.8–31.2 Bq·kg⁻¹ for the palm trunks and 17.6–27.3 Bq·kg⁻¹ for the fruit bush leaves, while, the ¹³⁷Cs activity values for the whole fruit were between 23.4 and 30.7 Bq·kg⁻¹; but, the value of the ¹³⁷Cs activity in the center of the fruit (the edible part) was 51.6 Bq·kg⁻¹, and the value of the ¹³⁷Cs activity for the fern leaves was 51.8 Bq·kg⁻¹. Thus, most of the ¹³⁷Cs activity values determined in the soil, black mat and vegetation samples from El Mirador (Lookout) were considered anomalously high with respect to those found near the equator and in other areas of Venezuela. Only the center of the fruit from the Clusia grandiflora bushes and the fern leaves had high activity ratios, about a factor of three and could be considered as biomonitors that concentrate and retain the ¹³⁷Cs. Finally, these anomalously high ¹³⁷Cs activities have been attributed not only to the rich organic soils, as sinks, but also due to the affect of the cloud forests.     

Host–Guest Complexation of <Emphasis Type="Italic">β</Emphasis>-, <Emphasis Type="Italic">γ</Emphasis>-Cyclodextrin with Alkyl Trimethyl Ammonium Bromides in Aqueous Solution

As a continuation of our previous investigation, interactions between cyclodextrin (β-CD), γ-cyclodextrin (γ-CD) and alkyl trimethylammonium bromides in aqueous solutions have been studied with titration calorimetry and ¹H NMR at 298.15 K. The results are discussed in terms of the amphiphilic interaction of CD with surfactants and the iceberg structure formed by water molecules existing around the hydrophobic tail of surfactant molecules. The stoichiometry of the β-CD–surfactant system is 1:1 whereas that of the γ-CD–surfactant system is 1:2. The corresponding formation enthalpy (negative) of the complexes of the two systems decreases with an increase in the number of carbon atoms (n) in hydrophobic chain of surfactant molecule, C _n H_2n+1, whereas the entropy increases with the enlargement of n.     

The Ethanol Tolerance of <Emphasis Type="Italic">Pachysolen tannophilus</Emphasis> in Fermentation on Xylose

The influence of ethanol on fermentation by Pachysolen tannophilus was studied. When xylose utilization rate was 80%, ethanol concentration began to decline. Fermentation of P. tannophilus was affected by ethanol addition in the beginning of fermentation; average xylose consumption rate was 0.065 g·l⁻¹·h⁻¹, and maximum specific growth rate was 0.07 h⁻¹ at 28 g·l⁻¹ ethanol, comparing with the average xylose consumption rate of 0.38 g·l⁻¹·h⁻¹ and maximum specific growth rate of 0.14 h⁻¹ in fermentation with no ethanol addition; P. tannophilus stopped growth at 40 g·l⁻¹ ethanol. When the initial ethanol concentration was 30 g·l⁻¹, the addition of glucose in xylose media made the growth of P. tannophilus better, and the most favorable glucose concentration was 15 g·l⁻¹ with the highest biomass of 1.51 g·l⁻¹ as compared with that of 0.95 g·l⁻¹ in pure xylose media.     

[1-B<Subscript>10</Subscript>H<Subscript>9</Subscript>N<Subscript>2</Subscript>]<Superscript>−</Superscript> and [1-CB<Subscript>9</Subscript>H<Subscript>10</Subscript>]<Superscript>−</Superscript> anions: an attempt of quantum chemical calculations

Comparative quantum chemical calculations of structural parameters, chemical shifts of ¹¹B NMR spectra, and atomic charges in 10-vertex boron hydride anions [1-CB₉H₁₀]⁻ and [1-B₁₀H₉N₂]⁻ were performed using the restricted Hartree-Fock method with the 6-31++G(D,P) basis set. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1853–1855, September, 2007.     

Initiation of ethylene polymerization on organoelement cations L<Subscript>2</Subscript>MMe<Superscript>+</Superscript> (M = Ge,Sn) with intramolecular coordination bonds: a theoretical study

The initiation of ethylene polymerization on L₂MMe⁺ cations (M = Ge, Sn; L = alkoxy, alkyl, phenoxyiminate, β-diketonate) was studied by the PBE/TZ2P density functional method. It was found that ethylene insertion into the M—C bond of the L₂MMe⁺ cations is energetically favorable (ΔG ⁰ = −7.6—−13.6 kcal mol⁻¹). The calculated energy barriers to reactions lie in a wide range 39.8 to 75.6 kcal mol⁻¹. The lowest energy barriers were obtained for tin cations bearing hexa- and heptafluoroacetylacetonate substituents. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1338–1347, July, 2008.     

Production of <Superscript>122</Superscript>Sb for the study of environmental pollution

This article presents, ¹²²Sb (T _1/2 = 2.723 days, I _β- = 97.59%) was produced via the ^natSn(p,xn) nuclear process at the AMIRS (Cyclone-30, IBA, Belgium). The electrodeposition experiments were carried out by potassium stannate trihydrate (K₂Sn(OH)₆) and potassium hydroxide. The optimum conditions of the electrodeposition of tin were as follows: 40 g/L ^natSn, 20 g/L KOH, 115 g/L K₂Sn(OH)₆, DC current density of 5 A/dm² with a bath temperature of 75 °C. The electroplated Tin-target was irradiated with 26.5 MeV protons at current of 180 μA for 20 min. Solvent extraction of no-carrier-added ¹²²Sb from irradiated Tin-natural target hydrochloric solution was investigated using di-n-butyl ether (C₈H₁₈O). Yields of about 3.61 MBq/μAh were experimentally obtained.     

Vertical inventories and fluxes of <Superscript>210</Superscript>Pb, <Superscript>228</Superscript>Ra and <Superscript>226</Superscript>Ra at southern South China Sea and Malacca Straits

Inventories and fluxes of ²¹⁰Pb, ²²⁸Ra and ²²⁶Ra were determined in sediment cores collected at nine stations covering of the southern South China Sea and Malacca Straits with the thickness of water column between 42 and 83 m depth. The inventories of ²¹⁰Pb, ²²⁸Ra and ²²⁶Ra were calculated range from 0.15–2.55 Bq cm⁻², 0.05–0.40 Bq cm⁻² and 6.83–83.63 Bq cm⁻², meanwhile the fluxes ranged from 0.005–0.079 Bq cm⁻² yr⁻¹, 0.009–0.048 Bq cm⁻² yr⁻¹ and 0.003–0.037 Bq cm⁻² yr⁻¹, respectively. The results show that the highest inventories and fluxes for ²¹⁰Pb, ²²⁸Ra and ²²⁶Ra were found at station WC 01 and EC 05. Because there are additional sources of ²¹⁰Pb, ²²⁸Ra and ²²⁶Ra, where water transport will brings more dissolved isotopes, influence of the transportation and deposition of suspended particles, fast rate of regeneration and greater production of those radionuclides and others.     

Solubility in the ternary system CaSO<Subscript>4</Subscript> + Na<Subscript>2</Subscript>SO<Subscript>4</Subscript> + H<Subscript>2</Subscript>O at 298.15 K

The solubility in the ternary system, aqueous mixture of CaSO₄ and Na₂SO₄, at T = 298.15 K comprises five different salts: calcium sulfate dihydrate, mirabilite, thenardite, glauberite and labile salt. Using the Extended Pitzer’s Ion Interaction model for pure and mixed electrolyte solutions and criteria of phase equilibria, predicted solubility behavior of salts was compared with experimental results from literature. The agreement between calculated and experimental solubilities was excellent in the ionic strength range up to 10.9062 mol kg⁻¹.     

Extraction and <Emphasis Type="Italic">ab initio</Emphasis> calculation studies on the complexation of Ca<Superscript>2+</Superscript> with valinomycin

From extraction experiments and γ-activity measurements, the exchange extraction constant corresponding to the equilibrium Ca²⁺ (aq)+1·Sr²⁺ (nb) ⇆ 1·Ca²⁺ (nb) + Sr²⁺ (aq) taking place in the two-phase water-nitrobenzene system (1 = valinomycin; aq = aqueous phase, nb = nitrobenzene phase) was evaluated as log K _ex (Ca²⁺, 1·Sr²⁺) = 2.4±0.1. Further, the stability constant of the valinomycin-calcium complex (abbrev. 1·Ca²⁺) in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log β _nb (1·Ca²⁺) = 8.3±0.1. By using quantum mechanical DFT calculations, the most probable structure of the 1·Ca²⁺·2H₂O complex species was predicted. In this complex, the “central” Ca²⁺ cation is bound by strong bonds to two oxygen atoms of the respective water molecules and to four ester carbonyl oxygens of the parent valinomycin ligand 1. Finally, the calculated binding energy of the considered complex 1·Ca²⁺·2H₂O is −319.2 kcal/mol, which confirms the relatively high stability of this cationic complex species.     

Novel large heteropolymetalate complexes formed from Ni(II) and cryptate [As<Subscript>4</Subscript>W<Subscript>40</Subscript>O<Subscript>140</Subscript><Superscript>28-</Superscript>

The heteropolytungstate (NH4)₂₀[Na2(H₂O)₂Ni(H₂O)₅{Ni(H₂O)}₂As₄W₄₀O₁₄₀] · 61H₂O is obtained by the reaction of Na₂₇[NaAs₄W₄₀O₁₄₀] · 60H₂O with NiCl₂ · 6H₂O and NH₄Cl in pH≈4.0. The structure and chemical composition are determined by X-ray diffraction analysis and element analysis. The crystal data and main structure refinement are: a = 1.33135(18) nm, b = 1.9722(3) nm, c = 3.6430(5) nm, α = 78.010(2)°, β = 82.145(2)δ, γ = 74.385(2)°, V = 8.978(2) nm³, triclinic crystal system, space group: P1, Z = 2, R1 = 0.0512, and wR2 = 0.0684(I >2σ). The four S2 sites of the big cyclic ligand [As₄W₄₀O₁₄₀]^28- are occupied by two Na⁺ and two Ni²⁺ respectively, and each site supplies four O_d coordinating to metal ion. The coordination number of Ni²⁺ is six, and that of two Na⁺ is five and six respectively. The third Ni²⁺ locates outside the cyclic [As₄W₄₀O₁₄₀]^28- and connects with one O_d, and its coordination number is six.