Nitrate ion transport across TBP-kerosene oil supported liquid membranes coupled with uranyl ions

The role of nitrate ions in uranyl ions transport across TBP-kerosene oil supported liquid membranes (SLM) at varied concentrations of HNO₃ and NaNO₃ has been studied. It has been found that nitrate ions move faster compared to uranyl ions at the uranium feed solution concentrations studied. The nitrate to uranyl ions flux ratio vary from 355 to 2636 under different chemical conditions. At low uranium concentration the nitrate ions transport as HNO₃ · TBP, in addition to as UO₂(NO₃)₂ · 2TBP type complex species. The flux of nitrate ions is of the order of 12.10 · 10^–3 mol · m^–2 · s^–1 compared to that of uranium ions (4.56 · 10^–6 mol · m^–2 · s^–1). The permeability coefficient of the membrane for nitrate ions varies with chemical composition of the feed solution and is in the order of 2.5 · 10^–10 m^–2 · s^–1. The data is useful to estimate the nitrate ions required to move a given amount of uranyl ions across such an SLM and in simple solvent extraction.     

Does the ion–molecule reaction between HCCH and HCN lead to CH2CH–CN? A computational and experimental study of the reverse process

The title ion–molecule reaction has been proposed to play an important role in interstellar chemistry if it yields acrylonitrile ions CH₂CH–CN⁺. This question was probed by examining the formation of HCCH⁺ and HCN from low-energy ions CH₂CH–CN⁺ and related isomers, using tandem mass spectrometry based experiments (D and ¹³C labelling) in conjunction with model chemistry calculations (CBS-QB3/APNO). We conclude that the title reaction is a barrierless multistep rearrangement that may not effectively compete with the straightforward formation of stable distonic ions HCCH–NCH⁺ from HCCH⁺(ion)–HCN(dipole) encounter complexes.     

Interaction of lignosulfonate with certain metal ions

The reaction of lignosulfonate with the Co²⁺, Ni²⁺, and Cu²⁺ ions has been studied by the methods of gel chromatography, potentiometric titration, and UV spectroscopy. Lignosulfonate forms polymer-metal complexes with the metal ions over a wide pH range. In this process the size of the macromolecule scarcely changes, thanks to the reticular structure of the lignosulfonate. The capacity of lignin with respect to Cu²⁺ ions has been determined.Institute of Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 676–679, September–October, 1990.     

Radiochemical investigation of the bioaccumulation of urea by the alga Hydrodictyon reticulatum

It has been found that the bioaccumulation of¹⁴C-urea in the light is connected with the increase of pH-value of the external medium, with the increase of the intracellular concentration of ammonium ions and with the decrease of the intracellular concentration of potassium ions. The uptake rate does not depend on the concentration of urea in the range from 0.1 to 2.0 mmol dm^–3 and it has a broad maximum at pH 6.5–8.0. The uptake rate of urea is a little higher compared with nitrite or nitrate anions, however it is at least three times lower in comparison with that of ammonium or hydrocarbonate ions. The uptake of urea in the dark leads to the increase of the intracellular concentration of ammonium ions, however, carbon dioxide formed is released from the cell.     

Liquid-liquid partition of cobalt between trilaurylamine N-oxide and aqueous thiocyanate solutions

In an attempt to gain an understanding of factors affecting the extraction of cobalt by trilaurylamine oxide, the equilibria between HX+SCN^– (where X=NO ₃ ^– , Cl^–, SO ₄ ^2– ) and benzene solutions of trilaurylamine oxide have been studied. Cobalt is quantitatively extracted by the oxide from aqueous 0.01–1M KSCN in 0.01M concentration of the acids. The extraction mechanism and the possible compositions of the extracted species are discussed. The effect of several anions on the extraction of the element from optimal aqueous solutions are reported and separation factors for a number of metal ions are given. The solvent has a potential for the group preconcentration of toxic metal ions from dilute aqueous solutions.     

Separation of fluoride ion by extraction with triphenyltin chloride. Application for NAA of fluorine by means of 14-MeV neutrons

The separation of fluoride by extraction with toluene solution of triphenyltin chloride has been studied. Quantitative isolation of fluoride from solutions with a wide acidity range (pH 4.0–11.5) has been established. It is suggested that interferences by Ca, Mg, Fe, and Al can be avoided by masking these elements using sulfate and hydroxyde ions. Interference by phosphate ions can be overcome in a similar fashion. The halogenated species can be masked by mercury nitrate. Detection limit for fluorine determination is about 3 g for a neutron generator flux of 2·11¹¹ n·cm^–1·s^–1. A method for fluorine assay in water using a neutron generator with a detection limit of 1 ppm has been developed.     

Adsorption of low level51Cr(VI) from aqueous solution by bismuth trioxide: Kinetic and IR study

Radiotracer technique has been used for the investigation of adsorption of chromium (VI) traces on bismuth trioxide from aqueous solution. The effect of pH (2–10), concentration of chromate solution (10^–6–10^–2M) and temperature (303–323 K) has been thoroughly investigated. The influence of certain foreign ions has also been studied. The calculated kinetic and thermodynamic parameters indicate the first order rate law, spontaneity and exothermic nature of the adsorption process. Further, IR studies have established the chemical interaction between the sorbate and sorbent and a possible mechanism of the sorption process based on ligand exchange has been proposed.     

Influence of some ions on the activity of cottonplant phytase

The activity of the phytase from cottonplant shoots has been studied. It has been shown that Ca²⁺ and Mg²⁺ ions in low concentrations weakly stimulate the activity of the phytase, while Fe³⁺, Zn²⁺, and Cu²⁺ ions are inhibitors. It is suggested that the Fe³⁺ and Cu²⁺ ions accumulating in the aleurone grains may fulfill the function of phytase inhibitors during the dormancy of the seeds.Tashkent Mirzo Ulugbek State University. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 341–342, May–June, 1998.     

Diffusion of iodide, cesium and strontium in charnockite rock mass

Experiments have been conducted to study the diffusion of iodide, cesium and strontium ions through intact and fractured rock samples of charnockite rock formation present at Kalpakkam, India. The diffusion coefficient (D _i ) of these ions for the intact and fractured rock samples has been evaluated and is found to be ranging from 0.76·10^–14 to 6.25·10^–14 m²/s and 0.67·10^–9 to 84.6·10^–9 m²/s, respectively. The study reveals that despite the sorbing nature of Cs and Sr, these ions diffuse comparatively faster than the iodide ion (non-sorbing) through the intact and fractured rock mass. The results have been validated vis-à-vis those reported in the literature and a good agreement has been noticed. This paper deals with details of the testing methodology developed to assess the radionuclide migration as well as the rock mass suitability for safe disposal of the radioactive waste.     

Nonempirical calculations of models of interstitial defects in an LiF crystal

Models of interstitial Li⁺ and F^– ions in an LiF crystal have been calculated by the nonempirical Hartree-Fock-Roothaan method with the 4-31G+ basis and with the aid of a nonempirical pairwise potential. It has been shown that the energies needed for the adiabatic transfer of Li⁺ and F^– ions from infinity to interstitial positions in Li₄F₄ cubes are equal to +2.3 and +8.1 eV, respectively. The energies required for the transfer of Li⁺ and F^– ions from infinity to interstitial positions in a large cubic cluster of 4000 LiF molecules (a cube with an edge consisting of 20 atoms) are determined to a considerable extent by the long-range interactions of nonelectro-static nature and are equal to –0.25 and +9.9 eV, respectively, without consideration of the relaxation of the lattice.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2272–2277, October, 1989.We express our thanks to P. Charskii for supplying his version of the HONDO-5 + MP2 program and to V. G. Zakzhevskii for supplying the GAUSSIAN-SM program.     

Ionic Linking of Carboxymethylcellulose

Binding of Al³⁺, Cu²⁺, and Co²⁺ ions by carboxymethylcellulose (CMC) macromolecules was studied by potentiometric titration. It has been shown that the metal ions bind electrostatically over a wide pH range. Viscosimetry has found that the effectiveness of intermacromolecular CMC binding increases with increasing initial CMC concentration and in the presence of polybasic acids.__________Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 71–73, January–February, 2005.     

Liquid chromatography with triple-quadrupole or quadrupole-time of flight mass spectrometry for screening and confirmation of residues of pharmaceuticals in water

LC–MS–MS has been performed with triple-quadrupole (QqQ) and quadrupole-time of flight (Q-ToF) instruments and has been used for screening and confirmation of pharmaceuticals in surface, drinking, and ground water. Screening was based on monitoring of one specific MS–MS ion of the target compounds. Confirmation of the identity of the pharmaceuticals was based either on the monitoring of two specific MS–MS ions and calculation of the ratio of their intensities, or on the exact masses of MS–MS product ions obtained for a molecular ion by use of LC–Q-ToF MS. The set of pharmaceuticals included four analgesics (acetylsalicylic acid, diclofenac, ibuprofen, and paracetamol), three antibiotics (sulfamethoxazole, erythromycin, and chloramphenicol), five blood-lipid regulators and beta-blockers (fenofibrate, bezafibrate, clofibric acid, bisoprolol, and metoprolol), and the anti-epileptic drug carbamazepine. Limits of quantification ranged from 5 to 25 ng L^–1. Fifty-six samples were analysed and residues of the pharmaceuticals were detected in almost all surface and groundwater and in some drinking water samples. The identity of the compounds could be confirmed by use of both QqQ- and Q-ToF-based LC–MS–MS. However, the latter technique has the distinct advantage that a large number of pharmaceuticals can be screened and confirmed at low concentrations (1–100 ng L^–1) in one run.     

Diffusion of iodide, cesium and strontium in charnockite rock mass

Experiments have been conducted to study the diffusion of iodide, cesium and strontium ions through intact and fractured rock samples of charnockite rock formation present at Kalpakkam, India. The diffusion coefficient (D _i ) of these ions for the intact and fractured rock samples has been evaluated and is found to be ranging from 0.76·10^–14 to 6.25·10^–14 m²/s and 0.67·10^–9 to 84.6·10^–9 m²/s, respectively. The study reveals that despite the sorbing nature of Cs and Sr, these ions diffuse comparatively faster than the iodide ion (non-sorbing) through the intact and fractured rock mass. The results have been validated vis-à-vis those reported in the literature and a good agreement has been noticed. This paper deals with details of the testing methodology developed to assess the radionuclide migration as well as the rock mass suitability for safe disposal of the radioactive waste.     

Singly excited bound states in continuum: a time-dependent perturbation approach

Summary Time-dependent coupled Hartree-Fock (TDCHF) scheme has been applied to study the behaviour of bound excited states embedded in the continuum for the negative ions Li^–, F^–, Na^– and Cl^–. The excited states have been obtained from the position of the poles of the dynamic polarizability values which are evaluated for all the ions within and beyond the normal dispersion region. Transition energies and dipole allowed oscillator strengths have been obtained for several transitions which lie in the continuum. Although the excited state functions are extremely diffuse, they show proper asymptotic behaviour and furnish correct number of nodes. Oscillator strengths are found to follow a different trend than observed in normal bound state calculations.     

Kinetic study of Cr(VI) sorption on MnO2

The kinetics of adsorption of chromate ions has been investigated radiometrically over a wide range of concentration of chromate ions (10^–6–10^–2M) and temperature (303–323 K). The kinetics of the process follows essentially a first order rate law with respect to adsorptive concentration and obeys the Freundlich adsorption isotherm in the concentration range studied. In addition, the kinetics of desorption of the preadsorbed species also follows a first order rate law and the activation energy for desorption is greater than that of the adsorption process. On the basis of an adsorption kinetic study, the thermodynamic parameters have been calculated. Infrared spectroscopy has shown the chemical interaction of chromate ions on the surface of MnO₂.     

Technetium-99m extraction and transport across tri-n-octylamine-xylene based supported liquid membranes

The nuclear properties of^99mTc radionuclide are ideal for organ imaging. Study of the technetium transport across supported liquid membranes has been performed to get data for its separation from other elements. Tri-n-octylamine diluted in xylene was used to constitute the liquid membranes, supported in polypropylene microporous films. Stripping on the product solution side was performed with dilute NaOH solutions. The effect of sulphuric acid, nitric acid and hydrochloric acid in the feed on transport of^99mTc as TcO ₄ ^– ions has been studied. The permeability of the given ions determined from kinetic activity data has been found to be in the order of PH₂SO₄>PHCl>PHNO₃. The flux values have been calculated based on this permeability data. The increase in carrier concentration has shown an increase in flux and permeability values to a given optimum concentration. The increase in temperature has been found to reduce the transport of Tc ions. The optimum conditions for transport of^99mTc for the given acid concentration have been determined. Mechanism of Tc ion transport has also been provided based on chemical reactions involved at the membrane interfaces and uptake of Tc ions by the membrane. MoO ₄ ^2– ions do not permeate through membrane under optimum conditions of transport for TcO ₄ ^2– ions from H₂SO₄ solution.     

Influence of metal ions on the activity and stability of the glucose isomerase from Streptomyces atratus

The influence of a number of bivalent metals on the activity ofStreptomyces atratus glucose isomerase has been studied. Mg²⁺ ions are activators and Co²⁺ ions are stabilizers of the glucose isomerase activity. The effective kinetic parameters for the action of the enzyme have been determined.Institute of Microbiology, Uzbek Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 838–842, November–December, 1991.     

Extractive radiometric procedure for the estimation of fluoride

A radiochemical method for the determination of fluoride has been developed. The effect of fluoride on the extraction of the Fe/III/ thiocyanate complex into TBP in nitrobenzene has been utilized. Microgram quantities of F^– have been determined. Effect of diverse ions has also been reported. The method is applied for the determination of F^– in a natural sample of apetite.     

Some characteristics of cotton plant protein kinase C

The change in the activity of the protein kinase C of cotton plant shoots as functions of the temperature, the time of incubation, and the concentration of Mg²⁺ ions has been investigated. It has been established that the maximum activity is shown at a temperature of 25–40°C an incubation time of 30 min, pH 7.0, and a Mg²⁺ concentration of 10 mM.Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 141–145, January–February, 1995. Original article submitted October 17, 1994.     

Transport study of V(V), Zn(II) and Be(II) using supported liquid membranes

V(V), Zn(II) and Be(II) have been studied to test oxine and tri-n-butylphosphate (TBP) as carriers for transport through supported liquid membranes in polypropylene film. All the three types of ions can be passed through such membranes using oxine in case of V(V) and TBP in case of Zn(II) and Be(II). Maximum flux of metal ions has been observed from 0.01M H₂SO₄ for V(V) (3.22·10^–6 mol·m^–2·s^–1) and 2M HCl containing 3M CaCl₂ for Zn(II) solution (1.4·10^–6 mol·m^–2·s^–1). Low flux was observed in case of Be(II) since the membrane was affected by sulphocyanide group and did not remain hydrophobic. Mechanism of transport for these metal ions have been proposed separately. Distribution coefficient data for V(V) have also been evaluated to determine theoretical values of the permeability coefficient, and compared with experimental values.