An ultrasensitive method for the determination of thiouracil and phenylthiouracil using capillary zone electrophoresis and laser-induced fluorescence detection

This paper reports the development of a method based on capillary electrophoresis with laser-induced fluorescence detection for the simultaneous determination of thiouracil (TU) and phenylthiouracil (PhTU) with high sensitivity (nanomolar range, i.e., attomoles detected). After derivatization with 5-iodoacetamidofluorescein, the analytes were separated by capillary zone electrophoresis using 20 mM phosphate buffer (pH 10.0) and quantified by fluorescence detection. The linearity range, precision, recovery, and detection limits were determined, and the method was shown to be applicable for the determination of TU and PhTU in spiked feed samples and urine.     

Regular Liesegang patterns and precipitation waves in an open system

We investigate the regular and moving Liesegang pattern formation phenomena in an open system. First, simulations have been performed at fixed coupling between the reactive medium and the reservoir, later this control parameter was varied during the simulations resulting in various phenomena. We predicted and monitored for the first time various--dynamically changing--precipitation structures and a spatial hysteresis phenomenon, which is beyond the scope of the Turing instability. The dynamics of the reaction is well detectable using specific quantities: the total amount of precipitate and its center of gravity.     

Sorption of caesium and strontium on clinoptilolite-and mordenite-containing sedimentary rocks

The sorption of caesium and strontium from its aqueous solutions by ten clinoptilolite-and mordenite-containing sedimentary materials from Slovakia, Bulgaria, Ukraine and Greece was investigated by batch-type procedure and radiotracer techniques. The concentration of the solutions, that were performed in and without the presence of competing cations (0.005 mol·dm⁻³ KCl) varied between 1·10⁻⁴ and 5·10⁻² mol·dm⁻³. The uptake and distribution coefficient (K _d ) values determined for the materials of the different origin, were correlated with their mineralogical composition and gross cation exchange capacity (CEC). The identification of the specific uptake sites was attempted on the basis of the sorption isotherms and the content of exchangeable cations. The experimental results provide information on the suitability of the individual materials for the treatment of radioactive wastes and their application as backfills in potential nuclear waste repositories.     

Energy Recovery from Municipal Solid Waste in Small Communities

The heating values of municipal solid waste generated in three towns with a population of less than 50 000, situated in Galicia (Spain), were measured with a static bomb calorimeter. Samples of raw refuse were burnt either as received or after sorting of the different combustible components. A study was made of samples from controlled and uncontrolled landfills. The calorific values were compared with those corresponding to a commercial residual derived fuel in order to study the possibility of using municipal solid waste as a source of recovered energy. This revised version was published online in July 2006 with corrections to the Cover Date.     

Determination of physical properties of bitumens by use of near-infrared spectroscopy with neural networks. Joint modelling of linear and non-linear parameters

The fact that bitumens behave as non-Newtonian fluids results in non-linear relationships between their near-infrared (NIR) spectra and the physico-chemical properties that define their consistency (viz. penetration and viscosity). Determining such properties using linear calibration techniques [e.g. partial least-squares regression (PLSR)] entails the previous transformation of the original variables by use of non-linear functions and employing the transformed variables to construct the models. Other properties of bitumens such as density and composition exhibit linear relationships with their NIR spectra. Artificial neural networks (ANNs) enable modelling of systems with a non-linear property-spectrum relationship; also, they allow one to determine several properties of a sample with a single model, so they are effective alternatives to linear calibration methods. In this work, the ability of ANNs simultaneously to determine both linear and non-linear parameters for bitumens without the need previously to transform the original variables was assessed. Based on the results, ANNs allow the simultaneous determination of several linear and non-linear physical properties typical of bitumens.     

Charge transfer across a polymer gel/liquid interface: determination of ionophores

An electrochemical method for the determination of the ionophores monensin and lasalocid was developed, based on the polarization of an agar gel/nitrobenzene electrolyte interface. The measured current corresponding to the facilitated ion transfer across this interface is directly proportional to the concentration of an ionophore dissolved in the organic phase. Using cyclic voltammetry in a three-electrode system the detection limit for both ionophores is about 3 × 10^?5 M.     

Thermal properties of hydrated lanthanum and yttrium polyvanadates

The study of thermal properties of La(HV₆O₁₆)₃.19.5H₂O and Y(HV₆O₁₆)₃.22H₂O showed, that the dehydration of both compounds is discontinuous. After release of last water amount, the parent structure is destabilized and products of thermal decomposition, V₂O₅ and corresponding orthovanadates, start to be formed. The decomposition of La(HV₆O₁₆)₃.19.5H₂O results in formation of V₂O₅ and LaVO₄, the temperatures of crystallization of which differ. The decomposition products of yttrium salt crystallize simultaneously. All compounds formed melt at 685°C. By crystallization of the melt, the mixtures V₂O₅-LaVO₄ and V₂O₅-YVO₄, respectively, are formed which are stable up to 1000°C.     

Inexpensive device for measurements with ion-selective and pH electrodes

The design and construction of a simple device for measuring ionic concentrations (or pH) with ion-selective electrodes are described. The automated system includes a special electronic circuit with an operational amplifier, a signal conditioner and a personalcomputer. A digital multimeter can be used if automation is not required. The results obtained in tests with iodide-, chloride- and nitrate-selective electrodes and glass electrodes show very good agreement with those obtained with sophisticated commercial apparatus.     

Esterification of C1−C8 carboxylic acids to n-butyl esters in aqueous solutions for their gas chromatographic analysis

Summary The esterification of C₁–C₈ fatty acid in aqueous solutions and in the presence of sulfuric or hydrochloric acid and with n-butanol is described. It has been established that the esterification can be used for the quantitative determination of these fatty acids in the concentration ratio range of [H₂O]/[n-BuOH]=0.01–5.3. In the concentration ratio range of 0.01–0.8 the water present does not interfere. In the concentration range of above 0.8 anhydrous sodium sulfate is used for binding the water, in the amount of [Na₂SO₄.anh.]/[H₂O]0.2.     

Discontinuous-flow potentiometric determination of chloride in a large-volume wall-jet cell using an ion-selective electrode based on a silver chloride film chemically deposited on a silver iodide support

A robust and sensitive chloride ion-selective electrode can be prepared by modifying the surface of an iodide-selective electrode using the chemical reaction with mercuric chloride in an oxidizing medium containing excess chloride. A thin film of silver chloride is thus formed ensuring a rapid and reproducible response to chloride. The analytical parameters of this electrode are similar to those of commercial silver chloride ion-selective electrodes, but its electrical impedance and signal noise are substantially lower and the response somewhat faster. Its sensitivity toward surfactants is somewhat suppressed. The electrode was used for discontinuous flow potentiometric (DFP) determinations in a large-volume wall-jet cell in which the electrode surface can be continuously reactivated by a cleaning solution contained in the cell. The method was applied to determination of chloride in ground waters from an industrial waste dumping site. The limit of determination is low 9 mug Cl(-)/l (2.6 x 10(-7)M), the precision good (the relative standard deviation varies from 0.6 to 3.0% for chloride contents from 2.90 to 0.15 mg/l, respectively) and the method correlates satisfactorily with the results of an indirect AAS determination of chloride. The sample throughput is high-90 measurements can be carried out per hour, corresponding to 30-40 determinations per hour.