Indirect measurement of brucine by adsorptive stripping voltammetry at mercury electrode

After reaction with nitric acid, brucine can be transformed into cacotheline, and then measured indirectly by adsorptive stripping voltammetry. This method is based on the adsorptive accumulation of cacotheline at a hanging mercury drop electrode, followed by cathodic linear sweep voltammetry. The cathodic peak potential is about -0.35 V (vs. saturated Ag AgCl ). The detection limit of 2.0 x 10(-9) M is obtained under optimized conditions. The electrochemical behaviour of cacotheline and the mechanism of the electrode reactions are discussed.     

Solvent extraction of Au(III) for preparation of a carrier-free multitracer and an Au tracer from an Au target

Separation of Au(III) and various carrier-free radionuclides by solvent extraction was investigated using an Au target irradiated by an energetic heavy-ion beam. Percentage extraction of Au(III) and coextraction of the radionuclides were determined with varying parameters such as kinds of solvent, molarity of HCl or pH, and Au concentration. Under the conditions where Au(III) was effectively extracted, namely extraction with ethyl acetate or isobutyl methyl ketone from 3 mol·dm^–3 HCl, carrier-free radionuclides of many elements were found to be more or less coextracted. Coextraction of radionuclides of some elements was found to increase with an increase in the concentration of Au(III). This finding is ascribed to the formation of strong association of the complex of these elements with chloroauric acid. In order to avoid serious loss of these elements by the extraction, lowering of the Au(III) concentration or the use of a masking agent such as sodium citrate is necessary. Gold(III) was shown to be effectively back extracted with a 0.1 mol·dm^–3 aqueous solution of 2-amino-2-hydroxymethyl-1,3-propanediol. Thus, a radiochemical procedure has been established for preparing a carrier-free multitracer and an Au tracer with carrier form from an Au target irradiated with a heavy-ion beam. Both tracers are now used individually for chemical and biological experiments.     

A new method for the measurement of spallogenic53Mn by neutron activation

Résumé Des recherches précises sur les noyaux de spallation de longue période et extrémement peu abondants, produits par l'interaction de rayons cosmiques et de matières exposées, sont d'un grand intérêt pour la géo et la cosmochimie. Ces produits de réaction sont utiles pour la recherche des profils de profondeur d'activité et l'estimation des périodes de radiation. Le⁵³Mn est prometteur par sa relativement forte section efficace de production et sa longue période de radioactivité. Ce noyau émetteur K est transformé par capture neutronique en⁵⁴Mn, facilement mesuré par son rayonnement γ. L'avantage de cette technique est que le niveau d'activité est accru d'un facteur >10⁴. On étudie systématiquement et on corrige les interférences dues aux réactions (n,p) et (n,2n). La constante de décroissance insuffisamment connue jusqu'ici a été recherchée par une transmutation partielle de⁵³Mn météoritique en⁵⁴Mn donnant⁵⁴Cr stable au moyen d'une intense irradiation dans un réacteur pendant 587 jours. Les différences constatées dans le niveau de production de⁵⁴Mn au début et à la fin de l'irradiation permettent alors de rechercher la section efficace de capture σ₅₃=66±7 barn. On en déduit le produit T₅₃·σ₅₃=(260·32)·10⁶ barn·années, conduisant alors à une période de décroissance de T₅₃=(3,9±0,6)·10⁶ années. La quantité absolue de⁵³Mn, produite dans des matériaux de la surface lunaire, est de l'ordre de 2 à 7·10⁻¹² g/g.      

Cupel assay of gold by an activation method

The difficulties of determining gold in rocks and ores are due to two causes: low gold concentrations in rocks (Clark 1 to 4·10⁻⁷%), and non-uniform distribution of gold in ores. A method is proposed which is based on neutron activation of the lead alloy obtained by cupel melting in the procedure of determining gold by cupel assay. Samples of 50 to 100 g are used for cupel melting. Such large samples guarantee their representativeness. Discs of 2 to 3 g are cut from the lead alloy block and activated in a neutron flux of 10¹¹ to 10¹³ n·cm⁻² sec⁻¹. The gold content is determined from the photopeak of¹⁹⁸Au using a standard for comparison. The sensitivity of the method is 0.02 g/metric ton, its accuracy at a gold content in the order of 1.0 g/metric ton is 10% relative. The method is distinguished by the fact that it is fast and requires little labour.     

Indirect method for the determination of aluminium by atomic-absorption spectrometry using an air-acetylene flame

The enhancement of the atomic-absorption signals of iron, cobalt, nickel and chromium in a fuel-rich air-acetylene flame by small amounts of aluminium makes possible the indirect determination of aluminium in the concentration range 0.01-10 ppm. The optimization of working conditions and the occurrence of interferences are reported.     

Neutron activation analysis: A primary method of measurement

Neutron activation analysis (NAA), based on the comparator method, has the potential to fulfill the requirements of a primary ratio method as defined in 1998 by the Comité Consultatif pour la Quantité de Matière — Métrologie en Chimie (CCQM, Consultative Committee on Amount of Substance — Metrology in Chemistry). This thesis is evidenced in this paper in three chapters by: demonstration that the method is fully physically and chemically understood; that a measurement equation can be written down in which the values of all parameters have dimensions in SI units and thus having the potential for metrological traceability to these units; that all contributions to uncertainty of measurement can be quantitatively evaluated, underpinning the metrological traceability; and that the performance of NAA in CCQM key-comparisons of trace elements in complex matrices between 2000 and 2007 is similar to the performance of Isotope Dilution Mass Spectrometry (IDMS), which had been formerly designated by the CCQM as a primary ratio method.     

Neutron activation analysis of detector components for the solar neutrino experiment BOREXINO

The proposed solar neutrino experiment BOREXINO requires detector components of high radiopurity. The acceptable levels for U and Th contaminations reach down to the sub-ppq region. To select suitable materials a very sensitive analysis method have to be applied. In this article a highly developed neutron activation analysis techniques are presented, which have been used to determine the K, Th and U content of detector components, namely nylon, water and liquid scintillator.     

微波溶样流动注射分光光度法在线测定金矿石中的金

采用微波溶样 流动注射在线泡塑富集分离 分光光度联用技术建立了在线快速测定金矿石中金的方法。比较了微波溶样法与传统电热板溶样法,二者结果基本一致。前者溶样时间近似为后者的1 9。确定了两条工作曲线:校正曲线范围为0 1～1.0μg mL,检出限2.2×10-2μg mL;校正曲线范围为1.0～9 0μg mL,检出限1.6×10-1μg mL。FI SP系统分散系数为3.78。对管理样GBW(E) 070014平行11次测定,其RSD为1.3%,对所得结果进行t检验,置信度95%时,无系统误差存在。     

Preparation of molybdenum target by centrifugal method

The molybdenum targets of 2–10 mg/cm² have been prepared on Al and Ti backings by centrifugal sedimentation. The thickness and purity of the produced targets were analysed with Rutherford back scattering measurements, scanning electron microscope and energy dispersive spectrometry. Targets were requested for pilot studies of an alternative accelerator way of ^99mTc production. Targets were tested with deuteron beam of 20 MeV energy and 10 nA intensity. They were irradiated for 10 min and showed no damage what proofed the targets suitability for irradiation with a weak beam of light projectiles.     

Neutron activation analysis by the monostandard method

The “absolute” quantitative processing of complex gamma-ray spectra has been made possible by the use of high resolution detectors and by irradiation with a well thermalized neutron flux. So, the simultaneous determination of many stable elements, either major or trace components is possible without destruction of the sample. The results of measurements on the irradiated samples show a threefold recurrence: (1) each element appears as often as it possesses activable isotopes, under the form of ray emitting nuclides, (2) each nuclide is determined as often as it presents ditinct emission lines, (3) all measurements are repeated in time. So under these conditions and with an original computer data processing, neutron activation analysis is a powerful analytical tool. The recurrence of the results gives access to the interpretation of the origin of various errors which consequently are better estimated. If applied to the study of ancients ceramics, this method should perhaps allow to evaluate the relationship between the geochemical imprint characteristic of the artifact and the original location, or even workshop.     

Ozone reduction at Nafion modified Au electrode and the measurement of ozone concentration in highly resistive solutions

The mass transport and charge transfer kinetics of ozone reduction at Nafion coated Au electrodes were studied in 0.5 mol/L H2SO4 and highly resistive solutions such as distilled water and tap water. The diffusion coefficient and partition coefficient of ozone in Nafion coating are 1.78×10-6 cm2·s-1 and 2.75 at 25℃ (based on dry state thickness), respectively. The heterogeneous rate constants and Tafel slopes for ozone reduction at bare Au are 4.1×10-6 cm·s-1, 1.0×10-6 cm·s-1 and 181 mV, 207 mV in 0.5 mol/L H2SO4 and distilled water respectively and the corresponding values for Nafion coated Au are 5.5×10-6 cm·s-1, 1.1×10-6 cm·s-1 and 182 mV, 168 mV respectively. The Au microelectrode with 3 μm Nafion coating shows good linearity over the range 0-10 mmol/L ozone in distilled water with sensitivity 61 μA·ppm-1 ·cm-2, detection limit 10 ppb and 95% response time below 5 s at 25℃. The temperature coefficient in range of 11-30℃ is 1.3%.     

Project of an internal target for the antiproton ring at FAIR

The case of the internal target for the hyper-nuclear experiment of the PANDA (antiproton Annihilation at Darmstadt) Collaboration at the High Energy Storage Ring of Facility for Antiproton and Ion Research is illustrated. After a discussion of the problems arising from the interaction of a solid internal target with an antiproton beam, the design of material, shape and sizes of a target satisfying the experimental requirements is presented. The techniques used to produce a prototype of this target are illustrated. Then the results of the tests performed on the prototype for investigating the properties (purity, radiation hardness, structure modifications after shaping) are reported and the plan of the future activity is pointed out.     

A new method for the determination of loratadine at an Au microelectrode in flowing systems with the use of fast continuous cyclic voltammetry

This research presents a new method for the fast monitoring of loratadine in pharmaceutical formulation. The method employs the fast Fourier transformation continuous cyclic voltammetry (FFTCV) at a gold microelectrode in a flowing-solution system. Three considerable advantages of the technique are demonstrated. First, there is not any requirement for the oxygen removal from the test solution; second, a subnanomolar detection limit is gained; and, finally, the speed of the method for the determination of a compound is in a broad range of chromatographic methods. A special computer-based numerical method is also introduced for the calculation of the analyte signal and noise reduction. The electrode response was calculated in accordance with the partial and total charge exchanges on the electrode surface after the background current subtraction from that of the noise. The integration range of the currents was set for all potential scan ranges, including the oxidation and reduction of the Au surface electrode in order to obtain a sensitive determination. The objective of the performed experiments was to study the effects of different parameters on the method sensitivity. It was concluded that the method had a linear concentration range of 40–765000 pg/mL (r = 0.999) with a limit of detection and quantitation of 12 and 40 pg/mL, respectively. For the achievement of these optimum results, the parameter values were set to 80 V/s for the scan rate, 0.7 s for the accumulation time, 300 mV for the accumulation potential, and 2 for the pH. The text was submitted by the authors in English.     

Synthesis of Au, Au/Ag, Au/Pt and Au/Pd nanoparticles using the microwave-polyol method

Gold, Au/Ag, Au/Pt and Au/Pd bimetallic nanoparticles with varying mol fractions were synthesized in ethylene glycol and glycerol, using the microwave technique in the presence of a stabilizer poly(N-vinylpyrrolidone) (PVP). It was found that bimetallic colloids of Au/Ag, Au/Pd and Au/Pt form an alloy either on co-reduction of respective metal ions or on mixing individual sols.     

Thermal lifetime of cellulose insulation material evaluated by an activation energy based method

A rapid method, based on a logarithmic degradation model of insulation material, is proposed to reduce the test duration in lifetime assessment of cellulose paper insulating materials. This method proposes the determination of the activation energy from a non-isothermal measurement made by differential scanning calorimetry or another thermal analysis technique and an aging test at a single elevated temperature. The use of the onset temperature of the exothermal peak at ca. 300 °C is proposed for evaluation of the activation energy of degradation. For comparison, the thermal aging of Kraft cellulose paper for power transformer insulation was performed according to the general standard IEC 60216-1/2001 at three different temperatures: 155, 135 and 115 °C, and subsequently, the lifetimes at different service temperatures were estimated. The experimental data proved to have good agreement between the applied methods, the differences being <10 % in terms of the estimated lifetime across the range of service temperatures. The novel proposed method is effective in terms of both energy and manpower costs as compared to the current method: a factor of around 10 in the case of reducing the aging time, a factor of 3 for the time needed for measurements, and a factor of 10 for the reduction of power intake.     

Indirect near-infrared spectrophotometric determination of silicate by the 2-amino-4-chlorobenzenethiol method

An indirect near-infrared spectrophotometric method for the determination of silicate, based on the absorbance of an equivalent amount of molybdenum-2-amino-4-chlorobenzenethiol complex in chloroform solution, has been developed. The green chloroform solution has an absorbance maximum at 715 nm. The development of the spectrophotometric method for the determination of silicate included a study of a buffer system for the purpose of maintaining the pH within a narrow optimum pH range, complex stability, effect of diverse ions, and conformity to Beer's law. The limit of detection is 0.034 mug of silicon per ml of aqueous heteropoly acid solution.     

Effect of water contact on the density distributions of thin supported polymer films investigated by an X-ray reflectivity method

The diffusion processes of water molecules into polymer films (PMMA/PS homopolymers and random copolymers) in contact with liquid water were investigated using gravimetric methods and X-ray reflectivity (XRR) analysis. Methods of water contact and XRR measurement were designed for studying the systems in the nonequilibrium state of diffusion. Gravimetric measurements confirmed the Fickian diffusion behavior of films in contact with water. Vertical density distributions in PMMA and methylmethacrylate-rich copolymer films demonstrate the existence of a water-rich layer at the interface. However, with further absorption of water into the film, the overall density increased throughout the film. The results suggest that the diffusion of water into the polymer film occurs to recover density uniformity with a high concentration of water molecules at the surface. Some XRR data for the PS- and styrene-rich copolymer films could not be fit and converted to a vertical density distribution because of their huge diffusion coefficients. However, the reflectivity curves for these films and the vertical density distribution after sufficient water contact suggested that the surfaces of these films were commonly diffused after water contact. Atomic force microscopy (AFM) analysis demonstrated that the surface roughness of these films actually increased with water content.     

Kinetic spectrophotometric method for the determination of trace amounts of oxalate by an activation effect.

A new, simple and inexpensive kinetic catalytic spectrophotometric method for the determination of oxalate is described. The method is based on an activation effect of oxalate on a catalytic effect of iron(II) on the oxidation of iodide by bromate. The reaction is monitored by measuring the absorbance of triiodide ion at lambda max = 352 nm. A calibration graph was obtained from 0.10 - 7.0 microg cm(-3) of oxalate with a detection limit of 0.080 microg cm(-3). The standard deviations for ten replicate determinations of 0.50, 1.0 and 5.0 microg cm(-3) of oxalate were 4.0, 2.6 and 1.8%, respectively. The applicability of the method was demonstrated by the determination of oxalate ion in real samples.