The electrochemical behavior and application of a new sensor, a silver solid amalgam paste electrode (AgSA-PE), based on the mixture of a fine silver solid amalgam powder (60:40 (w(Hg)/w(Ag))) and a suitable organic pasting liquid (Paraffin oil) in a ratio of 20:1 (w/w), was investigated in an aqueous-methanolic media (1:1). This alternative working electrode provides simple preparation and handling, adequate mechanical stability, easily renewable electrode surface, sufficiently wide cathodic potential window (up to -1200 mV within a pH range of 2.7-12.3), and sufficient sensitivity without any necessary pretreatment. The practical usability of the AgSA-PE was verified by the development of voltammetric methods for the determination of selected environmentally important pollutants (1,3-, 1,5-, and 1,8-dinitronaphthalenes) in an aqueous-methanolic media (1:1). The differential pulse voltammetric methods at AgSA-PE give linear concentration dependences in the range of 1-100 µmol l(-1) with limits of detection of about 1 µmol l(-1) in a mixture of Britton-Robinson buffer of appropriate pH and methanol (1:1).
- Publikační typ
- časopisecké články MeSH
An electrodeposited palladium and iridium/gold mixture has been investigated as a chemical modifier for mercury determination in environmental samples by solid sampling electrothermal atomic absorption spectrometry. Electrochemical procedures of platform surface modification performed in a cell with 20 ml of solution, and in a drop of modifier solution have been optimized. Simple electrolysis in a drop was found to be the most consistent, taking the reproducibility as the major criterion. A total mass of 250 µg of electrodeposited palladium or an iridium/gold mixture was used. The lifetime of 60 - 70 firings for a deposited iridium/gold mixture was smaller than that for palladium with a lifetime of 100 - 120 firings. The detection limit was 120 pg Hg. Different sample masses of between 0.1 and 10 mg were weighed into modified platforms according to the mercury content. The results obtained for mercury in environmental samples as soils, sediments and plant, using solid sampling and calibration against aqueous standards stabilized by potassium permanganate, were in good agreement with those achieved by using the thermal deposition of modifiers and with measurements by pyrolysis atomic absorption spectrometry with gold amalgamation.
- MeSH
- elektrochemické techniky * MeSH
- extrakce na pevné fázi MeSH
- grafit * chemie MeSH
- iridium chemie MeSH
- kalibrace MeSH
- látky znečišťující životní prostředí analýza MeSH
- palladium chemie MeSH
- pokovování galvanické MeSH
- rtuť analýza MeSH
- spektrofotometrie atomová * MeSH
- vysoká teplota MeSH
- zlato chemie MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Názvy látek
- grafit * MeSH
- iridium MeSH
- látky znečišťující životní prostředí MeSH
- palladium MeSH
- rtuť MeSH
- zlato MeSH
Non-evaporable Ti-Zr-V ternary getters (NEGs) were studied by means of excitation energy resolved photoelectron spectroscopy (ERXPS). We attempted a quantitative study of the in-depth redistribution of the NEG components during activation. The samples were prepared ex-situ by DC magnetron sputtering on a stainless-steel substrate. The ERXPS measurements were carried out at two incident photoelectron beam angles at energies of 110, 195, 251, 312, 397 and 641 eV. Besides these photon energies, also standard X-ray photoelectron spectroscopy (XPS) was used at a photon energy of 1254 eV. We accumulated Ti 3s, Ti 3p, Ti 3d, V 3s, V 3p, V 3d, Zr 3p, Zr 3d, Zr 4s, Zr 4p, Zr 4d, C 1s, O 1s and O 2s photoelectron peak intensities as functions of the kinetic energies given to them. Under simplifying assumptions, Monte-Carlo calculations of the activated sample concentration profiles were performed to fit the measured spectra intensities. The results proved an in-depth redistribution of the components during the activation process. This way we also contributed to a further development of non-destructive depth profiling by electron spectroscopy techniques.
- Publikační typ
- časopisecké články MeSH
This paper reviews work done of the influence of non-ideal surface topography on electron spectral intensities of surface-sensitive electron spectroscopic methods: primarily X-ray induced photoelectron spectroscopy (XPS) and concise Auger electron spectroscopy (AES), electron energy loss spectroscopy in the reflection mode (REELS), and elastic peak electron spectroscopy (EPES). Several attempts to solve the problem are mentioned, where (i) the effect of surface roughness is corrected using a single parameter, (ii) computer simulations based on a model of surface roughness composed of regular geometrical units are used for electron spectral intensity calculations, and finally, (iii) a semi-empirical method based on careful surface mapping of analyzed sample by atomic force microscopy (AFM) is discussed in greater detail. The first approach was found to be rather simple to properly include any complex surface topography. The second technique can help us to understand surface topography related phenomena. The latter method, suitable for arbitrary rough solid surfaces covered by conformal overlayer(s), can be incorporated in current quantitative procedures valid for ideally flat surfaces.
- Publikační typ
- časopisecké články MeSH
A simple and reliable HPLC method for determination of rat plasma levels of clinically used acetylcholinesterase (AChE) reactivators (HI-6 and obidoxime) is presented in our study. Separation was carried out by HPLC using an octadecyl silica stationary phase and a mobile phase consisting of 24% acetonitrile and containing 5 mM sodium octanesulfonate and 5 mM tetramethylammonium chloride (pH 2.3). Following intramuscular administration of equimolar doses of both oximes (22.23 mg/kg), the maximum of HI-6 concentration in rat plasma was reached in about 20 min giving 15.26 +/- 1.71 microg/mL. The distribution of obidoxime was fast; the single maximum 23.62 +/- 3.563 microg/mL was recorded at about 10 min. HPLC with UV detection presented in our study is a general method which could be applied for quick measurements of bisquaternary AChE reactivators in rat plasma.
- MeSH
- indikátory a reagencie MeSH
- injekce intramuskulární MeSH
- kalibrace MeSH
- krevní proteiny chemie MeSH
- krysa rodu Rattus MeSH
- kyselina trichloroctová chemie MeSH
- obidoxim chlorid krev farmakokinetika MeSH
- oximy krev farmakokinetika MeSH
- potkani Wistar MeSH
- pyridinové sloučeniny krev farmakokinetika MeSH
- reaktivátory cholinesterasy krev farmakokinetika MeSH
- reprodukovatelnost výsledků MeSH
- spektrofotometrie ultrafialová MeSH
- vysokoúčinná kapalinová chromatografie MeSH
- zvířata MeSH
- Check Tag
- krysa rodu Rattus MeSH
- mužské pohlaví MeSH
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Názvy látek
- asoxime chloride MeSH Prohlížeč
- indikátory a reagencie MeSH
- krevní proteiny MeSH
- kyselina trichloroctová MeSH
- obidoxim chlorid MeSH
- oximy MeSH
- pyridinové sloučeniny MeSH
- reaktivátory cholinesterasy MeSH
A possible replacement of previously recommended Spheron-Thiol resin gel for measuring mercury by diffusive gradients in a thin film (DGT) was studied. Duolite GT73 resin and newly prepared 6-mercaptopurine modified Iontosorb AV as binding phases were tested. The preparation procedure of resin-embedded gels was optimized and DGT with new resin gels verified. The verified DGT containing new resin gels was used for in situ mercury measurement in Svitava River.
- Publikační typ
- časopisecké články MeSH
This paper describes how the K(alpha)/K(beta) count rate ratio of the characteristic X-rays of a given element can be applied to determine the depth at which a layer or a grain of that element is located. The theoretical background and a basic description of the K(alpha)/K(beta) technique are given in the introduction. The experimental part of the paper deals with measurements of thick standard pure iron, intermediately thick iron foils, and layers prepared with a powder of Prussian blue. All these specimens were analyzed alone, and they were also analyzed overlaid with a low Z matrix. The light matrix consisted of sheets of paper of known thickness. Paper was chosen, because we take into account the subsequent application of this technique to surveys of historical monuments. The relation between the K(alpha) count rate, the K(alpha)/K(beta) count rate ratio, and the distribution of iron in the paper matrix are presented here.
- Publikační typ
- časopisecké články MeSH
This paper gives two empirical correlations of formation Gibbs energies of gaseous clusters DeltaG(f)n as function of number of solvent molecules attached to the ion, n, and one correlation connecting the DeltaG(f)n for each individual cluster with the total DeltaG(o)hydr value. The experimental ratios of DeltaG(f)2/DeltaG(f)1 and DeltaG(f)3/DeltaG(f)1 for both alkali metal and halide ions are on average equal to 0.75 and 0.5, respectively. DeltaG(f)n values for n > or = 4 are correlated with n as DeltaG(f)n = [a/(n - 1)] DeltaG(f)1 + b DeltaG(f)1. For all available data on cluster energies and each individual cluster, the DeltaG(f)n's are straight-line functions of DeltaG(o)hydr. This well corresponds to another empirical rule stating that the Gibbs energies of transfer of ions between two solvents are often as well straight-line functions of DeltaG(o)(hydr) [J. Rais and T. Okada, J. Phys. Chem. A, 2000, 104, 7314]. Tentative models of the found behavior are proposed. A full data set of the gaseous cluster energies of formation based on inclusion of new, usually not used entries from the literature is provided.
- Publikační typ
- časopisecké články MeSH
The testing of various types of carbon paste electrodes (CPEs) for their use in stripping potentiometry was carried out by means of specially proposed procedures and by using various model analyte systems. CPEs containing three different pasting liquids (paraffin oil, silicone oil, tricresyl phosphate) were tested as supports for mercury- and gold films, and as substrates for electrolytic, adsorptive, ion-pair forming, and extractive accumulation. Test measurements in organic solvent-containing media and studies of some irreversible electrochemical reactions were performed as well. Individual examples to be studied allowed one to formulate and outline some perspectives of CPEs in potentiometric stripping analysis and related constant current stripping analysis.
- Publikační typ
- časopisecké články MeSH
