Selectrode—the universal ion-selective electrode : Part VII. A valinomycin-based potassium electrode with nonporous polymer membrane and solid-state inner reference system

A potassium electrode utilizing a solution of valinomycin in diphenylether and a porous membrane is compared with selectrodes in which the diphenylether has been replaced by a suitable plasticizer and the porous membrane support by a polymer net-work. The development of the polymer membrane allows the use of simplified selectrode construction with a “solid-state” calomel reference system; Rules for a successful choice of a suitable solvent-polymer combination are suggested and used for development of new Polyvinylchloride- and polyurethane-based membranes.     

Mercury Speciation in Fish by High-Performance Liquid Chromatography (HPLC) and Post-Column Ultraviolet (UV)-Photochemical Vapor Generation (PVG): Comparison of Conventional Line-Source and High-Resolution Continuum Source (HR-CS) Atomic Absorption Spectrometry (AAS)

An ultraviolet-photochemical generator (UV-PVG) capable of post-column on-line transformation of both organic and inorganic mercury species to cold vapor (Hg⁰) with subsequent detection by quartz tube-atomic absorption spectrometry (QT-AAS) was developed. Mercury(II), methylmercury(I), ethylmercury(I), and phenylmercury(I) were successfully detected after separation by reversed-phase high-performance liquid chromatography (RP-HPLC). Two types of AAS detectors were compared. The first was a commonly used line-source instrument while the second was a high-resolution continuum source (HR-CS) AAS. The latter provided better limits of detection: 0.47?µg?L^?1 for Hg(II), 0.84?µg?L^?1 for methylmercury(I), 0.80?µg?L^?1 for ethylmercury(I), and 2.0?µg?L^?1 for phenylmercury(I). The repeatability at 30?μg?L^?1 was 3.6%, 4.1%, 6.2%, and 4.5% for these species (n?=?10). These figures of merit were comparable with those reported for more sensitive atomic fluorescence spectrometry. Nine sample extraction procedures were investigated. Extraction by tetramethylammonium hydroxide and HCl at 75?°C was selected as the only method compatible with the proposed separation and detection steps providing high extraction efficiency and no changes in mercury speciation. The applicability of the proposed high-performance liquid chromatography–ultraviolet-photochemical vapor generation–quartz tube-atomic absorption spectrometry method was demonstrated using fish samples and certified reference materials (CRM) DOLT-4 (dogfish liver) and ERM-CE464 (tuna fish). The results were comparable to those obtained by a reference method based on L-cysteine extraction and high-performance liquid chromatography–inductively coupled plasma-mass spectrometry (HPLC–ICP-MS) determination.     

The surface catalytic mechanism: a comparative study with square-wave and staircase cyclic voltammetry

A pseudo-first-order catalytic mechanism in which both reactant and product of a redox reaction are strongly immobilized on an electrode surface is theoretically analysed under conditions of square-wave (SWV) and staircase cyclic voltammetry (SCV). A mathematical procedure is developed under diffusionless conditions. The relationships between the properties of the voltammetric response and both the kinetic parameters of the redox reaction and the parameters of the excitation signal are studied. The phenomenon of the quasi-reversible maximum is discussed. A comparative study between SWV and SCV is presented and the limitations and advantages of both techniques, from analytical and kinetic points of view, are discussed. The theoretical predictions are experimentally confirmed by the redox reaction of azobenzene in the presence of hydrogen peroxide as an oxidizing agent. Electronic Publication     

Study of radioactive labelled chromium (III) ion adsorption on stearic acid monomolecular layer

A study of chromium(III) ion adsorption on a stearic acid monomolecular layer (MML), spread on the surface of a⁵¹CrCl₃ aqueous solution, is presented. From the analysis of the experimental results it can be concluded that MML saturation is achieved at CrCl₃ concentrations above 10^?6M. When the maximum adsorption pH value of Cr(III) ions on MML is 6.7, MML is completely ionized and chromium ion is bonded as Cr(OH) ₂ ⁺ . The kinetics of Cr(III) ion adsorption on MML could be expressed as A^S=A _∞ ^S (1?e^{?k t}).     

Deconvolution of lignin fluorescence spectra: A contribution to the comparative structural studies of lignins

In this work, we deconvoluted the fluorescence spectra of lignin and a lignin model compound using a combination of one symmetric (Gaussian) and the most appropriate number of asymmetric (Log-normal) models. We aimed to obtain new data on the structural characteristics of lignin as a complex molecule using fluorescence spectroscopy in combination with FTIR spectra. We analyzed the emission spectra of the lignin model compound, DHP, and isolated lignins from a deciduous tree, poplar, and a coniferous tree, spruce. The number of applied asymmetric components was varied for each sample until the component positions obtained from deconvolution of a series of spectra became constant. The lignin model compound contains fewer components in the emission spectrum. The same components in the spectra of all three samples show that they contain the same fluorophores. The small shift of the peak position can be attributed to the influence of different environments. The FTIR spectra of the three polymers show a small difference between their structures. The main difference among the IR spectra of the three samples is in the intensity of some peaks. The text was submitted by the authors in English.     

Synthesis,characterization and DNA-binding properties of zinc(II) and nickel(II) Schiff base complexes

A new ligand, 2-carboxybenzaldehyde-(4’-hydroxy)benzoylhydrazone(H₂L) and its Zn^II and Ni^II complexes have been synthesized and characterized on the basis of elemental analyses, molar conductivities, ¹H-NMR, IR spectra and thermal analyses. In addition, DNA-binding properties of these two metal complexes were investigated using spectrometric titrations, ethidium bromide displacement experiments, and viscosity measurements. The results show that the two complexes, especially the Ni^II complex, strongly bind with calf-thymus DNA, presumably via an intercalation mechanism. The intrinsic binding constants of the Zn^II and Ni^II complexes with DNA are 2.46 × 10⁵ and 7.94 × 10⁵ M ⁻¹, respectively.     

The separation of some Bi- and tervalent cations on zirconium phosphate columns

Summary On small columns filled with the inorganic cation-exchanger zirconium phosphate, Zn²⁺-Cd²⁺ were quantitatively and Ni²⁺-Co²⁺ partly separated. The exchanger was in the NH₄+ form, and 0.5–4N NH₄Cl served as eluent. With the exchanger in the H+ form, U0₂ ²⁺ was separated from bivalent cations and ferric iron by stepwise elution with 0.1, 0.5 and 4N HCl solutions.

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Zusammenfassung An kleinen Säulen des anorganischen Kationenaustauschers Zirkoniumphosphat wurden Zn²⁺ und Cd²⁺ quantitativ, Ni²⁺ und Co²⁺ teilweise getrennt. Der Austauscher lag in der NH₄+-Form vor, 0,5-bis 4-n Ammoniumchlorid diente als Eluent. Mit der H+-Form des Austauschers wurde UO₂ ²⁺ von zweiwertigen Kationen und von Fe³⁺ durch schrittweise Elution mit 0,1-, 0,5- und 4-n Salzsäure getrennt.

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Résumé On a séparé Zn²⁺-Cd²⁺ quantitativement et Ni²⁺-Co²⁺ partiellement sur de petites colonnes remplies de phosphate de zirconium comme échangeur minéral cationique. L'échangeur se trouvait sous forme NH₄+ et l'on a pris NH₄Cl 0,5-4N comme éluant. Avec l'échangeur sous forme H⁺, on a séparé UO₂ ²⁺ des cations bivalents et de l'ion ferrique par élution graduelle avec des solutions chlorhydriques 0,1, 0,5 et 4N.

     

On the behaviour of cerium(III) in hydrochloric acid

Summary The sorption of Ce³⁺ from hydrochloric acid and its chromatography on a column filled with Dowex 50 X8 was studied. The break-through volumes and elution volumes, together with the sorption profile and band broadening were determined at different temperatures and are discussed. The Chromatographic results are interpreted in terms of cerium complex formation.

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Über das Verhalten von Cerium(III) in salzsaurer Lösung

Zusammenfassung Die Sorption von Ce³⁺ aus salzsaurer Lösung in einer mit Dowex 50 X8 gefüllten Säule sowie dessen Chromatographie wurden untersucht. Die Durchbruchs- und Elutionsvolumina wurden bestimmt und diskutiert. Die Ergebnisse wurden im Sinne einer Komplexbildung interpretiert.

     

Effect of film thickness on the electro-reduction of molecular oxygen on electropolymerized cobalt tetra-aminophthalocyanine films

We studied the electrocatalytic activity of cobalt tetra-aminophthalocyanine (CoTAPc) for the reduction of molecular oxygen (O₂) on adsorbed monomeric and on electropolymerized films of different thicknesses on glassy carbon (GC) electrode. The polymeric films, denoted poly-CoTAPc, were first characterized by electrochemical impedance spectroscopy and it appears that the types of phenomena revealed to be occurring depend less on the film thickness in basic than in acid media. For O₂ reduction, the results showed that poly-CoTAPc is more active than the monomeric CoTAPc adsorbed on GC. Indeed, rotating ring-disk electrode data showed that polymeric CoTAPc promotes the four-electron reduction of O₂ to water in parallel to a two-electron reduction to give peroxide. On monomeric and thin films of poly-CoTAPc, a two-electron reduction mechanism predominates. In basic media the activity increases very slightly with thickness, whereas in acid media this increase is more pronounced. This parallels the observed behavior revealed by electrochemical impedance spectroscopy.     

Sorption of uranium by non-living water hyacinth roots

Summary Many studies have shown that water hyacinth (Eichhornia crassipes) roots can be used to accumulate high concentrations of organic as well as inorganic pollutants. They are currently used to remediate aquatic environments and aqueous solutions. In the present study, sorption of uranium from aqueous solutions by using dried roots of water hyacinth has been investigated. The sorption of uranium was examined as a function of initial concentration, pH, weight of roots and contact time. Five different concentrations 20, 40, 60, 80, and 100 μg ^. ml^-1 were used. Sorption proves to be very rapid and depend on pH, weight of roots and concentration of uranium. Maximum sorption capacity of water hyacinth roots was 64,000 U⁶⁺ μg/g. The sorption of uranium by water hyacinth roots follows a Langmuir isotherm.