Formation Thermodynamics of Binary and Ternary Lanthanide(III) Complexes with 1,10-Phenanthroline and Chloride in N,N-Dimethylformamide

Formation thermodynamics of binary and ternary lanthanide(III) (Ln = La, Ce, Nd, Eu, Gd, Dy, Tm, Lu) complexes with 1,10-phenanthroline (phen) and the chloride ion have been studied by titration calorimetry and spectrophotometry in N,N-dimethyl-formamide (DMF) containing 0.2 mol-dm^–3 (C₂H₅)₄NClO₄ as a constant ionic medium at 25°C. In the binary system with 1,10-phenanthroline, the Ln(phen)³⁺ complex is formed for all the lanthanide(III) ions examined. The reaction enthalpy and entropy values for the formation of Ln(phen)³⁺ decrease in the order La > Ce > Nd, then increase in the order Nd < Eu < Gd < Dy, and again decrease in the order Dy > Tm > Lu. The variation is explained in terms of the coordination structure of Ln(phen)³⁺ that changes from eight to seven coordination with decreasing ionic radius of the metal ion. In the ternary Ln³⁺-Cl^–-phen system, the formation of LnCl(phen)²⁺, LnCl₂(phen)⁺, and LnCl₃(phen) was established for cerium(III), neodymium(III), and thulium(III), and their formation constants, enthalpies, and entropies were obtained. The enthalpy and entropy values are also discussed from the structural point of view.     

Properties of Ce–Zr–La–O nano-system with ruthenium modified surface

Structural peculiarities of Ce–Zr–La–O and Ce–Zr–La–O/Ru samples in mean of catalytic properties are compared. The samples (Ce:Zr = 1:1, La = 10÷30 mol.%, Ru = 1.5 wt.%) were obtained by sol–gel method (X-samples) and co-precipitation (P-samples). It is shown that Ce_0.45Zr_0.45La_0.1O_2−δ/Ru X-samples are characterized by high thermal stability and the highest catalytic activity in partial methane oxidation reaction. According to XRD, BET, FTIR, EPR and XPS data it is concluded that the difference in the samples catalytic activity is caused by various disposition of Ru-containing phase on the support surface. The distinction in the dimension of Ru-containing particles (3D or 2D) is conditioned by structural peculiarities of Ce_0.45Zr_0.45La_0.1O_2−δ and Ce_0.35Zr_0.35La_0.3O_2−δ P- and X-samples.     

动力学电位法测定硼

本文根据硼酸，苯乙醇酸，孔雀绿形成三元离子缔合型配合物的反应，用孔雀绿离子选择性电极监测反应速率，在最佳实验条件下，用固定时间法，电位变化与硼量在０．２－５．０μｇ／ｍＬ范围呈线性关系，用於测定标准钢样和玻璃标样中的硼，结果与标准值十分接近。     

Analytical study of highly condensed non ionic surfactants. Separation on cation exchangers

Summary This study was aimed at optimizing the separation of non-ionic surfactants, resulting from the condensation of ethylene oxide with natural fatty alcohols in the C₁₆ and C₁₈ range (saturated and unsaturated), and presenting a high degree of condensation, i.e. 20 and 25 ethylene oxide units (Brij 99 and KM 25). The cation exchange stationary phase is a partially ionized silica, conditioned in different ways. We have studied the influence of the nature of cations on the separation selectivity. Cations studied included alkali metals (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺), alkaline earth metals (Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺), transition metals (Zn²⁺, Cd²⁺, Hg²⁺, Pb²⁺, Cu²⁺), and quaternary ammonium (NH ₄ ⁺ , NMe ₄ ⁺ ) ions as well as a proton (acetic acid). The influences of ionic strength, pH and addition of cosolvent were examined. A study of the influence of temperature on the system selectivity evidenced a strong interdependance of these two parameters. The optimized conditions [mobile phase: CH₃CN/H₂O (92/8), pH 7.4, sodium acetate 5.10^–3 M; temperature gradient between 25 and 50°C] allowed for the first time the distributions of Brij 99 and KM 25 to be obtained.     

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.     

Computer simulation of the steady state currents at enzyme doped carbon paste electrodes

The plate-gap model of porous enzyme doped electrode has been proposed and analyzed. It was suggested that reaction diffusion conditions in pores of bulk electrode resemble particular conditions in thin gap between parallel conducting plates. The model is based on the diffusion equations containing a nonlinear term related to the Michaelis–Menten kinetic of the enzymatic reaction inside gap. Steady state current was calculated for the wide range of given parameters and substrate concentrations. All dependences of current on substrate concentration were approximated by hyperbolas in order to obtain “apparent” parameters (maximal currents and apparent Michaelis constants) of modelled biosensors. Simple approximate relationships between given and apparent parameters were derived. The applicability of theoretical plate-gap model was tested for the case of carbon paste electrodes which were doped with PQQ – dependent glucose dehydrogenase. It was found, that soluble glucose dehydrogenase based biosensors exhibit characteristic features of the theoretical plate-gap biosensors.     

A dual-electrode approach for highly selective detection of glucose based on diffusion layer theory: experiments and simulation

A dual-electrode configuration for the highly selective detection of glucose in the diffusion layer of the substrate electrode is presented. In this approach, a glassy carbon electrode (GCE, substrate) modified with a conductive layer of glucose oxidase/Nafion/graphite (GNG) was used to create an interference-free region in its diffusion layer by electrochemical depletion of interfering electroactive species. A Pt microelectrode (tip, 5 microm in radius) was located in the diffusion layer of the GNG-modified GCE (GNG-G) with the help of scanning electrochemical microscopy. Consequently, the tip of the electrode could sense glucose selectively by detecting the amount of hydrogen peroxide (H2O2) formed from the oxidization of glucose on the glucose oxidase layer. The influences of parameters, including tip-substrate distance, substrate potential, and electrolyzing time, on the interference-removing efficiency of this dual-electrode approach have been investigated systematically. When the electrolyzing time was 30 s, the tip-substrate distance was 1.8 a (9.0 microm) (where a is the radius of the tip electrode), the potentials of the tip and substrate electrodes were 0.7 V and 0.4 V, respectively, and a mixture of ascorbic acid (0.3 mM), uric acid (0.3 mM), and 4-acetaminophen (0.3 mM) had no influence on the glucose detection. In addition, the current-time responses of the tip electrode at different tip-substrate distances in a solution containing interfering species were numerically simulated. The results from the simulation are in good agreement with the experimental data. This research provides a concept of detection in the diffusion layer of a substrate electrode, as an interference-free region, for developing novel microelectrochemical devices.     

Microstructural and physicochemical study of the buried Fe/AlGaAs(100) interface by transmission electron microscopy and x‐ray emission spectroscopy

Among the magnetic metal/semiconductor contacts, the Fe/GaAs system has been widely studied owing to its potential applications in electronic devices. In contrast, there are not many studies concerning the Fe/Al_xGa_1?xAs contact, and in particular there are no reports concerning the changes induced in the interfacial zone by the presence of Al. In this work, thin polycrystalline iron films were deposited by ion beam sputtering at room temperature on a 300 nm thick Al_0.25Ga_0.75As layer grown by molecular beam epitaxy onto GaAs(001). X‐ray diffraction analysis showed that the iron films are polycrystalline, and indications of a (002) texture of the film were observed. The fine scale analysis of the interface was achieved by high‐resolution transmission electron microscopy (HRTEM) observations, the results of which are compared with the physicochemical information obtained from electron‐induced x‐ray emission spectroscopy, by analysing the Al 3p valence states at the Fe/Al_xGa_1?xAs interface. The HRTEM experiments on cross‐section samples indicate that the interfacial zone between iron and AlGaAs is limited to <1.5 nm in thickness. X‐ray emission spectroscopy showed the presence of Al atoms in an FeAl‐like environment at the interface, and the existence of wrong bonds and point defects. The estimated width of the perturbed interface (2.0 ± 0.5 nm) is in agreement with the HRTEM results. Copyright © 2003 John Wiley & Sons, Ltd.     

Synthesis of thiol chelating resins and their adsorption properties toward heavy metal ions

A series of chelating resins, derived from a macroreticular styrene-divinylbenzene (2%) copolymer beads grafted with various poly(ethylene glycols) HO? (? CH₂? CH₂? O? )_n? H(n = 0, 4, 9, 13) and containing thiol groups as chelating functions, have been synthesized in a three-step reaction sequence. The structure of the functionalized resins was confirmed by IR spectrophotometry, elemental analysis, and differential scanning calorimetry. The complexation behavior of these thiol resins was investigated towards Hg(II), Cu(II), and Pb(II) ions in aqueous solution by a batch equilibration technique. The influence of pH on adsorption capacity was also examined. The adsorption values for metal ions' intake followed the order Hg(II) > Cu(II) > Pb(II). The affinity of these polymers towards Hg(II) ions was so high that the total mercury level in the liquid decreased from 20 ppm to below 10 ppb after 2 h of treatment. Polymers can be regenerated by washing with a solution of hydrochloric acid (6N) and 10% by weight of an aqueous solution of thiourea. © 1994 John Wiley & Sons, Inc.     

Polypyrrole Bilayers: Charge Trapping and Application for Amperometric Ions Sensing

Bilayers composed of polypyrrole: doped by perchlorate ions (PPy(ClO₄) – anion exchanging inner layer) and by dodecyl sulfate ions (PPy(DS) – cation exchanging outer layer) are very effective charge trapping systems that are usually not observed for other bilayers comprised of polypyrrole. Chronopotentiometric experiments carried out for oxidation and reduction showed that the trapping effect in the inner layer resulted from different ion exchange properties of the component polymers, leading to a low permeability of the reduced outer layer towards anions. Estimated diffusion coefficients of Cl^? anions in the oxidized and reduced PPy(DS) are in the range of 10^?9 and lower than 10^?10 cm² s^?1, respectively. The presence of the outer layer limiting the ion transfer was found to be beneficial to improve the signal resolution in amperometric mode of ion sensing within wide KCl concentration range, from 10^?5 M up to 3 M. The influence of experimental conditions (film thickness, response time) on optimization of this novel kind of polymeric bilayer ion sensors was studied.