Probes and Polymers for Optical Sensing of Oxygen

Oxygen detection techniques are used in various fields, such as chemical or clinical analysis and environmental monitoring. Recently, a variety of devices and sensors based on photo-luminescent or photoexcited state quenching of organic dyes have been developed to measure oxygen partial pressure on the solid surface. Many optical oxygen sensors are composed of organic dyes, such as polycyclic aromatic hydrocarbons (pyrene, pyrene derivative etc.), transition metal complexes (Ru²⁺, Os²⁺, Ir³⁺ etc.), metalloporphyrins (Pt²⁺, Pd²⁺, Zn²⁺ etc.) and fullerene (C₆₀ and C₇₀) immobilized in oxygen permeable polymer films. In this review, the properties of various oxygen permeable polymers for matrix of optical oxygen sensor and various dye probes for oxygen sensing are described.Received November 19, 2002; accepted May 14, 2003 published online August 22, 2003     

Electrochemical properties of lanthanum nickel oxide

Electrochemical properties of lanthanum nickel oxide, LaNiO₂₈₄, were studied in alkaline solutions. It was concluded that redox reactions of Ni⁴⁺/Ni³⁺ and Ni³⁺/Ni²⁺ in a solid surface layer took place at 0.4 V and ?0.4 V (vs. Hg/HgO), respectively. As the conductivity of the oxide is a function of the oxygen concentration due to σ^* bond formation, the resistivity of the electrode was changed depending on polarization potentials. The catalytic activity for oxygen reduction of a preoxidized electrode seemed to be higher than that of an electrode not intentionally oxidized, and the activity depended on the concentration of the alkaline solution. It was presumed that Ni³⁺ cations which form the σ^* bond with oxygen have an important role in the electrocatalysis of oxygen reduction on lanthanum nickel oxide.     

Radiopolarographic determination of the stability constant of 18-crown-6 complex for Ra2+

The interaction of Ra²⁺, Sr²⁺ and Ba²⁺ with 1,4,7,10,13,16-hexaoxacyclooctadenace /18-crown-6/ in an aqueous solution was investigated by radio- and dc polarography. It was found that all these ions form 11 complexes with 18-crown-6 and their stability constants, lg K, are 3.43 for Ra²⁺, 2.40 for Sr²⁺ and 3.67 for Ba²⁺, respectively. The stability constant for Am²⁺ was estimated from the relationship between lg K for Sr²⁺, Ba²⁺, Ra²⁺, Eu²⁺, Yb²⁺ and Cf²⁺ and the ionic radii.     

State of manganese ions in the structure of corundum synthesized in supercritical water fluid

The kinetics and formation mechanism of doped corundum (α-Al₂O₃) from hydrargillite (γ-Al(OH)₃) in supercritical water fluid (SCWF) in the presence of manganese ions are studied. It was ascertained that due to the reversible dehydroxylation in an aqueous medium, solid-phase transformation of hydrargillite into boehmite (γ-AlOOH) and then into corundum occurs with the formation of well-faceted corundum micro-crystals that are uniformly doped with manganese. It was found that when Mn²⁺ or MnO₄⁻ ions are introduced into the reaction medium, Mn⁵⁺, Mn⁴⁺, Mn³⁺, and Mn²⁺ ions are observed in the synthesized corundum. Meanwhile, the manganese ions form a complex defect in the corundum structure, which comprises oxygen vacancies and hydroxyl groups. The defects in corundum that emerge upon doping with manganese in SCWF are different from those in corundum doped during high-temperature synthesis.     

Cobalt Element Effect of Ternary Mesoporous Cerium Lanthanum Solid Solution for the Catalytic Conversion of Methanol and CO2 into Dimethyl Carbonate

A citric acid ligand assisted self-assembly method is used for the synthesis of ternary mesoporous cerium lanthanum solid solution doped with metal elements (Co, Zr, Mg). Their textural property was characterized by X-ray diffraction, transmission electron microscopy, N₂ adsorption-desorption, X-ray photoelectron spectroscopy and TPD techniques, and so on. The results of catalytic testing for synthesis of dimethyl carbonate (DMC) from CH₃OH and CO₂ indicated that the DMC yield reached 316 mmol/g on Ce-La-Co solid solution when the reaction temperature was 413 K and the reaction pressure was 8.0 MPa. It was found that Co had synergistic effect with La and Ce, doping of Co on the mesoporous Ce-La solid solution was helpful to increase the surface area of the catalyst, promote CO₂ adsorption and activation, and improve the redox performance of solid solution catalyst. The conversion of Co²⁺ to Co³⁺ resulted in the continuous redox cycle between Ce⁴⁺ and Ce³⁺, and the oxygen vacancy content of the catalyst was increased. Studies have shown that the catalytic performance of Ce-La-Co solid solution is positively correlated with oxygen vacancy content. On this basis, the reaction mechanism of DMC synthesis from CO₂ and CH₃OH on the catalyst was speculated.     

Effect of dopant addition on oxygen sorption properties of La-Sr-Co-Fe-O perovskite type oxide

The paper reports on effect of doping Ag⁺, Ni²⁺, Ca²⁺, Ba²⁺ or Zr⁴⁺ in La_0.1Sr_0.9Co_0.9Fe_0.1O_3−δ (LSCF1991) on its oxygen sorption capacity and desorption rate. The dopant can be incorporated into LSCF1991 matrix causing lattice expansion. The oxygen sorption capacity and tendency for the disordered perovskite to ordered brownmillerite phase transition for these samples decrease in the order: LSCF1991 > LSCF-Ag > LSCF-Ni > LSCF-Ca > LSCF-Ba > LSCF-Zr. The oxygen desorption rate also decreases in the same order for the doped samples. Doping increases the tendency of the disorder to order phase transition and enhances oxygen desorption rate during oxygen desorption step. Doping Ag and Ni provides more pronounced enhancement in oxygen desorption rate. The results suggest that Ag and Ni doped LSCF1991 samples are promising sorbents for use in a high temperature sorption process for air separation.     

Synthesis of Macroporous Ellagitannic Acid Resin and Its Chelating Properties for Metal Ions

A new type of macroporous ellagitannic acid resin (EAR) can be prepared from macroporous crosslinked chloromethylated polystyrene beads and ellagic acid in the presence of NaOH and KI as catalysts. The synthetic route and structure of the polymer were examined. The structure of EAR was confirmed by elementary analysis and IR spectra. The oxygen content of EAR was 7.06%, and the functional group capacity of EAR was 0.441 mol EA/g EAR. The conversion of functional groups was 8.33%. Cu²⁺, Fe³⁺, Ce³⁺, and La³⁺ can be easily adsorbed by EAR. The adsorption capacities for these metal ions per g EAR were 0.609 mmol Cu²⁺, 1.523 mmol Fe³⁺, 0.320 mmol Ce³⁺, and 1.561 mmol La³⁺. The influence of pH, acidity, ionic concentration, adsorption time, and temperature on the percentage of adsorption was investigated.     

Thermodynamics of oxygen in CaMnO3 − δ

The experimental data for equilibrium oxygen content were used in order to extract increments of partial molar thermodynamic functions of oxygen with changes of oxygen stoichiometry in calcium manganite CaMnO_3???δ . It is shown that along with the oxygen exchange reaction, thermal excitation of Mn⁴⁺ cations plays an important role in equilibration of charged manganese species that appear in response to the loss of oxygen at heating. The interrelation of partial molar enthalpy and entropy of oxygen with electron and ion defect formation parameters is obtained in approximation of the point defect model. The nearly linear changes of oxygen partial molar enthalpy are shown to directly reflect thermally driven changes in concentration of Mn³⁺ cations.     

Kinetics and Mechanism of the Oxidative Conversion of <Emphasis Type="Italic">n</Emphasis>-Amyl Alcohol to Valeric Acid on a Modified Zeolite Catalyst

The catalytic activity of natural and synthetic mordenites modified with Cu²⁺, Zn²⁺, and Pd²⁺ cations via ion exchange was studied in the oxidative conversion of n-amyl alcohol to valeric acid under the action of oxygen. It is established that the highest activity and selectivity in this reaction is exhibited by mordenite hydrothermally synthesized from kaolinite and containing 3.0 wt % Cu²⁺, 0.1 wt % Pd²⁺, and 2.0 wt % Zn²⁺. The kinetics of this catalytic reaction is studied. Based on the experimental data, a possible stepwise mechanism is proposed, and a theoretically grounded kinetic model of the process is developed.     

Polarographic detection by reverse-pulse amperometry in cation-exchange chromatography without interference from dissolved oxygen

Reverse-pulse amperometry (r.p.a) at a static dropping mercury electrode (SDME) is applied for detection in high-performance cation-exchange chromatography for Cu²⁺, Zn²⁺, Ni²⁺, Pb²⁺, Cd²⁺ and Fe²⁺ using a tartrate eluent (pH 3.5–4.5). The technique of r.p.a. as applied eliminates the need for removal of dissolved oxygen because the anodic signals for oxidation of the reduction products are measured at a potential at which oxygen is not electroactive. Typical detection limits (S/N = 2) for a 100-μl sample are illustrated by the values 13 μg l^?1 Zn²⁺ (1.3 ng) and 64 μg l^?1 Cu²⁺ (6.4 ng). The detection limits are decreased by ca. 2 orders of magnitude by using preconcentration from a 10.0-ml sample on a cation-exchange fore-column.     

冠醚聚合物的研究 Ⅱ.以聚硫醚为主链的硫杂冠醚聚合物的合成及其络合性能

 本文报道了一种合成硫杂冠醚聚合物的新方法。以聚(2′-氯乙基-2,3-环硫丙基醚)为预聚物与二巯基化合物通过大分子反应直接环化,一步法合成了四种以聚硫醚为主链的新型硫杂冠醚聚合物(PD1-PD4)。并测定了它们对Ag⁺、Au³⁺)、Pd²⁺、Pt⁴⁺、Cu²⁺、Hg²⁺、Zn²⁺、Cd²⁺、Pb²⁺、Mg²⁺、K⁺、Ns⁺等金属离子的络合性能。结果表明:它们除不络合K⁺、Na⁺、Mg²⁺、Pb²⁺外,对其它八种离子有不同程度的络合,其中对Ag⁺、Au³⁺、Pd²⁺等贵金属离子的络合容量较高。     

The complexing ability and structure of Si-substituted silatranes

The proton NMR spectra of Si-substituted silatranes, a new class of biologically active compounds, measured in the presence of Co²⁺, Ni²⁺ and Eu³⁺ ions are examined. These silatranes coordinate with Co²⁺ and Ni²⁺ through a nitrogen atom and with Eu³⁺ through an oxygen atom mainly without transition to the exo-form. The electronic structure of nitrogen in silatranes is the same as that of pyrrol nitrogen. This suggests that in silatranes a nitrogen lone pair and oxygen lone pairs form common electron system analogous, for example, to the π-system of unsaturated cycles.     

Semiquantitative determination of thirty cations by circular thin-layer chromatography

Summary A comprehensive scheme for the semiquantitative determination of 30 metal ions (Ag⁺, Pb²⁺, W⁶⁺, Tl⁺, Fe³⁺, Au³⁺, Mo⁶⁺, Ga³⁺, Sb⁵⁺, Ge⁴⁺, Te⁴⁺, Pt⁴⁺, Pd²⁺, Ru³⁺, Rh³⁺, Cu²⁺, Co²⁺, Ni²⁺, Zn²⁺, Cd²⁺, Cr⁶⁺, Mn²⁺, U⁶⁺, V⁵⁺, Sn⁴⁺, Bi³⁺, Hg²⁺, Ti⁴⁺, Se⁴⁺ and As³⁺) is described. It is based on circular thin-layer chromatographic technique. The error is ± 5% and 16 other metal ions, not included in the analysis scheme because of the non-availability of spray reagents, do not interfere. The determination of each cation has been made with different spray reagents separately and the mean error has been calculated. The analysis of the same cation with different spray reagents provides a useful check on the results. The method holds an excellent promise for the study of airborne particulates and for the determination of trace elements from blood, tissue and bone.

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Zusammenfassung Ein umfassender Analysengang für die halb quantitative Bestimmung von 30 Metallionen wurde beschrieben. Die Ringchromatographie auf Dünnschichten wurde hierzu verwendet. Der Fehler beträgt ±5%. 16 weitere Metallionen, die in Ermangelung geeigneter Sprühreagenzien in den Analysengang nicht aufgenommen wurden, stören nicht. Die Bestimmung jedes einzelnen Kations wurde mit verschiedenen Sprühmitteln vorgenommen; der mittlere Fehler wurde dann berechnet. So ist eine gute Überprüfung der Ergebnisse möglich. Das Verfahren dürfte sich für die Untersuchung der Luftverschmutzung sowie für die Bestimmung von Spurenelementen in Blut, Gewebe und Knochen eignen.

     

Analytical aspects of some organic acids

Summary A direct titrimetric method for the estimation of iron(III) has been developed, which involves the adjustment of concentration of iron(III) andPh, dilution, addition of 1 ml of 2% indicator solution and titration with EDTA (30° to 35° C). It is based on the fact that the iron(III) forms a blue coloured complex which is destroyed at the 11 molar ratio making the end-point of the titration. Quantity of iron(III) as small as 23.2 mg can be titrated accurately when present in a volume of 100 ml. Study of interferences revealed that quite a number of elements like Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, UO₂ ²⁺ and Mn²⁺ does not interfere, whereas much interference is caused by Cu²⁺, Zn²⁺, Pb²⁺, Fe²⁺, Co²⁺, Ni²⁺, ZrO²⁺, V0²⁺, Al³⁺, Cr³⁺, Ti⁴⁺, Ce⁴⁺ and Th⁴⁺. The method proposed for iron(III) is selective and should be of considerable use in many cases.Part III: See Z. analyt. Chem. 167, 332 (1959).     

The phase diagram and tetragonal superstructures of the rare earth cobaltate phases Ln1−xSrxCoO3-δ (Ln=La, Pr, Nd, Sm, Gd, Y, Ho, Dy, Er, Tm and Yb)

Single phase perovskite-based rare earth cobaltates (Ln_1−xSr_xCoO_3−δ) (Ln=La³⁺, Pr³⁺, Nd³⁺, Sm³⁺, Gd³⁺, Dy³⁺, Y³⁺, Ho³⁺, Er³⁺, Tm³⁺ and Yb³⁺; 0.67?x?0.9) have been synthesized at 1100°C under 1 atmosphere of oxygen. X-ray diffraction of phases containing the larger rare earth ions La³⁺, Pr³⁺ and Nd³⁺ reveals simple cubic structures; however electron diffraction shows orientational twinning of a local, tetragonal (I4/mmm; a_p×a_p×2a_p) superstructure phase. Orientational twinning is also present for Ln_1−xSr_xCoO_3−δ compounds containing rare earth ions smaller than Nd³⁺. These compounds show a modulated intermediate parent with a tetragonal superstructure (I4/mmm; 2a_p×2a_p×4a_p). Thermogravimetric measurements have determined the overall oxygen content, and these phases show mixed valence (3⁺/4⁺) cobalt oxidation states with up to 50% Co(IV). X-ray diffraction data and Rietveld techniques have been used to refine the structures of each of these tetragonal superstructure phases (Ln=Sm³⁺-Yb³⁺). Coupled Ln/Sr and oxygen/vacancy ordering and associated structural relaxation are shown to be responsible for the observed superstructure.     

Synthesis,characterization and interaction with DNA of mononuclear metal complexes with oxolinic acid

Seven new neutral mononuclear metal complexes of VO²⁺, Mn²⁺, Fe³⁺, Co²⁺, Ni²⁺, Zn²⁺ and Cd²⁺ with the quinolone antibacterial agent oxolinic acid (=Hoxo) have been prepared and characterized with physicochemical and spectroscopic techniques. In all the complexes, oxolinic acid acts as a bidentate deprotonated ligand bound to the metal through the pyridone oxygen and one carboxylate oxygen. The metals in all the complexes are six-coordinate with slightly distorted octahedral geometry. The lowest energy model structures of the complexes Fe(oxo)₃, VO(oxo)₂(H₂O) and Mn(oxo)₂(H₂O)₂ have been determined with molecular modeling calculations. The ability of all the complexes to bind to calf-thymus DNA has been investigated with diverse spectroscopic techniques.     

Statistical evaluations of single-ion Gibbs energies of transfer

A statistical approach for the evaluation of single-ion Gibbs energies of transfer of the cations Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Ba²⁺, Ag⁺, Tl⁺, Cu⁺, Zn²⁺, Cu²⁺, Cd²⁺, Hg²⁺ and Pb²⁺ into 40 solvents based on the principal component analysis is presented. It is shown that the Gibbs energies of transfer depend both on the nature of the cation and on the donor site of the respective solvent molecule. Correlation of the data for the investigated cations required separating the solvents into subgroups according to their donor atoms in the solvent molecule. Gibbs energies of transfer into oxygen donor solvents could be correlated with the Born term [N _L(z _i e ₀)²/(8πε₀ r _i )]. Several cation parameters were investigated with respect to the transfer data into nitrogen and sulfur donor solvents. No correlations were found. Thus the use of cation parameters derived from the statistical analysis are proposed to account for the Gibbs energies of transfer into nitrogen and sulfur donor solvents. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 1, pp. 9–17. The text was submitted by the authors in English.     

Changes in thermodynamic functions in the two-temperature process of concentration and purification of electrolyte solutions on KB-4P2 polymethacrylic ionite

Temperature dependences of the differential Gibbs energies and sorption enthalpies of water on KB-4P2 polymethacrylic ionite in Ca²⁺, Mg²⁺, Ni²⁺, and Na⁺ forms are determined. It is shown that during the two-temperature concentration and purification of electrolyte solutions, the content of the so-called “free” water in the ionite, the absorption of which by the latter is characterized by very low differential values of the Gibbs energy and enthalpy, changes with a change in the temperature of the polymethacrylic cationite suspension and electrolyte solution. It is established that the rather energy-consuming step of heating the phase of ionite and solution contributes mainly to the enthalpy of this process. Equations for the temperature dependences of the activity of water for solutions of sodium, magnesium, calcium, and nickel chlorides of various concentrations are given.     

Vacancy contents and phase equilibria of Ti-substituted MnZn ferrite

Measurement of the divalent iron content in acid dissolved MnZn ferrites, fired in controlled atmospheres at various temperatures and quenched, allows calculation of cation vacancy contents. Addition of Ti⁴⁺ to these ferrites resulted in the introduction of vacancies at the rate of about 0 to 0.3 per Ti⁴⁺ depending on heat treatment conditions. Data are presented whereby the vacancy content with Ti⁴⁺ can be calculated based on the oxygen content of the undoped ferrite as available in the literature. Ti⁴⁺ stabilizes the hexagonal hematite-like structure and the phase boundary is presented as a function of Ti⁴⁺ and temperature. The vacancy contents at the phase boundary in Ti⁴⁺-doped ferrite as a function of temperature are in agreement with those calculated from the literature for undoped MnZn ferrites. Finally, the total oxygen content of coexisting spinel and hexagonal phases is presented.     

EPR Studies of Photoreduction of Ni/TiO2 Catalysts

Irradiations of Ni/TiO₂ catalyst by UV in hydrogen at 77 K produced not only Ni⁺ ions on the catalyst surface, but also Ni³⁺ and Ti³⁺ species in bulk or near the interface between nickel and titania. These photo-generated species were detected and characterized by low temperature electron paramagnetic resonance (EPR) spectroscopy. Relative spin concentrations of the photogenerated paramagnetic species (Niⁿ⁺ and Ti³⁺) varied with the nickel content in titania. A high nickel content in the sample resulted in a high peak intensity ratio of Niⁿ⁺ to Ti³⁺. It was found that the photoinduced self-redox reaction of Ni²⁺ ions to form Ni⁺ and Ni³⁺ ions has a priority over the photoreduction of Ti⁴⁺ to Ti³⁺ ions. The characteristic EPR spectrum of the Ni³⁺ (3d⁷) ions with g₁ = 2.268, g₂ = 2.237, and g₃ = 2.045 indicates that the Ni³⁺ ions are most likely located in the substitutional sites of TiO₂, possibly near the surface rutile phase. The Ni⁺ species (3d⁹) with g₄ = 2.130 and g₁ = 2.063 are on the surface of TiO₂. Both Ni⁺ and Ni³⁺ ions are quite stable in hydrogen. The Ni³⁺ ions seem to be responsible for anchoring the nickel ions onto titania and stablizing the Ni⁺ species on the surface. The Ni⁺ ions are thus free from oxygen poisoning and still show a high activity toward olefin oligomerization.