Color Centers in Alkali Borate Glasses Containing Cobalt,Nickel, or Copper

The absorption spectra and the magnetic moments of Co²⁺, Ni²⁺, and Cu²⁺ in alkali borate glasses of various compositions and in halide-containing glasses have been explained from the point of view of the ligand field theory. Spectra and magnetic moments are highly dependent on the composition of the base glass; this must be ascribed to the change in the coordination of the transition-metal ions. There are far-reaching analogies with corresponding complexes in solution or in the crystalline state.     

Comprehensive ion-exchange and adsorption study of the distribution of exchanging inorganic cations over the interlayer gaps of vermiculite

The exchange of Co²⁺ ions on Na-vermiculite has been comprehensively studied by the ionexchange, adsorption, and X-ray diffraction methods. It has been shown that vermiculite is distinguished by high selectivity to Co²⁺ cations and Kielland dependence log $\tilde K_m (\theta )$ increasing with filling of ion-exchange sites with sorbed cations rather than a decreasing one that is observed for common systems. It has been established that the ion exchange is accompanied by segregation of Na+ and Co²⁺ cations in separate interlayer gaps of vermiculite with the final formation of a disordered layered “cake” composed of separate silicate layers and interlayer gaps enriched with Na⁺ and Co²⁺ ions.     

EPR of Mn2+ in [Co(H2O)6] PtCl6 single crystals: Estimation of Co2+ spin-lattice relaxation time

EPR of Mn²⁺ in single crystals of [Co(H₂O)₆]PtCl₆ has been studied from room temperature to 77 K at ∼ 9.35 GHz. Mn²⁺ has been found to substitute for Co²⁺ exhibiting a unique magnetic complex. The observation of resolved Mn²⁺ spectra has been interpreted in terms of a random modulation of the interaction between the Mn²⁺ and Co²⁺ ions by the rapid spin-lattice relaxation of Co²⁺ ions. It has been found that the effective spin-relaxation time T₁αT⁻ⁿ where n = 1.8 for 105 < T< 293 K.     

Study of some metallic silicates as ion-exchangers

The extraction of ammine complexes of Cu²⁺, Cd²⁺, Ni²⁺, Co²⁺ and Zn²⁺ by synthesised manganese, nickel and zinc silicates has been studied at different pH and ionic concentrations in the external solution. It has been found that the uptake of the metal ion Co²⁺, Cu²⁺ and Zn²⁺ increases with increase in pH of the external solution, attains a maximum and then decreases. However, the uptake for Cd²⁺ and Ni²⁺ increases continuously. The q_A values of all the silicates increases with the increase in the concentration of the exchanging ion and its order for the investigated metal ions is Ni²⁺ < Co²⁺ < Cd²⁺ < Zn²⁺ < Cu²⁺.     

Changes in Coordination Number of Co Ion and Fluorescence Spectrum of 1-Naphthol during the Sol-Gel Reaction of TEOS

Changes in coordination number of Co²⁺ and fluorescence spectra of 1-naphthol during the sol-gel transitions of TEOS have been investigated as a function of time. The change in the coordination number of Co²⁺ has been observed as follows. Six-coordinated Co²⁺ decreased quickly within several hours in the first stage of the reaction corresponding to water consumption by initial hydrolysis reaction. Then six-coordinated Co²⁺ increased around gelation due to polycondensation. After the gelation four-coordinated Co²⁺ increased, where isomorphous-replacement of Co²⁺ into the –O–Si–O– networks occurred. In the Co²⁺/1-naphthol mixed system, separate ion pair of 1-naphthol is preferentially coordinated on the six-coordinated Co²⁺ where water molecule(s) plays an important role to geometrical relaxation of excited-state 1-naphthol.     

Metal Ions as Activators of Hypoxia Inducible Factor

Activation of antihypoxic program under the action of a number of transition and heavy metals has been studied using cell-based HIF1 ODD-luc and HRE-luc reporters. It has been demonstrated that Au³⁺, Pb²⁺, Sn²⁺, Hg²⁺ are weak HIF1 ODD-luc activators, likely reflecting their weak competition for the ironbinding site in the active center of HIF prolyl hydroxylase. Metals capable of replacing iron–Mn²⁺, Zn²⁺, Cu²⁺ и Ni²⁺–activate at high submillimolar concentrations, which indicates low permeability of the cell membrane for transition metals. The highest activation is observed for Co²⁺ and Cd²⁺, however, Cd²⁺ is highly toxic even at 10 μM, in contrast to Co²⁺, which activates both reporters without toxicity signs up to 25 μM for 24 h. A significant activation by Co²⁺ is observed already in low micromolar range of concentrations, which can be recommended for use in hypoxia mimicking.     

Triplet state interaction of Safranine T with inorganic cations in different solvents

The triplet-triplet absorbance of Safranine T (3,7-Diamino-2,8-dimethyl-5-phenylphenaznium chloride) has been studied in a series of polar and non-polar solvents. When non-aqueous solvents are gradually added to the aqueous solution of Safranine T (ST) the lifetime of the triplet state decreases. It has been established that the dye forms weak complex with the solvent molecules. The quenching of triplet state of ST by Fe²⁺, Co²⁺ and Mn²⁺ has been studied in different solvents. The double protonated long-lived triplet species of ST; absorbs at 580 nm. The decay of the triplets follows first order kinetics. The quencher generates reduced semidye from ³ST by electron transfer mechanism. The reduction of ³ST by Mn²⁺ and Fe²⁺ is thermodynamically allowed but electron transfer from Co²⁺ to ST is endoergic. The mechanism of quenching by Co²⁺ can be explained as compensation by charge transfer mechanism between ³ST and Co²⁺.     

Selective cation exchange isolation of radioactive mercury from cobalt,scandium and europium

Distribution of Hg²⁺, Co²⁺, Sc³⁺ and Eu³⁺ between the cation exchanger Dowex-50X8, [H⁺] (100–200 mesh), and 1M HNO₃ solution containing different benzylamine (BA) concentrations has been studied. The distribution coefficient, D, for Co²⁺, Sc³⁺ and Eu³⁺ is very small and does not vary seriously with the BA concentration. It is also found that Hg²⁺ is highly taken by the resin from the media studied. In this respect, D increases with increasing BA concentration to reach a maximum at 0.5% BA in 1M HNO₃. This behaviour is explained by the exchange of molecular species between the cation exchanger and the aqueous phase. Based on the results, a radiochemical separation procedure for the selective isolation of Hg²⁺ from Co²⁺, Sc³⁺ and Eu³⁺ has been developed. The radiochemical purity is not less than 99.8% and the chemical yield more than 95% for the separated²⁰³Hg.     

60Co sorption-desorption in Mexican montmorillonites

The ability of some antural Mexican clays to sorb radioactive Co from aqueous solution and then desorb it has been measured. The clay cations seem to be exchanged with cations present in the solution. It was observed that the amount of sorbed Co²⁺ depends nearly linearly on the Na⁺+K⁺ content in the montmorillonites. It was found that the crystallinity was not altered after Co²⁺ sorption. Crystallinity of clays, before and after cobalt exchange, was determined by X-ray diffraction.     

Luminescent properties of Tb3+ and Gd3+ ions doped aluminosilicate oxyfluoride glasses

Tb³⁺ and Gd³⁺ ions doped lithium–barium–aluminosilicate oxyfluoride glasses have been prepared. The transmission, emission and excitation spectra were measured. It has been found that those Tb³⁺-doped lithium–barium–aluminosilicate oxyfluoride glasses exhibit good UV-excited luminescence. The luminescence intensity of Tb³⁺ ion increases for those (Tb³⁺, Gd³⁺)-codoped glasses. Energy transfer process from Gd³⁺ ion to Tb³⁺ ion is indicated.     

Interaction of dinucleotides with divalent metal ions: A circular dichroism study

The interactions between NAD⁺ and NADP⁺ and the divalent ions Mg²⁺, Mn²⁺ and Co²⁺ have been studied by circular dichroism in the UV range. A visible C.D. study has been carried on the Co²⁺ complexes.The observed changes of the UV and C.D. as a function of temperature clearly show that the metal ion does not bridge the purine base and the nicotinamide.The observed changes of the UV C.D. as a function of temperature clearly show that the metal ion does not bridge the purine base and the nicotinamide.The strong modification of the UV C.D. and the appearance of visible C.D. in 0.1 M NAD⁺ or NADP⁺ solutions in presence of Co²⁺ which occurs when the N(1) adenine atom is deprotonated, has been ascribed to the formation of a 1:2 Co²⁺-dinucleotide complex where the two adenine bases are stacked.     

Structural characterization and ionic conductivity of Co2+-stabilized β″-alumina

Single crystals of Co²⁺-stabilized β″-alumina were synthesized by a flux growth technique using Bi₂O₃ as the flux and subsequent X-ray crystallographic studies showed that the Co²⁺ ions substitute only at the Al(2) sites. Optical absorption spectroscopic measurement also supports the concept that the dopant ions are in distorted tetrahedral environment. Co²⁺-doped β-alumina crystals were made by a skull melting technique. Chemical analysis of these two materials indicated that the Co²⁺ ion concentration may be important in the formation of one phase over the other. The temperature-dependent ionic conductivity of Co²⁺-stabilized β″-alumina, Co²⁺-doped β-alumina, and undoped β-alumina has been measured and compared between 25 and 450°C. The detailed conductivity analysis was made by a phase-synchronous detection system in the frequency range 100 Hz-10 MHz. The conductivity is highest in the stabilized β″-alumina and lowest in the undoped β-alumina. For Co²⁺-doped β-alumina, a slight bend in the conductivity at around 200°C is noted. The analysis of the conductivity and the effect of the dopant Co²⁺ ions on the resulting conductivity is discussed.     

Synthesis and characterization of La1+xSr2−xCoMnO7−δ (x=0,0.2; δ=0,1)

The n=2 Ruddlesden-Popper phases LaSr₂CoMnO₇ and La_1.2Sr_1.8CoMnO₇ have been synthesized by a sol-gel method. The O6-type phases LaSr₂CoMnO₆ and La_1.2Sr_1.8CoMnO₆ were produced by reduction of the O7 phases under a hydrogen atmosphere. The materials crystallize in the tetragonal I4/mmm space group with no evidence of long-range cation order in the neutron and electron diffraction data. Oxygen vacancies in the reduced materials are located primarily at the common apex of the double perovskite layers giving rise to square pyramidal coordination around cobalt and manganese ions. The oxidation states Co³⁺/Mn⁴⁺ and Co²⁺/Mn³⁺ predominate in the as-prepared and reduced materials, respectively. The materials are spin glasses at low temperature and the dominant magnetic interactions change from ferro- to antiferromagnetic following reduction.     

Selectivity and thermodynamic characteristics of doubly charged cations on zirconium titanate from aqueous and alcoholic solutions

The ion-exchange isotherms of Ni²⁺/H⁺ and Co²⁺/H⁺ have been determined with a solution of 0.1 ionic strength for both forward and backward reactions at 25^°C by a batch technique. The thermodynamic equilibrium constants for the exchange process have been calculated using the Gains and Thomas equation. The preference Ni²⁺>Co²⁺ has been shown. The ion exchange selectivity for exchange of Ni²⁺ and Co²⁺ ions with hydrogen ions on zirconium titanate has been investigated as a function of [HCl] from aqueous and 25% of methanol and/or ethanol solutions. The values of the thermodynamic functions for the studied systems have been reported. This revised version was published online in July 2006 with corrections to the Cover Date.     

Influence of MgO (CaO) on the structure of silicate-phosphate glasses

Thermal and structural properties of model silicate-phosphate glasses containing the different amounts of the glass network modifiers, i.e. Mg²⁺ and Ca²⁺ were studied. To explain the changes of the parameters characterizing the glass transition effect (T_g, Δc_p) and the crystallization process (T_c, ΔH) depending on the cations modifiers additions, analysis of the bonds and chemical interactions of atoms in the structure of glasses was used. ³¹P MAS-NMR spectra of SiO₂–P₂O₅–MgO(CaO)–K₂O glasses show that the phosphate complexes are mono- and diphosphate. It has been found that increasing amounts of Mg²⁺ or Ca²⁺ cations in the structure of glasses causes the reduction of the degree of polymerization of the phosphate framework (Q¹→Q⁰). The influence of increasing of modifiers in the structure of silicate- phosphate glasses on the number of non-bridging oxygens per SiO₄ tetrahedron and density of glasses was presented.     

Plasma‐Engraved Co3O4 Nanosheets with Oxygen Vacancies and High Surface Area for the Oxygen Evolution Reaction

Co₃O₄, which is of mixed valences Co²⁺ and Co³⁺, has been extensively investigated as an efficient electrocatalyst for the oxygen evolution reaction (OER). The proper control of Co²⁺/Co³⁺ ratio in Co₃O₄ could lead to modifications on its electronic and thus catalytic properties. Herein, we designed an efficient Co₃O₄‐based OER electrocatalyst by a plasma‐engraving strategy, which not only produced higher surface area, but also generated oxygen vacancies on Co₃O₄ surface with more Co²⁺ formed. The increased surface area ensures the Co₃O₄ has more sites for OER, and generated oxygen vacancies on Co₃O₄ surface improve the electronic conductivity and create more active defects for OER. Compared to pristine Co₃O₄, the engraved Co₃O₄ exhibits a much higher current density and a lower onset potential. The specific activity of the plasma‐engraved Co₃O₄ nanosheets (0.055 mA cm^?2_BET at 1.6 V) is 10 times higher than that of pristine Co₃O₄, which is contributed by the surface oxygen vacancies.     

Crystallographic study of YCo3+1−2xCo2+xPt4+xO3 and DyCo3+1−2xCo2+xPt4+xO3

The crystal structures of single crystals of YCo³⁺_.36Co²⁺_.32Pt⁴⁺_.32O₃ and DyCo³⁺_.36Co²⁺_.32Pt⁴⁺_.32O₃ have been examined at room temperature, and shown to be isostructural with GdFeO₃, which belongs to space group Pbnm. The overall expansion of octahedra caused by substitution of platinum enhances the distortion of rare-earth dodecahedra by moving 4 out of 12 oxygens further away from the rare-earth ions, as shown by the rotation of octahedra along the [110] axis. No order has been found for Co²⁺, Co³⁺, and Pt⁴⁺.     

Decay of Ru(BPY)3 3+ in thin nafion layers catalyzed by Co(II)

Catalytic oxidation of water by Ru(bpy)₃ ³⁺ in the presence of Co²⁺ ions, well known in homogeneous solution, has been investigated in thin Nafion layers. Nafion layers on ITO electrodes were equilibrated with Ru(bpy)₃ ²⁺. Ru(bpy)₃ ³⁺ was produced by electrochemical oxidation after which the electrode was transferred into the reaction cell containing buffered Co²⁺ solution. The build up of Ru(bpy)₃ ²⁺ absorbance at 454 nm was followed spectrophotometrically. The reaction rate is proportional to [Ru(III)], [Co²⁺] and [HPO₄ ^2-]. We found no evidence for a pH effect in the range 6–8, and no inhibition by Ru(II). A limiting rate of formation of Ru(II) is observed at high Co²⁺ or phosphate ion concentrations. At high local concentration of the Ru complex in the Nafion layer (~ 0.5 M), two Ru(II) formation processes are observed, their rates differ by one order, but other features (effects of [Ru(III)], [Ru(II)], [Co²⁺], phosphate and pH) remain unchanged. These results are in contrast with homogeneous solution where the rate of build up of Ru(II) has been previously reported to be proportional to [Ru(III)], [Co²⁺] and [OH^-]², and inversely proportional to [Ru(II)]. A mechanism is proposed which accounts for these observations.     

Pes study of spin-state transitions in d6 transition metal complexes and oxides

Transitions from the low-to the high-spin state in Fe²⁺ and Co³⁺ compounds have been examined by X-ray and UV photoelectron spectroscopy. It has been shown that the core-level bands in XPES, in particular the metal 3s band, as well as the valence bands, are diagnosis in the study of spin-state transitions.     

Analytical reactions of substituted cyanoferrates : I. Na3[Fe(CN)5(NH3)]

The reagent pentacyanoamminoferrate (PCAF) in its aqueous reactions with some common cations and anions produces colored species in solution. It has been observed that the reactions of Fe³⁺, Fe²⁺, Co²⁺, VO²⁺, Mo⁶⁺, S₂O₃²⁻, and NO₂⁻ are sensitive enough to permit their colorimetric determinations. In addition, the reagent has been found useful in the simultaneous trace analysis of Fe³⁺ and VO²⁺ present in the same solution.A comparative study has been made of the reactions of PCAF and the other unsubstituted cyanoferrates(II) and (III).