Low temperature synthesis and characterization of Mn3O4 nanoparticles

Heating hydrous manganese (II) hydroxide gel at 85 °C for 12 hours produces Mn₃O₄ nanoparticles. They were characterized by X-ray powder diffraction (XRD) and infrared spectroscopy (FTIR). The particle size estimated from the SEM and X-ray peak broadening is approximately 32 nm, showing them to be nanocrystalline. EPR measurements confirm a typical Mn²⁺signal with a highly resolved hyperfine structure.      

Separation of Ga(III) from Cu(II), Ni(II) and Zn(II) in aqueous solution using synthetic polymeric resins

Poly (acrylamide-acrylic acid-dimethylaminoethylmethacrylate), p(AM-AA-DMAEM) and Poly(acrylamide-acrylic acid)-ethylenediaminetetracetic acid disodium, p(AM-AA)-EDTANa₂ were prepared by gamma radiation-induced template polymerization technique and used for the separation of Ga (III) from Cu (II), Ni (II), and Zn (II) in aqueous media. The effect of pH and contact time on the separation process was studied. The optimum pH value for the separation process is 3–3.5. The result shows that Ga (III) is first extracted while Cu (II), Ni (II) and Zn(II) are slightly extracted at this pH value. The recovery of metals using HCl, HNO₃ and H₂SO₄ has been studied. The resins may be regenerated using 2M HCl solutions.      

Oxidation of UO2(s) in aqueous solution

In this review the kinetics and mechanism of oxidative dissolution of UO₂(s), mainly under conditions of relevance for the safety assessment of a deep geological repository for spent nuclear fuel, are discussed. Rate constants for the elementary processes involved (oxidation of UO₂ and dissolution of oxidized UO₂) are used to calculate the rates of oxidative UO₂(s) dissolution under various conditions (type of oxidant, oxidant concentration and HCO₃ ⁻/CO₃ ²⁻ concentration) for which experimental data are also available. The calculated rates are compared to the corresponding experimental values under the assumption that the experimental numbers reflect the steady-state conditions of the system. The agreement between the calculated rates and the corresponding experimental ones is very good, in particular for the higher rates. In general, the calculated rates are somewhat higher than the experimental numbers. This can be due partly to the use of initial concentrations rather than steady-state concentrations in the calculations. The kinetic data are also used to quantitatively discuss the dynamics of spent nuclear fuel dissolution under deep geological repository conditions.      

Determination of p-nitroaniline by the tartrate-acetone-Mn2+-KBrO3-H2SO4 double organic substrate oscillating system using non-equilibrium stationary state

This paper described the determination of p-nitroaniline in a double organic substrate oscillating system of tartrate-acetone-Mn²⁺-KBrO₃-H₂SO₄. Under the optimum conditions, temperature was chosen as a control parameter to design the bifurcation point and proposed a convenient method for determination of p-nitroaniline. Results showed that the system consisting of 3.5 mL 0.06 mol L⁻¹ tartrate, 4.0 mL 0.7 mol L⁻¹ H₂SO₄, 1.5 mL 1.5×10⁻⁴ mol L⁻¹ MnSO₄, 4.0 mL 0.4 mol L⁻¹ acetone and 7.0 mL 0.05 mol L⁻¹ KBrO₃ was very sensitive to the surrounding at 33.5°C. A good linear relationship between the potential difference and the negative logarithm concentration of p-nitroaniline was obtained to be in the range of 2.50×10⁻⁷∼3.75×10⁻⁵ mol L⁻¹ with a lower detection limit of 2.50×10⁻⁸ mol L⁻¹.      

The binary system PbO - BiVO4

Phase equilibria established in the PbO - BiVO₄ system over the whole component concentration range up to 1000°C have been investigated. A phase diagram has been constructed using DTA and XRD.      

Electrospinning of the hydrophilic poly (2-hydroxyethyl methacrylate) and its copolymers with 2-ethoxyethyl methacrylate

The goal was to electrospin 2-hydroxyethyl methacrylate — based biocompatible polymers and prepare submicron fibres (nanofibers) for biomedicinal applications. Syntheses of poly(2-hydroxyethyl methacrylate) (HEMA) and its copolymer with 2-ethoxyethyl methacrylate (EOEMA), and their characterization by viscometry and molecular weight are described. Their relation to electrospinning is discussed. Electrospinning of HEMA homopolymer from water-ethanol is successful for molecular weights 6.31 × 10⁵ and 1.80 × 10⁶ g/mol. Electrospinning of HEMA/EOEMA copolymers is feasible from ethanol.      

Heterobimetallic complexes containing iron (II) and hexa-coordinated organosilicon

Heterobimetallic complexes of the type R₂Si(HL)Cl₂ and R₂SiL₂ (where R = Me, Et, Ph; L = ferrocenyl aroylhydrazone) have been synthesized at 40 °C to 50 °C and at room temperature (25 °C), respectively, and characterized by elemental analysis, molar conductance, infrared and NMR (¹H, ¹³C and ²⁹Si) spectral data. The ligands behave as bidentate, coordinating through the azomethine nitrogen and the oxygen in the amidic and the imidic acid forms of the ligand at low temperature and at room temperature, respectively. The ligands and their organosilicon complexes have been evaluated for the antifungal activity against Alternaria alternata, Fusarium oxysporum and Rhizoctonia solani, as well as antibacterial activity against gram negative, Escherichia coli and gram positive, Bacillus subtilis, at 28 °C. Organosilicon complexes of ferrocenyl aroylhydrazone were found to be more potent than the parent ligands.      

The effect of calcium substitution on the afterglow of Eu2+/Dy3+ doped Sr4Al14O25

The effect of calcium substitution on the afterglow of tetrastrontium aluminate phosphors (Sr₄Al₁₄O₂₅:Eu²⁺, Dy³⁺) was investigated. A series of (Sr₁-_xCa_x)O⊎nAl₂O₃:Eu²⁺(1%), Dy³⁺(0.5%), with variation of calcium content (x = 0 − 1), were synthesized by a high temperature solid state reaction in a reducing atmosphere. The photoluminescence, persistent luminescence (afterglow), and lumen equivalents of these materials were studied and compared. It turned out that the afterglow properties of the phosphors were strongly dependent on the Sr/Ca ratio. As the Ca content increased, a phase transition and blue shift in emission spectra were observed.      

Synthesis and pharmacological properties of 3-(2-methyl-furan-3-yl)-4-substituted-Δ<Superscript>2</Superscript>-1,2,4-triazoline-5-thiones

By the reaction of 2-methyl-furan-3-carboxylic acid hydrazide with isothiocyanates, 1-[(2-methyl-furan-3-yl)carbonyl]-4-substituted thiosemicarbazides 1 were obtained. Further cyclization with 2% NaOH led to the formation of 3-(2-methyl-furan-3-yl)-4-substituted-Δ²-1,2,4-triazoline-5-thiones 2. The pharmacological effects of 2 on the central nervous system in mice were investigated. Strong antinociceptive properties of the investigated derivatives were observed in a wide range of doses.      

Synthesis, structures, and spectroscopic properties of copper(I) complexes bearing 7-acetamido-4-methyl-1,8-naphthyridin-2-carbaldehyde azine and 1,2-bis(diphenylphosphino)ethane ligands

A new ligand napaa (napaa = 7-acetamido-4-methyl-1,8-naphthyridin-2-carbaldehyde azine) and its two dinuclear copper(I) complexes, Cu₂(napaa)(dppe)₂(ClO₄)₂ (1) and Cu₂(napaa)(PPh₃)₄(BF₄)₂ (2) (dppe = 1,2-bis(diphenylphosphino)ethane) and PPh₃ = triphenylphosphine) were synthesized and characterized, and the structure of 1 was determined by X-ray crystal analysis. Each copper atom in 1 has a distorted tetrahedral geometry in which the metal center is associated to napaa and dppe ligands displaying chelating coordination modes and the naphthyridine rings of napaa are almost coplanar. The two complexes exhibit similar electronic absorption spectra with λ_max at about 366 nm, which can be tentatively assigned to metal-to-ligand charge-transfer (MLCT) transition. The assignment was further supported by density functional theory (DFT) calculations.      

Surface analysis of the size-fractioned urban aerosols by secondary ion mass spectrometry (ToF-SIMS)

The secondary ion mass spectrometry method (ToF-SIMS) has been applied to the analysis of some mineral and organic species on the surface layers of airborne urban particulates. Particulate matter was collected on aluminum sheets of the 8-stage Anderson type cascade impactor from three different sampling sites in the city of Lodz, Poland, which were different in terms of aerosol source apportionment. The obtained results show that vehicle combustion products occur mainly in fine fraction with aerodynamic diameters below 1μm. The main contribution to the mineral components comes from direct and traffic related soil resuspension.      

Analysis of vibratinal spectra of 8-hydroxyquinoline and its 5,7-dichloro, 5,7-dibromo, 5,7-diiodo and 5,7-dinitro derivatives based on density functional theory calculations

The geometry, frequency and intensity of the vibrational bands of 8-hydroxyquinoline and its 5,7-dichloro, 5,7-dibromo, 5,7-diiodo and 5,7-dinitro derivatives were obtained by the density functional theory (DFT) calculations with Becke3-Lee-Parr (B3LYP) functional and 6-31G* basis set. The effects of chloride, bromide, iodide and nitro substituent on the vibrational frequencies of 8-hydroxyquinoline have been investigated. The assignments have been proposed with aid of the results of normal coordinate analysis. The observed and calculated spectra are found to be in good agreement.      

Macrocyclic host cyclophosphazenes from aminolysis of N3P3CI6 by bis-(2-ortho-aminophenoxyethyl)ether

Aminolysis of N₃P₃CI₆ by an oxodiamine, bis-(2-ortho-aminophenoxyethyl) ether, has been carried out under various experimental conditions and new products with different architectures have been obtained. The reaction in diethyl ether when using a Na₂CO₃-water interface process gives the mono-BINO as major product. Reaction on Al₂O₃/KOH leads to the spirocyclic compound, while, when the reaction is carried out in toluene in the presence of NEt₃, a mixture of mono- and di-BINO products are obtained. These new products have been characterized by IR, ¹H and ³¹P NMR spectroscopy.      

Copper(II) complexes of the antihypertensive drug nadolol

The complexation of the non-selective β-blocker nadolol, HL, 1 with copper(II) leads to formation of mono-and dinuclear complexes depending mainly on the metal-to-ligand molar ratio. The mononuclear violet complex CuL₂·2Solv, 2, was obtained in a soluble form at metal-to-ligand molar ratio Cu(II): HL ≤ 1: 10 in methanolic or slightly alkaline aqueous solutions. The dinuclear green complex Cu₂L₂Cl₂·H₂O, 3 was synthesized at Cu(II): HL ≥ 1: 2 molar ratio in methanolic solutions. The complexes were studied using spectral (UV-Vis, FT-IR, EPR), magnetochemical, thermogravimetric methods and elemental analysis. In the complexes nadolol acts as a monoanionic bidentate ligand coordinated to copper(II) through the NH-and the deprotonated OH-groups of its aminoalcohol fragment.      

Alkylation of ambident indole anion in ionic liquids

Alkylation of indole salts in different ionic liquids is reported. Ionic liquids increase the alkylation reaction rate of ambident indole anion and reduce the effects of counter ions and/or additives, the alkylation reaction rates being independent of the presence of small amounts of protic solvents or water.      

Indirect determination of lutetium by differential pulse anodic stripping voltammetry at a hanging mercury drop electrode

Lutetium has been determined by differential pulse anodic stripping voltammetry in an acidic solution containing Zn-EDTA. Lutetium (III) ions liberated zinc (II), which was preconcentrated on a hanging mercury drop electrode and stripped anodically, resulting in peak current linearly dependent on lutetium (III) concentration. Less than 0.4 ng mL⁻¹ lutetium could be detected after a 2 min deposition.      

Phase transitions of K<Subscript>2</Subscript>TaF<Subscript>7</Subscript> within 680–800°C

Three thermal effects on heating/cooling of K₂TaF₇ in the temperature interval of 680–800°C were investigated by the DSC method. The values determined for the enthalpy change of the individual processes are: Δ_transIIH_m(K₂TaF₇; 703°C) = 1.7(2) kJ mol⁻¹, Δ_transIH_m(K₂TaF₇; 746°C) = 19(1) kJ mol⁻¹ and Δ_transIIIH_m(K₂TaF₇; 771°C) = 13(1) kJ mol⁻¹. The first thermal effect was attributed to a solid-solid phase transition; the second to the incongruent melting of K₂TaF₇ and the third to mixing of two liquids. These findings are supported by in situ neutron powder diffraction experiments performed in the temperature interval of 654–794°C.      

Synthesis and proton conductivity of anhydrous dendritic electrolytes

Water soluble PEG cored dendritic hexa-acid which comprises peripheral carboxylic acidic groups were prepared via nucleophilic substitution reactions. Novel anhydrous proton conducting electrolytes were prepared by incorporation of the heterocyclic protogenic solvent imidazole (Im) into PEG cored dendritic hexa acid, (PEG-HA), at several molar ratios of Im to-COOH units of PEG-HA. The complexation of PEG-HA and Im was illustrated by infrared spectroscopy (FT-IR). The materials are thermally stable up to 150 °C as evidenced by thermogravimetry analysis (TGA). Differential scanning calorimetry (DSC) results verified that the organic electrolytes are homogeneous and amorphous. The proton conductivities were characterized by means of AC impedance spectroscopy and a maximum conductivity of 1 × 10⁻³ S/cm was measured at 120 °C in the anhydrous state.      

Determination of europium by using the chemical oscillating system of Ce(IV)-KBrO<Subscript>3</Subscript>-acetone-oxalic acid-H<Subscript>2</Subscript>SO<Subscript>4</Subscript>

A sensitive and convenient method for the determination of trace europium ions using an oscillating chemical reaction involving Ce(IV) - KBrO₃ - acetone - oxalic acid - H₂SO₄ was proposed. The results indicated that the changes in oscillating period (T) was linearly proportional to the negative logarithmic concentration of Eu³⁺ (-log C) in the range of 1.41 × 10⁻⁸ ˜ 1.41 × 10⁻⁴ mol L⁻¹ (r = 0.9982) with a detection limit of 1.04 × 10⁻⁹ mol L⁻¹. The recoveries were limited to the range of 99.5% to 100.8%. Under the same conditions, other rare earth ions did not interfere with the determination of Eu³⁺. In addition, a perturbation mechanism was also discussed briefly.      

Preparation of nanostructured porous SiO2-Al2O3 oxycarbonitride materials obtained by a new chemical precursor method

Nanostructured hybrid materials containing Al₂O₃ were synthesized via a sol-gel method through hydrolysis and co-condensation reactions using trimethylsilyl isocyanate (TMSI) as a new silica source in the presence of tetramethoxysilane (TMOS) and three different quantities (10, 20 and 30 wt.%) of aluminum sec-butoxide (Al(OBu^sec)₃ as a modifying agent. The xerogel nanostructured materials are pyrolyzed in nitrogen atmosphere in the temperature range from 400°C to 1100°C. The transformation of the xerogel hybrid networks into Al-Si oxycarbonitride materials has been investigated by XRD, FTIR, SEM, AFM, and ²⁹Si MAS-NMR. To the best of our knowledge, the work reported here is the first synthesis of porous di-urethanesils modified with aluminum and one of the few examples of alumosilica oxycarbonitride materials