Luminescence quenching by iron in barium aluminoborate glasses

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Characterization and catalytic activity of iron(III) mono(4-N-methyl pyridyl)-tris(halophenyl) porphyrins in homogeneous and heterogeneous systems

The synthesis, characterization and catalytic activity of the cationic iron porphyrins Fe[M(4-N-MePy)TDCPP]Cl-2 and Fe[M(4-N-MePy)TFPP]Cl-2 in the epoxidation of (Z)-cyclooctene by PhIO in homogeneous solution and supported on silica gel (SG), imidazole propyl gel (IPG) or SG modified with 2-(4-sulfonatophenyl)ethyl groups (SiSO3) have been accomplished. When supported on IPG, both cationic FeP bind to the support via Fe-imidazole coordination. Fe[M(4-N-MePy)TDCPP]IPG contains a mixture of low-spin bis-coordinated (FeP)-P-III and high-spin mono-coordinated (FeP)-P-III species, whereas Fe[M(4-N-MePy)TFPP]IPG only contains high-spin mono-coordinated (FeP)-P-III. These FePIPG catalysts also contain (FeP)-P-II species, whose presence was confirmed by EPR spectroscopy using NO as a paramagnetic probe. Both cationic FePs coordinate to SG through Fe-O ligation and they are present as high-spin (FeP)-P-III species. The cationic FePs supported on SiSO3- are also high-spin (FeP)-P-III species and they bind to the support via electrostatic interaction between the 4-N-methylpyridyl groups and the SO3- groups present on the matrix. In homogeneous solution, both Fe[M(4-N-MePy)TDCPP]Cl-2 and Fe[M(4-N-MePy)TFPP]Cl-2 have similar catalytic activity to Fe(TDCPP)Cl and Fe(TFPP)Cl, leading to cis-epoxycyclooctane yields of 92%. When supported on inorganic matrices,both FePs lead to epoxide yields comparable to their homogeneous analogues and their anchoring enables catalyst recovery and re-use. Recycling of Fe[M(4-N-MePy)TDCPP]SiSO3- shows that this FeP maintains its activity in a second reaction. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Ashcroft model potential study of lattice dynamics of α-iron and barium

Ashcroft model potential has been used to compute phonon dispersion relations along the three principal symmetry directions, i.e. [k00], [kk0] and [kkk] for alpha-iron and barium. The computed phonons gave a reasonable agreement with the experimental ones in all the three principal summetry directions expect for the T-2 branch in [KK0] direction where the present study failed to reproduce the experimental findings.

Electroactive layer-by-layer films of iron tetrasulfonated phthalocyanine

Electroactive films of iron tetrasulfonated phthalocyanine (FeTsPc) were assembled via the electrostatic layer-by-layer technique (LBL), in which FeTsPc layers were alternated with the polycationic poly(allylamine hydrochloride) (PAN). The multilayer formation was monitored via UV-Vis spectroscopy by measuring the increase in the Q Band of FeTsPc at 676 nm. Film thickness was estimated by profilometry as ca. 10 Angstrom per bilayer. Fourier transform infrared and UV-Vis absorption spectroscopy suggested specific interactions between FeTsPc and PAR Cyclic voltammograms showed reproducible pairs of oxidation-reduction peaks at 0.92 mV and 0.70 mV, respectively, for a 50-bilayer PAH/FeTsPc film at 50 mV/s (vs Ag/AgNO3).

Magnetic properties of acicular ultrafine iron particles

Magnetic properties of acicular (similar to60 and similar to200 nm) iron particles, obtained by reduction of alumina-coated goethite particles, are reported. X-ray diffraction and Mossbauer spectroscopy showed that the particles consist of a alpha-Fe core and a thin surface layer of maghemite. Magnetization data indicated an improvement of similar to28% in the saturation magnetization, coercive field, and squareness for particles with similar to60 nm. This magnetic property enhancement of the present particles, whose size is 40% smaller than those commercially available, could result in a similar decrease of the bit-size for higher density of magnetic media.

THE ELECTROCHEMICAL OXIDATION OF (BENZYLIDENEACETONE)DICARBONYL(PHOSPHINE)IRON(0) AND (BENZYLIDENEACETONE)DICARBONYL(PHOSPHITE)IRON(0) COMPLEXES IN DIMETHYL FORMAMIDE

The electrochemical oxidation of (benzylideneacetone)dicarbonyl(phosphine)iron(0) and benzylideneacetone)dicarbonyl(phosphite)iron(0) complexes was studied by cyclic voltammetry and controlled potential electrolysis in 0.5 M NaClO4 (dimethyl formamide). The results suggest that the electrode process involves a complicated mechanism, the species formed in the first oxidation step being highly unstable and its decomposition producing free benzylideneacetone, free phosphine or phosphite, solvated iron(II) species and carbon monoxide which adsorbs on the platinum electrode. A linear relationship between E(p/2)ox and the ligand parameter P(L) was obtained with E(s) = 0.41 V and beta = 0.964, where E(s) and beta-denote electron-richness and polarizability of the metal centre, respectively.

Iron(II) djenkolate: synthesis and properties

Djenkolate complex of iron, [Fe(C(7)H(12)N(2)O(4)S(2))]. H(2)O, has been synthesized by the reaction of potassium djenkolate with Fe(SO(4)). 7H(2)O under nitrogen atmosphere. X-Ray diffraction pattern has been indexed in orthorhombic system with lattice parameters: a=11.24 Angstrom, b=7.50 Angstrom and c=6.96 Angstrom. According to IR spectroscopy, coordination is performed through COO(-) and NH(2) groups. An octahedral geometry for Fe ion is suggested by UV-Vis and Mossbauer spectroscopies. Thermal decomposition leads to the formation of Fe(2)O(3) (hematite). The compound shows poor solubility in water and in common organic solvents. (C) 2000 Elsevier B.V. S.A. All rights reserved.

From Plinthic Acrisols to Plinthosols and Gleysols: iron and groundwater dynamics in the tertiary sediments of the upper Amazon basin

Topography has been reported to be the major factor ruling the spatial distribution of Acrisols, Plinthosols and Gleysols on the seasonally flooded, low elevation plateaux of the upper Amazon basin occupied by Tertiary (Ica & Solimoes) sediments. In this study, detailed morphological and mineralogical investigations conducted in a representative 25-ha site were combined with hydro-geochemical data to relate the vertical and lateral soil differentiations observed to the hydro-geological history of that part of the basin. As a result of the uplift of the Andes, several cuts in the extensive Tertiary marshlands have formed, at first, slightly incised plateaux of low elevation. There, weathering under hot and humid climates would have generated a reddish, freely drained and bioturbated topsoil layer and the vertical differentiation in subsoil sediments of a plinthite over an iron-depleted mottled clay. The second episode of soil differentiation is linked to the replacement of the forest by a savannah under the drier climates of the late Pleistocene, which favours surface runoff and the infill of the incisions by fine particles. This infill, combined with the return to the present humid climate, has then enabled the local groundwater to rise on the plateaux and to generate episaturation at the topsoil/subsoil transition close to the depressions. Nowadays, ferrous iron is released from the partly iron-depleted topsoil weathering front at high water levels during the rainy seasons. It moves from footslope to low-lying positions and from top to bottom in the soil profile according to the groundwater dynamics. The present general trend is thus to the lateral export of iron at high water levels due to subsurface and overland flows, its vertical transfer during the recession of the groundwater and accumulation in a nodular plinthite. In the latter, ferrous iron is adsorbed onto its softest iron masses where it feeds the neoformation of ferrihydrite that rapidly dehydrates into haematite.

Serum iron and plasma fibrinogen concentrations as indicators of systemic inflammatory diseases in horses

Background: Detection of systemic inflammation, which is important for proper diagnosis and prompt treatment, can be challenging.Hypothesis: Measurement of plasma iron concentration is a sensitive method for detecting systemic inflammation in horses compared with measurements of plasma Fibrinogen concentration, a traditional marker for inflammation in the horse.Animals: Ninety-seven horses hospitalized with diseases causing systemic inflammation, 22 horses with localized inflammation, and 12 clinically normal horses were included in this study.Methods: A retrospective study was made on hospitalized horses that had both plasma iron and fibrinogen concentrations measured on hospital admission.Results: Plasma iron concentration was lower in horses with systemic inflammation (64 +/- 45 mu g/dL) than the reference interval minimum (105 mu g/dL) and were significantly lower (P = .001) than the value in a group of horses with local inflammation (123 +/- 45 mu g/dL) and in healthy transported horses (143 +/- 29 mu g/dL). Low plasma iron and high fibrinogen concentrations were both sensitive indicators of systemic inflammation in horses with sensitivity of 90 and 82%, respectively. There was a similar correlation between either continued decreases in iron concentration (R-sp of 0.239) or increases in fibrinogen concentration (R-sp of 0.280) during hospitalization and a worse prognosis.Conclusions and Clinical Importance: Measurement of plasma iron concentration better reflected acute inflammation than did fibrinogen concentration.

Effect of iron on inhibition of acid demineralisation of bovine dental enamel in vitro

Objectives: Iron ions (Fe2+) have been shown to be cariostatic in many studies particularly by their ability to reduce bacterial metabolism. Nevertheless, the role of iron ions on dissolution of enamel is unexplored. The aim of the present study was therefore to investigate the protective effect of increasing concentrations (0-120 mmol/L) of Fe2+ on the dissolution of enamel.Design: Enamel powder was subjected to acetic acid made with increasing concentrations with respect to FeSO4 center dot 7H(2)O. In order to determine the amount of enamel dissolved, the phosphate released in the medium was analysed spectrophotometrically using the Fiske-Subarrow method. Data were tested using Kruskall-Wall and Dunn's tests (p < 0.05). The degree of protection was found to approach maximum at about 15 mmol/L Fe2+. Higher concentrations of Fe2+ did not have an extra effect on inhibition of dissolution of enamel powder. In the next step, the protective effect of 15 mmol/L Fe2+ against mineral dissolution of the bovine enamel was evaluated using a simple abiotic model system. Enamel blocks were exposed to a sequence of seven plastic vials, each containing 1 mL of 10 mmol/L acetic acid. The acid in vial 4 was made 15 mmol/L with respect to FeSO4 center dot 7H(2)O. The mineral dissolved during each challenge was thus determined by phosphate released as described above. Data were tested using two-way ANOVA (p < 0.05). Results: Lower demineralisation (around 45%) was found in vial 4 (with Fe) that continued stable until vial 7.Conclusions: Thus, our data suggest that Fe2+, can be effective on inhibition of dissolution of enamel and that this effect may be durable. (c) 2006 Elsevier Ltd. All rights reserved.

Structural and magnetic transformation of monodispersed iron oxide particles in a reducing atmosphere

Uniform metal iron ellipsoidal particles of around 200 nm in length were obtained by reduction and passivation of alumina-coated alpha-Fe2O3 (hematite) particles under different conditions of temperature and hydrogen flow rate. The monodispersed hematite particles were prepared by the controlled hydrolysis of ferric sulfate and further coated with a homogeneous thin layer of Al2O3 by careful selection of the experimental conditions, mainly pH and aluminum salt concentration. The reduction mechanism of alpha-Fe2O3 into alpha-Fe was followed by x-ray and electron diffraction, and also by the measurements of the irreversible magnetic susceptibility. The transformation was found to be topotactic with the [001] direction of hematite particles, which lies along the long axis of the particles, becoming the [111] direction of magnetite and finally the [111] direction of metal iron. Temperature and hydrogen flow rate during the reduction have been found to be important parameters, which determine not only the degree of reduction but also the crystallite size of the final particles. Magnetic characterization of the samples shows that the only parameters affected by the crystallite size are the saturation magnetization and magnetic time-dependence effect, i.e., activation volume. (C) 2002 American Institute of Physics.

Small-angle X-ray scattering and X-ray absorption near-edge structure study of iron-doped siloxane-polyoxyethylene nanocomposites

The local and medium-range structures of siloxane-POE hybrids doped with Fe(III) ions and prepared by the sol-gel process were investigated by X-ray absorption near-edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) and small-angle X-ray scattering (SAXS), respectively. The experimental results show that the structure of these composites depends on the doping level. EXAFS data reveal that, for low doping levels ([O]/[Fe] > 40, oxygens being of the ether-type of the POE chains), Fe(III) ions are surrounded essentially by a shell of chlorine atoms, suggesting the formation of FeCl4- anions. At high doping levels ([O]/[Fe] < 20), Fe(III) ions interacts mainly with oxygen atoms and form FeOx species. The relative proportion of FeOx species increases with iron concentration, this result being consistent with the results of SAXS measurements showing that increasing iron doping induces the formation of iron-rich nanodomains embedded in the polymer matrix.

Polymeric organic-inorganic hybrid material containing iron(III) porphyrin using sol-gel process

Here we describe the preparation of iron(II) porphyrinosilica in a simple one-pot reaction, where the -SO2Cl groups present in the phenyl rings of FeTDCSPP+ react with 3-aminopropyltriethoxysilane and tetraethoxysilane in the presence of a nitrogenous base, leading to iron(III) porphyrinosilica. In this same procedure, molecular cavities containing regularly spaced functional groups are created through the molecular imprinting technique, in which the nitrogenous base coordinated to the iron(III) porphyrin serves as a template. The removal of such template in a Soxhlet extractor leads to a cavity with the same shape and size as the nitrogenous base, enabling the construction of shape-selective catalysts mimicking cytochrome P-450. Five different imprinting molecules have been used: imidazole, 1-methylimidazole, 2-methylbenzimidazole, 4-phenylimidazole and miconazole and ultra-violet/visible absorption spectroscopy, thermogravimetric analysis and electron paramagnetic resonance carried out. (C) 1999 Elsevier B.V. B.V. All rights reserved.