Structure of magnetic poly(oxyethylene)-siloxane nanohybrids doped with Fe-II and Fe-III

Hybrid organic - inorganic nanocomposites doped with Fe-II and Fe-III ions and exhibiting interesting magnetic properties have been obtained by the sol - gel process. The hybrid matrix of these ormosils ( organically modified silicates), classed as di-ureasils and termed U( 2000), is composed of poly( oxyethylene) chains of variable length grafted to siloxane groups by means of urea crosslinkages. Iron perchlorate and iron nitrate were incorporated in the diureasil matrices, leading to compositions within the range 80 greater than or equal to n greater than or equal to 10, n being the molar ratio of ether-type O atoms per cation. The structure of the doped diureasils was investigated by small-angle X-ray scattering (SAXS). For Fe-II-doped samples, SAXS results suggest the existence of a two-level hierarchical structure. The primary level is composed of spatially correlated siloxane clusters embedded in the polymeric matrix and the secondary, coarser level consists of domains where the siloxane clusters are segregated. The structure of Fe-III-doped hybrids is different, revealing the existence of iron oxide based nanoclusters, identified as ferrihydrite by wide-angle X-ray diffraction, dispersed in the hybrid matrix. The magnetic susceptibility of these materials was determined by zero-field-cooling and field-cooling procedures as functions of both temperature and field. The different magnetic features between Fe-II- and Fe-III-doped samples are consistent with the structural differences revealed by SAXS. While Fe-II-doped composites exhibit a paramagnetic Curie-type behaviour, hybrids containing Fe-III ions show thermal and field irreversibilities.

Pre-concentration of Cd(II), Cr(III), Cu(II) and Ni(II) on a column packed with oxycellulose.

Oxycellulose (OXICEL) was packed in a glass column to pre-concentrate metal cations from aqueous solutions. The pre-concentrated metal cations are directly eluted from the column using 5.0 mL of 1.0 mol L(-1) hydrochloric acid. The optimum pre-concentration conditions are given and the retention efficency achieved is higher than 95%. The enrichment factor is 10 for sample volumes of 50 mL.

Design of Gaussian basis sets to the theoretical interpretation of IR-spectrum of hexaaquachromium (III) ion, tetraoxochromium (IV) ion, and tetraoxochromium (VI) ion

The Generator Coordinate Hartree-Fock (GCHF) method is employed to design 16s, 16s10p, 24s17p13d, 25s17p13d, and 26s17p Gaussian basis sets for the H ((2)S), O ((3)P), O(2-) ((1)S), Cr(3+) ((4)F), Cr(4+) ((3)F), and Cr(6+) ((1)S) atomic species. These basis sets are then contracted to (4s) for H ((2)S), (6s4p) for O ((3)P), and O(2-) ((1)S), (986p3d) for Cr(3+) ((4)F), (10s8p3d) for Cr(4+) ((3)F), and (13s7p) for Cr(6+) (1S) by a standard procedure. For evaluation of the quality of those basis sets in molecular calculations, we have accomplished studies of total and orbital (HOMO and HOMO-1) energies at the HF-Roothaan level for the molecular species of our interest. The results obtained with the contracted basis sets are compared to the values obtained with our extended basis sets and to the standard 6-311G basis set from literature. Finally, the contracted basis sets are enriched with polarization function and then utilized in the theoretical interpretation of IR-spectrum of hexaaquachromium (III) ion, [Cr(H(2)O)(6)](3+), tetraoxochromium (IV) ion, [CrO(4)](4-), and tetraoxochromium (VI) ion, [CrO(4)](2-). The respective theoretical harmonic frequencies and IR-intensities were computed at the density functional theory (DFT) level. In the DFT calculations we employed the Becke's 1988 functional using the LYP correlation functional. The comparison between the results obtained and the corresponding experimental values indicates a very good description of the IR-spectra of the molecular ions studied, and that the GCHF method is still a legitimate alternative for selection of Gaussian basis sets. (C) 2003 Elsevier B.V. All rights reserved.

Thermal studies of solid 4-chlorobenzylidenepyruvates of heavy lanthanides(III) and yttrium(III)

Solid-state compounds of general formula LnL(3).2H(2)O, where Ln is heavier trivalent lanthanides and yttrium, L is 4-chlorobenzylidenepyruvate have been synthetised.On heating these compounds decompose in steps. They lose the hydration water in the first step and the thermal decomposition of the anhydrous compounds occurs with the formation of oxochloride (Eu, Gd); mixture of oxide and oxochloride that decrease with increasing of atomic number of metal (Tb-Tm); or oxide (Yb, Lu, Y) as final residue, up to 900degreesC. The dehydration enthalpies found for terbium, holmium, ytterbium and yttrium compounds were: 34.93, 42.40, 57.39 and 62.24 kJ mol(-1), respectively.

Synthesis and some properties of hybrid gels of titanium oxide containing europium (III)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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.

Negative temperature coefficient thermistor based on Bi3Zn2Sb3O14 ceramic: An oxide semiconductor at high temperature

Bi1.5ZnSb1.5O7 dielectric ceramic with pyrochlore structure was investigated by impedance spectroscopy from 400 to 750 degreesC. Pyrochlore was synthesized by the polymeric precursor method, a chemical synthesis route derived from Pechini's method. The grain or bulk resistance exhibits a sensor temperature characteristic, being a thermistor with a negative temperature coefficient (NTC). Only a single region was identified on the resistance curve investigated. The NTC thermistor characteristic parameter (beta) is equal to 7140 degreesC, in the temperature range investigated. The temperature coefficient of the resistance (alpha) was derived, being equal to -4.46x10(-2) degreesC(-1) at 400 degreesC. The conduction mechanism and relaxation are discussed. (C) 2003 American Institute of Physics.