79 resultados para Fe(3)O(4)
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Pós-graduação em Educação - IBRC
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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Pós-graduação em Odontologia - FOA
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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(1) C6H2N3O7- center dot C5H12NO2+, Mr = 346.26, P2(1)/c, a = 7.2356(6), b = 10.5765(9), c = 19.593(2) angstrom, 3 beta=95.101(6)degrees, V = 1493.5(2) angstrom(3), Z = 4, R-1 = 0.0414; (2) C6H2N3O7- center dot C6H8NO+, Mr = 38.24, P2(1)/n, a = 7.8713(5), b = 6.1979(7), c = 28.697(3) angstrom, beta = 90.028(7)degrees, V = 1400.0(2) angstrom(3), Z = 4, R-1 = 0.0416. The packing units in both compounds consist of hydrogen bonded cation-anion pairs. The (hyper)polarizabilities have been calculated for the crystallographic and optimized molecules, by AM1 and at the DFT/B3LYP(6-31G**) level.
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The thermal behaviour of polymetallic metal carbonyls containing Fe-Fe, Fe-Hg and Hg-Hg bonds and Lewis bases, such as [Fe-3(CO)(8)(L)(2)] (L = 1,10-phenantroline,2,2'-bipyridine), [Fe(CO)(4)(HgCl)(2)] and [Fe(CO)(4)(HgCl)(2)(L)(2)] (L = 1,10-phenantroline,2-quinolinethiol), have been investigated by thermal analysis (TG), Thermal studies give evidence that the thermal decomposition mechanisms and starting temperatures are strongly influenced by the Lewis bases. The thermal decompositions under synthetic air yielded, in all cases, the final solid product Fe2O3 which presence was confirmed by X-ray powder diffraction technique.
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The kinetics of the hexacyanoferrate(III)-N,N′-dimethyl-4,4′-bipyridinium radical (MV+) reaction was studied by a laser flash photolysis technique. The radical was generated, in the presence of Fe(CN)6 3-, by quenching the excited state *Ru(bpy)3 2+ with MV2+. The second-order rate constant for the Fe(CN)6 3--MV+ reaction is (7.6 ± 0.5) × 109 M-1 s-1 at 23°C and ionic strength 0.10 M. Comparison with the rate constants calculated for the diffusion-controlled reaction (4.7 × 109 M-1 s-1) and the activation-controlled reaction (5.2 × 1012 M-1 s-1, on the basis of self-exchange rate constants of 8.0 × 105 M-1 s-1 and 1.9 × 104 M-1 s-1 for the MV2+/+ and Fe(CN)6 3-/4- couples, respectively) leads to the conclusion that the Fe(CN)6 3--MV+ reaction is diffusion controlled. The rate constant for the Fe(CN)6-MV2+ reaction, calculated from the rate constant for the Fe(CN)6 3--MV+ reaction and the appropriate equilibrium constant, is 2.4 × 10-5 M-1 s-1 at 23°C and ionic strength 0.10 M. Microscopic reversibility considerations require that the Fe(CN)6 4--MV2+ reaction be controlled by the dissociation of the successor complex Fe(CN)6 3-|MV+. The thermal and optical electron transfers in the ion pair Fe(CN)6 4-|MV2+ and in related systems are analyzed and discussed. © 1982 American Chemical Society.
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The Archean (3.45-2.70Ga) rocks of the São José do Campestre Massif (SJCM) in the Borborema Province (NE Brazil) make up a small area (~6000km2) and are composed of granitoids and metasupracrustal rocks that define a complex magmatic and deformational history. The massif provides the opportunity to study mantle- and crustal-derived magmas generated since the Palaeoarchean. The orthogneisses of the SJCM are composed of: (1) tonalite to granodiorite with diorite enclaves (Bom Jesus gneiss, 3412±8Ma; TDM Nd model ages from 4.1 to 3.5Ga and negative epsilon Nd values); (2) biotite and ferroan-diopside monzogranite (Presidente Juscelino complex, 3356±21Ma and 3251±44Ma; TDM model ages range from 4.1 to 3.4Ga and epsilon Nd values that are slightly positive to negative); (3) hornblende tonalite to granodiorite (Brejinho complex, 3333±77Ma and 3187±8Ma; dominantly positive epsilon Nd values and TDM ages from 3.6 to 3.2Ga); (4) biotite monzogranite (São Pedro do Potengi gneiss, 3120±22Ma; TDM =3.5Ga; negative epsilon Nd value); (5) ferroan-diopside-grossular anorthosite and metagabbro (Senador Elói de Souza complex, 3033±3Ma); and (6) quartz diorite to syenogranite (São José do Campestre complex; 2685±9Ma and 2655±4Ma; negative epsilon Nd values and TDM ages from 3.9 to 3.3Ga). The orthogneisses are subalkaline to faintly alkaline, magnesian to ferroan, M- and I-type granitoids that follow either the K-enrichment or the trondhjemite trends. Each group has a subset with REE characteristics similar to Archean TTG and another that is analogous to Phanerozoic granitoids. They have negative Ta-Nb and Ti anomalies and have trace element contents of granitoids from subduction zones. Geochemical and Nd isotope data suggest that subducted oceanic crust and a depleted and metasomatised mantle wedge both acted as the magma sources. We propose a convergent tectonic model in which hybridisation of the upper mantle occurs through interactions with adakitic or trondhjemitic melts and recycling of earlier crust. The results imply that both the subducted oceanic crust and the mantle wedge played major roles in continent formation throughout successive episodes of arc accretion in Palaeo- and Mesoarchean times. The Archean rocks of the SJCM shares some similarities with the Pilbara, Kaapvaal, West African, and São Francisco cratons. However, the most reliable comparisons with the SJCM are with the neighbouring basement of the Nigeria and Cameroon shields. © 2012 Elsevier B.V.
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Complexes of the type [PdX(PPh3)(1)]X [1 = 4-phenyl-3- thiosemicarbazide; X = Cl- (2), Br- (3), I- (4), and SCN- (5)] have been synthesized and characterized by elemental analyses and IR, UV/Vis, and 1H and 13C NMR spectroscopy. The molecular structure of complex 4 was determined by single-crystal X-ray diffraction. The binding of the complexes with a purine base (guanosine) was investigated by 1H NMR spectroscopy and mass spectrometry, which showed the complexes to coordinate to guanosine through N7. A gel electrophoresis assay demonstrated the ability of 2-5 to cleave DNA plasmid. All the complexes were tested in vitro by means of the MTT assay for their cytotoxicity against two murine cell lines, LM3 (mammary adenocarcinoma) and LP07 (lung adenocarcinoma), and compared with cisplatin. Complexes 2-5 exhibited good cytotoxicity that surpasses that of cisplatin in the case of LM3. A series of thiosemicarbazide/phosphane palladium(II) complexes have been synthesized and fully characterized. These complexes are able to cleave DNA plasmid and show cytotoxicity against adenocarcinoma (mammary LM3 and lung LP07), surpassing the cytotoxicity of cisplatin in the case of LM3. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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Pós-graduação em Ginecologia, Obstetrícia e Mastologia - FMB
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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A new procedure was developed in this study, based on a system equipped with a cellulose membrane and a tetraethylenepentamine hexaacetate chelator (MD-TEPHA) for in situ characterization of the lability of metal species in aquatic systems. To this end, the DM-TEPHA system was prepared by adding TEPHA chelator to cellulose bags pre-purified with 1.0 mol L-1 of HCl and NaOH solutions. After the MD-TEPHA system was sealed, it was examined in the laboratory to evaluate the influence of complexation time (0-24 h), pH (3.0, 4.0, 5.0, 6.0 and 7.0), metal ions (Cu, Cd, Fe, Mn and Ni) and concentration of organic matter (15, 30 and 60 mg L-1) on the relative lability of metal species by TEPHA chelator. The results showed that Fe and Cu metals were complexed more slowly by TEPHA chelator in the MD-TEPHA system than were Cd, Ni and Mn in all pH used. It was also found that the pH strongly influences the process of metal complexation by the MD-TEPHA system. At all the pH levels, Cd, Mn and Ni showed greater complexation with TEPHA chelator (recovery of about 95-75%) than did Cu and Fe metals. Time also affects the lability of metal species complexed by aquatic humic substances (AHS); while Cd, Ni and Mn showed a faster kinetics, reaching equilibrium after about 100 min, and Cu and Fe approached equilibrium after 400 min. Increasing the AHS concentration decreases the lability of metal species by shifting the equilibrium to AHS-metal complexes. Our results indicate that the system under study offers an interesting alternative that can be applied to in situ experiments for differentiation of labile and inert metal species in aquatic systems. (c) 2006 Elsevier B.V. All rights reserved.