Caracterização estrutural das substâncias húmicas aquáticas extraídas dos rios itapanhaú e ribeira de iguape

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Multimethod study of the degree of humification of humic substances extracted from different tropical soil profiles in Brazil's Amazonian region

This work consisted of determining the degree of humification of humic substances (HS) extracted from six different Amazonian soils collected from flooded and unflooded regions at different depths (0-10, 10-20, 20-40, and 60 cm). The humic substances were extracted according to procedures recommended by the International Humic Substances Society and characterized using elemental analysis, electron paramagnetic resonance (EPR), and fluorescence spectroscopy. The findings on semiquinone-type free radical concentrations in HS showed variations of 0.10-7.55x10(18) spins g(-1) of carbon (g C)(-1), indicating considerable differences between the humification levels of HS extracted from Amazonian soils. The results showed an average of 1.71 +/- 0.04 x 10(18) spins (g C)(-1), which is congruent with other data reported in the literature on Tropical soils. It was found that, on average, HS extracted from flooded soil contained higher semiquinone-type free radical concentrations than HS extracted from unflooded soils, indicating the influence of humidity in the humification process of organic matter. The humification process varies according to the profile, and the 10-20- and 0-10-cm profiles generally showed more humified HS. The degree of humification of the HS studied here displayed a similar behavior when exposed to fluorescence (excitation at 465 nm) and EPR (R=0.85). However, the low correlation between the C/H, C/O, and C/N atomic ratios and the semiquinone-type free radical concentration/fluorescence intensities indicated that data obtained by these techniques with regard to the degree of humification of HS may lead to different conclusions. (c) 2004 Elsevier B.V. All rights reserved.

Characterization of humic acids from a Brazilian Oxisol under different tillage systems by EPR, C-13 NMR, FTIR and fluorescence spectroscopy

The importance of soil organic matter functions is well known, but structural information, chemical composition and changes induced by anthropogenic factors such as tillage practices are still being researched. In the present paper were characterized Brazilian humic acids (HAs) from an Oxisol under different treatments: conventional tillage/maize-bare fallow (CT1); conventional tillage/maize rotation with soybean-bare fallow (CT2)-, no-till/maize-bare fallow (NT1); no-till/maize rotation with soybean-bare fallow (NT2); no-till/maize-cajanus (NT3) and no cultivated soil under natural vegetation (NC). Soil HA samples were analyzed by electron paramagnetic resonance (EPR), solid-state C-13 nuclear magnetic resonance (C-13 NMR), Fourier transform intra-red (FTIR) and UV-Vis fluorescence spectroscopies and elemental analysis (CHNS). The FTIR spectra of the HAs were similar for all treatments. The level of semiquinone-type free radical determined from the EPR spectra was lower for treatments no-till/maize-cajanus (NT3) and noncultivated soil (1.74 X 10(17) and 1.02 x 10(17) spins g(-1) HA, respectively), compared with 2.3 X 10(17) spins g(-1) HA for other soils under cultivation. The percentage of aromatic carbons determined by C-13 NMR also decreases for noncultivated soil to 24%, being around 30% for samples of the other treatments. The solid-state C-13 NMR and EPR spectroscopies showed small differences in chemical composition of the HA from soils where incorporation of vegetal residues was higher, showing that organic matter (OM) formed in this cases is less aromatic. The fluorescence intensities were in agreement with the percentage of aromatic carbons, determined by NMR (r = 0.97 P < 0.01) and with semiquinone content, determined by EPR (r = 0.97 P < 0.01). No important effect due to tillage system was observed in these areas after 5 years of cultivation. Probably, the studied Oxisol has a high clay content that offers protection to the clay-Fe-OM complex against strong structural alterations. (C) 2003 Elsevier B.V. All rights reserved.

The role of oxygen vacancies on the microstructure development and on the electrical properties of SnO2-based varistors

Variations on the microstructure development and on the electrical properties of SnO2-based varistors are discussed on the basis of the oxygen vacancies created or annihilated by the presence of different additives. Electron paramagnetic resonance (EPR) analysis of sintered samples evidenced a substantial increase in the paramagnetic oxygen vacancies concentration when Nb2O5 is added to the SnO2 center dot Co3O4 system. on the other hand, the observed diminution in the concentration of such species after the addition of Fe2O3 indicates solid solution formation. The quantification of paramagnetic oxygen vacancies allowed to confirm the proposed substitutions taking place in the lattice during sintering. These findings are supported by scanning electron microscopy, by density measurements and by current density versus electric field curves. The characterization of secondary phases through EDS assisted SEM and TEM is also reported in this work.

A laser-induced fluorescence spectroscopic study of organic matter in a Brazilian Oxisol under different tillage systems

Laser-induced fluorescence (LIF) spectroscopy has been proposed as new method for determining the degree of humification of organic matter (OM) in whole soils. It can be also used to analyze the OM in whole soils containing large amounts of paramagnetic materials, and which are neither feasible to Electron Paramagnetic Resonance (EPR) nor to C-13 Nuclear Magnetic Resonance (NMR) spectroscopy. In the present study, 3 LIF spectroscopy was used to investigate the OM in a Brazilian Oxisol containing high concentration of Fe+3. Soil samples were collected from two areas under conventional tillage (CT), two areas under no-till management (NT) and from a non-cultivated (NC) area under natural vegetation. The results of LIF spectroscopic analysis of the top layer (0-5 cm) of whole soils showed a less aromatic OM in the non-cultivated than in the cultivated soils. This is consistent with data corresponding to HA samples extracted from the same soils and analyzed by EPR, NMR and conventional fluorescence spectroscopy. The OM of whole soils at 5-10 and 10-20 cm depth was also characterized by LIF spectroscopy.Analysis of samples of NT and NC soils showed a higher OM aromatic content at depth. This is a consequence of the accumulation of plant residues at the soil surface in quantities that are too large for microorganisms to metabolize fully, thus, resulting in less aromatic or less hurnified humic substances. In deeper soil layers, the input of residues was lower and further decomposition of humic substances by microorganisms continued, and the aromaticity and degree of humification increased with soil depth. This data indicates that the gradient of humification of OM in the NT soil was similar to those observed in natural soils. Nevertheless, the degree of humification of the OM in the soils under no-till management varied less than that corresponding to non-cultivated soils. This may be because the former have been managed under these practices for only 5 years, in contrast to the continuous humification process occurring in the natural soils. on the other band, LIF spectroscopic analysis of the CT soils showed less pronounced changes or no change in the degree of humification with depth. This indicates that the ploughing and harrowing involved in CT lead to homogenization of the soil and thereby also of the degree of humification of OM throughout the profile. (c) 2006 Elsevier B.V. All rights reserved.

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.

Organic complexation and translocation of ferric iron in podzols of the Negro River watershed. Separation of secondary Fe species from Al species

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

CeO2 nanoparticles synthesized by a microwave-assisted hydrothermal method: evolution from nanospheres to nanorods

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Er(3+) doped phosphoniobate glasses and planar waveguides: structural and optical properties

Phosphoniobate glasses with composition (mol%) (100-x) NaPO(3)-xNb(2)O(5) ( x varying from 11 to 33) were prepared and characterized by means of thermal analysis, Fourier transform infrared spectroscopy, Raman scattering and (31)P nuclear magnetic resonance. The addition of Nb(2)O(5) to the polyphosphate base glass leads to depolymerization of the metaphosphate structure. Different colors were observed and assigned as indicating the presence of Nb(4+) ions, as confirmed by electron paramagnetic resonance measurements. The color was observed to depend on the glass composition and melting temperature as well. Er(3+) containing samples were also prepared. Strong emission in the 1550 nm region was observed. The Er(3+4)I(15/2) emission quantum efficiency was observed to be 90% and the quenching concentration was observed to be 1.1 mol%( 1.45 x 10(20) ions cm(-3)). Planar waveguides were prepared by Na(+)-K(+)-Ag(+) ion exchange with Er(3+) containing samples. Optical parameters of the waveguides were measured at 632.8, 543.5 and 1550 nm by the prism coupling technique as a function of the ion exchange time and Ag(+) concentration. The optimized planar waveguides show a diffusion depth of 5.9 mu m and one propagating mode at 1550 nm.

Photoluminescence in quasi-amorphous Pb0.8X0.2Zr0.53Ti0.47O3 (X = Ca, Sr and Ba) powders: An optical and structural study

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Synthesis, characterization, crystal structure, and biological studies of vanadium complexes with glycolic acid

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Structural conditions that leads to photoluminescence emission in SrTiO3: An experimental and theoretical approach

Complex cluster [TiO5 center dot V-O(z)] and [SrO11 center dot V-O(z)] (where V-O(z)=V-O(X), V-O(center dot), V-O(center dot center dot)) vacancies were identified in disordered SrTiO3 powders prepared by the polymeric precursor method, based on experimental measurements by x-ray absorption near edge structure spectroscopy. The paramagnetic complex states of [TiO5 center dot V-O(center dot)] and [SrO11 center dot V-O(center dot)] with unpaired electrons were confirmed by electron paramagnetic resonance spectroscopy. The disordered powders showed strong photoluminescence at room temperature. Structural defects of disordered powders, in terms of band diagram, density of states, and electronic charges, were interpreted using high-level quantum mechanical calculations in the density functional framework. The four periodic models used here were consistent with the experimental data and explained the presence of photoluminescence. (C) 2008 American Institute of Physics.

The role of oxygen vacancy in the photoluminescence property at room temperature of the CaTiO3

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Doping of polyaniline and derivatives induced by X-ray radiation

Thin films of chemically synthesized polyaniline and poly(o-methoxyaniline) were exposed to ionizing X-ray radiation and characterized by radiation induced conductivity measurements, ultraviolet-visible spectroscopy, electron paramagnetic resonance, electrical conductivity and solubility measurements. Samples irradiated in vacuum or dry Oxygen atmosphere did not have their electronic spectra changed. However, under humid atmosphere the energy of the excitonic transition was decreased and accompanied by a great conductivity increase. The results indicate that doping of polyaniline can be induced by X-ray radiation which might be of great interest for applications on lithography and microelectronics.

EPR of Mn as densifying agent in SnO2 powders

Electron Paramagnetic Resonance (EPR) spectra have been obtained at room temperature and at X-band in powders of SnO2 doped with Mn from 0.3 to 10% and submitted to heat treatment from 500 to 900 °C. Mn ions are probably located at particle surfaces as Mn2+, evidenced by its single EPR line which narrows by the exchange interaction effect due to particle growth observed by the BET technique. In samples doped above 1% formation Of Mn3O4 is detected on particle surfaces and a small quantity of Mn is thermally diffused into the bulk as Mn4+. Powders compacted and sintered at 1300 °C confirmed that Mn2+ ions remain at grain boundaries acting as densifying agent.