Determination of selenium in nutritionally relevant foods by graphite furnace atomic absorption spectrometry using arsenic as internal standard

A method has been developed for the direct determination of Se in nutritionally relevant foods by graphite furnace atomic absorption spectrometry. Tungsten/rhodium carbide coating on the integrated platform of a transversely heated graphite atomizer or W coating with co-injection of Pd(NO3)(2) were used as a permanent modifiers. Samples and reference solutions were spiked with 500 mu g L-1 As and absorbance variations due to changes in experimental conditions were minimized. For 20 mu L aqueous analytical solutions delivered into the graphite tube, analytical curves in the 5.0-40 mu g L-1 with good linear correlation were established. Pyrolysis and atomization temperatures were evaluated using pyrolysis and atomization curves, respectively. The optimized heating program (temperature, ramp time, hold time) of the graphite tube of the Perkin-Elmer SIMAA 6000 atomic absorption spectrometer was: dry steps (110 degrees C, 5 s, 10 s; 130 degrees C, 15 s, 15 s); air-assisted pyrolysis step (600 degrees C, 20 s, 40 s; 20 degrees C, 1 s, 40 s); pyrolysis step (1300 degrees C, 10 s, 20 s); atomization step (2100 degrees C, 0 s, 4 s); clean step (2550 degrees C, 1 s, 5 s). The method was applied for Se determination in coconut water, coconut milk, soybean milk, cow milk, tomato juice, mango juice, grape juice and drinking water samples and four standard reference materials and results were in agreement at 95% confidence level. The lifetime of the tube was 500 firings and the relative standard deviations of measurements of typical samples containing 25 mu gL(-1) Se were 3.0% and 6.0% (n = 12) with and without internal standardization, respectively. The limits of detection were in the 0.35 mu g L-1-0.7 mu g Se L-1 range. The accuracy of the proposed method was evaluated by an addition-recovery experiment and all recovered values were in the 98-109% range. (c) 2004 Elsevier Ltd. All rights reserved.

Femtosecond nonlinear optical properties of lead-germanium oxide amorphous films

The nonlinear (NL) response of lead-germanium oxide amorphous films was investigated using a Ti:saphire laser delivering pulses of approximate to 150 fs at 800 nm. The Kerr shutter technique was employed to reveal the time response of the nonlinearity that is smaller than 150 fs. The sign and magnitude of the nonlinearity were obtained using a novel technique called thermally managed eclipse Z scan which allows the simultaneous characterization of cumulative and noncumulative NL effects. The NL refractive index of electronic origin, n(2)approximate to 2x10(-17) m(2)/W, and the NL absorption coefficient, alpha(2)approximate to 3x10(3) cm/GW, were determined. (c) 2007 American Institute of Physics.

Correlation between the surface morphology and structure and the photoluminescence of amorphous PbTiO3 thin films obtained by the chemical route

A polymeric precursor method was used to synthesis PbTiO3 amorphous thin film processed at low temperature. The luminescence spectra of PbTiO3 amorphous thin films at room temperature revealed an intense single-emission band in the visible region, the visible emission band was found to be dependent on the thermal treatment history, Photoluminescence properties Versus different annealing temperatures were investigated. The experimental results (XRD, AFM, FL) indicate that the nature of photoluminescence (PL) must be related to the disordered structure of PbTiO3 amorphous thin films, Copyright (C) 2000 John Wiley & Sons, Ltd.

Correlation among order-disorder, electronic levels, and photoluminescence in amorphous CT : Sm

Ca0.95Sm0.05TiO3 (CT:Sm) powder was prepared by the polymeric precursor method (PPM). Order-disorder at short and long range has been investigated by means of Raman spectroscopy, X-ray diffraction (XRD), and photoluminescence emission (PL) experimental techniques. The broad PL band and the Sm emission spectrum measured at room temperature indicate the increase of structural order with annealing temperature. The measured PL emission reveals that the PL intensity changes with the degree of disorder in the CT: Sm. The electronic structures were performed by the ab initio periodic method in the DFT level with the hybrid nonlocal B3LYP approximation. Theoretical results are analyzed in terms of DOS, charge densities, and Mulliken charges. Localized levels into the band gap of the CT: Sm material favor the creation of the electron-hole pair, supporting the observed room-temperature PL phenomenon.

Luminescence effect in amorphous PLT

Amorphous and crystalline powder of PLT phase was synthesized by using the Pechini method. Infrared (FTIR) analysis of the polymeric resin shows intense bands of organic materials from 250 to 1620 cm(-1). X-ray diffraction (XRD) and Raman spectra of calcined powder at different temperatures show amorphous phase at 450 degrees C/3 h, semi-crystalline phase at 550 degrees C/3 h and a crystalline phase at 800 degrees C/3 h. Luminescence effect was observed in amorphous powder calcined from 300 to 350 degrees/3 h with broad absorption peaks in 579 nm at 300 degrees C/3 h and 603 rum at 350 degrees C/3 h, respectively. The photoluminescence effect is attributed to emissions of Ti -> 0 directly from the oxygen 2p orbital (valence band) to the titanate 3d orbital (conduction bands). (c) 2004 Elsevier Ltd. All rights reserved.

Photoluminescence in amorphous TiO2-PbO systems

Photoluminescence (PL) at room temperature has been achieved in amorphous thin films and powders of the TiO2-PbO system. They were prepared by the polymeric precursor method with [PbO]/[TiO2] molar ratios ranging from 0.0 to 1.0. The energy position of maximum PL emission and the PL intensity showed dependence on Pb concentration. The Pb addition suggests an increase in the number of nonbridging oxygens (NBO) in the amorphous TiO2 network. These results support the relationship between photoluminescence and structure in TiO2-based amorphous materials.

A hydride generation flow system for determination of arsenic and selenium by total reflection X-ray fluorescence spectrometry

In this work, a preconcentration and separation system based on continuous flow hydride generation is proposed to improve the determination of As and Se by total reflection X-ray fluorescence spectrometry. The generated hydrides are continuously separated from the liquid phase and collected in a chamber containing 250 mul of HCI/HNO3 1:1 (v/v) solution. Hydride generation conditions and collection of the hydrides were evaluated. Under optimised conditions, enrichment factors of 55 for As and 82 for Se were attained. Detection limits of 0.3 mug l(-1) for As and Se were obtained when 20 ml of sample was used. Analysis of a natural water standard reference material from National Institute of Standard and Technology (SRM-1640) was in agreement with the certified values at the 95% confidence level. (C) 2004 Elsevier B.V. All rights reserved.

Low temperature annealing of amorphous gallium arsenide films

This work reports the changes in the optical properties produced by annealing of amorphous GaAs at temperatures smaller than or just sufficient to produce crystallization of the material. The films were grown by the flash evaporation technique on glass substrates at room temperature. Optical and structural changes of our samples were monitored through photothermal deflection spectroscopy, optical transmittance and reflectance and X-ray diffraction (XRD). The structural results from XRD detected no crystallization of the films for temperatures up to 240 degreesC. We have observed consistent changes in the optical gap and Urbach energy of the annealed film. The optical gap increases with increasing annealing temperature from 1.17 to 1.32 eV. The Urbach energy decrease from 120 meV (as-grown film) to 105 meV (anneal at 200 degreesC). We propose that these changes are due to a diminution of the tail state defects and/or the relaxation of strained bonds. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Photoluminescence in amorphous PLZ

Amorphous and crystalline powder of PLZ was prepared by using the polymeric precursor method. TGA-DSC (Thermal analysis and Differential Scanning Calorimetry) shows the decomposition of polymeric resin, an amorphous phase and the crystallization of powder. Raman scattering of powder shows an amorphous and semicrystalline phase at 450 and 550 degreesC, respectively. XRD (X-ray diffraction pattern) of powder shows high crystallinity at 700 degreesC/3 h. PL (Photoluminescence) analysis of powder at 300 degreesC/3 h shows a broad asymmetric peak at 585 nm and increases of calcining time led to intense peaks of PL at 300 degreesC/6 h. This emission could be attributed to Zr --> O from the oxygen-2p orbitals to the zirconate-3d orbitals. (C) 2003 Elsevier Ltd and Techna S.r.l. All rights reserved.

Low-temperature, self-nucleated growth of indium-tin oxide nanostructures by pulsed laser deposition on amorphous substrates

Indium-tin oxide nanostructures were deposited by excimer laser ablation in a nitrogen atmosphere using catalyst-free oxidized silicon substrates at 500 degrees C. Up to 1 mbar, nanowires grew by the vapor-liquid-solid (VLS) mechanism, with the amount of liquid material decreasing as the deposition pressure increased. The nanowires present the single-crystalline cubic bixbyite structure, oriented < 100 >. For the highest pressure used, pyramids were formed and no sign of liquid material could be observed, indicating that these structures grew by a vapor-solid mechanism. (c) 2006 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Preparation of Fe-Cr-P-Co amorphous alloys by electrodeposition

The effects of bath composition and electroplating conditions on structure, morphology, and composition of amorphous Fe-Cr-P-Co deposits on AISI 1020 steel substrate, priorly plated with a thin Cu deposit, were investigated. The increase of charge density activates the inclusion of Cr in the deposit. However, above specific values of the charge density, which depend on the deposition current density, the Cr content in the deposit decreases. This Cr content decreasing is probably due to the significant hydrogen evolution with the increasing of deposition cur-rent and charge density. The effect of charge density on the content of Fe and Co is not clear. However, there is a tendency of increasing of Fe content and decreasing of Co content with the raising of current density. The Co is more easily deposited than the P, and its presence results in a more intense inhibition effect on the Cr deposition than the inhibition effect caused by P presence. Scanning electron microscope (SEM) analysis showed that Co increasing in the Fe-Cr-P-Co alloys analyzed does not promote the susceptibility to microcracks, which led to a good quality deposit. The passive film of the Fe-Cr-P-Co alloy shows a high ability formation and high protective capacity, and the results obtained by current density of corrosion, j(cor), show that the deposit with addition of Co, Fe31Cr11P28Co30, presents a higher corrosion resistance than the deposit with addition of Ni, Fe54Cr21P20Ni5. (C) 2004 Published by Elsevier B.V.

Photoluminescence in amorphous (PbLa)TiO3 thin films deposited on different substrates

Pb1-XLaXTiO3 thin films, (X = 0.0; 13 and 0.27 mol%) were prepared by the polymeric precursor method. Thin films were deposited on Pt/Ti/SiO2/Si (1 1 1), Si (1 0 0) and glass substrates by spin coating, and annealed in the 200-300degreesC range in an O-2 atmosphere. X-ray diffraction, scanning electron microscopy and atomic force microscopy were used for the microstructural characterization of the thin films. Photoluminescence (PL) at room temperature has been observed in thin films of (PbLa)TiO3. The films deposited on Pt/Ti/SiO2/Si substrates present PL intensity greater than those deposited on glass and silicon substrates. The intensity of PL in these thin films was found to be dependent on the thermal treatment and lanthanum molar concentration. (C) 2002 Elsevier B.V. B.V. All rights reserved.

A Simple Method Based on ICP-MS for Estimation of Background Levels of Arsenic, Cadmium, Copper, Manganese, Nickel, Lead, and Selenium in Blood of the Brazilian Population

Throughout the world, biomonitoring has become the standard for assessing exposure of individuals to toxic elements as well as for responding to serious environmental public health problems. However, extensive biomonitoring surveys require rapid and simple analytical methods. Thus, a simple and high-throughput method is proposed for the determination of arsenic (As), cadmium (Cd), copper (Cu), manganese (Mn), nickel (Ni), lead (Pb), and selenium (Se) in blood samples by using inductively coupled plasma-mass spectrometry (ICP-MS). Prior to analysis, 200 l of blood samples was mixed with 500 l of 10% v/v tetramethylammonium hydroxide (TMAH) solution, incubated for 10 min, and subsequently diluted to 10 ml with a solution containing 0.05% w/v ethylenediamine tetraacetic acid (EDTA) + 0.005% v/v Triton X-100. After that, samples were directly analyzed by ICP-MS (ELAN DRC II). Rhodium was selected as an internal standard with matrix-matching calibration. Method detection limits were 0.08, 0.04, 0.5, 0.09, 0.12, 0.04, and 0.1 g//L for As, Cd, Cu, Mn, Ni, Pb, and Se, respectively. Validation data are provided based on the analysis of blood samples from the trace elements inter-\comparison program operated by the Institut National de Sante Publique du Quebec, Canada. Additional validation was provided by the analysis of human blood samples by the proposed method and by using electrothermal atomic absorption spectrometry (ETAAS). The method was subsequently applied for the estimation of background metal blood values in the Brazilian population. In general, the mean concentrations of As, Cd, Cu, Mn, Ni, Pb, and Se in blood were 1.1, 0.4, 890, 9.6, 2.1, 65.4, and 89.3 g/L, respectively, and are in agreement with other global populations. Influences of age, gender, smoking habits, alcohol consumption, and geographical variation on the values were also considered. Smoking habits influenced the levels of Cd in blood. The levels of Cu, Mn, and Pb were significantly correlated with gender, whereas Cu and Pb were significantly correlated with age. There were also interesting differences in Mn and Se levels in the population living in the north of Brazil compared to the south.

EFFECTS of SELENIUM SUPPLEMENTATION on CATTLE ANTI-RABIES HUMORAL IMMUNE RESPONSE and LEVELS of SERUM SELENIUM and CORTISOL

This study evaluated the effect of different concentrations of selenium (Se) supplementation on cattle anti-rabies humoral immune response, serum Se concentrations and cortisol levels. Sixty uncastrated male Nelore calves from 10 to 12 months grazing on Brachiaria decumbens forage were studied. The animals were assigned to one of four groups (n = 15 each), which received non-supplemented diets (Gc) or supplemented with daily and individual Selenium ( Se) concentrations of 3.6 mg (G(3.6)), 5.4 mg (G(5.4)) or 6.4 mg (G(6.4)). The calves were immunized on day 0 with one dose of commercial liquid inactivated rabies vaccination. on days 15, 30, 60, 90 and 120, the cattle underwent the same stressing procedures used for vaccination in the corral. Cattle blood samples were collected after vaccination and stressing procedures to determine serum Se levels, rabies antibody titers and serum cortisol. Se levels were also determined in forage samples collected from the paddocks in which the cattle were held. Se concentration in B. decumbens was 0.04 mg of Se/kg dry matter. Baseline Se levels obtained on day 0 were higher in Gc than in G(5.4) and G(6.4) (P = 0.005). Serum Se levels decreased in Gc throughout the experiment (P < 0.004), increased in G(3.6) (P < 0.000) and G(5.4) (P < 0.000) and were kept high from day 60 on in group G(6.4) (P < 0.002). Rabies antibody titers did not differ among control and supplemented groups. However, 120 days after vaccination rabies antibody titers were kept above protective levels (>= 0.5 UI/mL) only in group G(3.6) (P < 0.00002), whereas they dropped in the other groups (P < 0.05). Serum cortisol levels did not differ among the experimental groups (P = 0.79), reached peak levels on day 90 and returned close to baseline levels on day 120. Se and cortisol levels were not markedly correlated. Serum cortisol and rabies antibody titers were correlated only in group G(6.4), on day 60 (R = 0.513; P = 0.05) and 120 (R = 0.644; P = 0.009). Serum Se and rabies antibody titers were correlated only in group G(6.4), on day 60 (R = -0.580; P = 0.023). In conclusion: a) the profile of Se variation is different among groups receiving different concentrations of this element; b) the supplementation dosage of 3.6 mg Se/animal/day is efficient to treat/prevent marginal Se deficiency; c) individual supplementation with daily concentrations of 3.6 mg Se enhances the maintenance of rabies antibody titers in cattle; d) individual supplementation with daily concentrations of 3.6; 5.4 and 6.4 mg Se are ineffective in reducing serum cortisol; e) repeated cattle handling in corrals stress animals that adapt to these procedures, although serum cortisol does not return to baseline levels by 120 days; and f) the stress generated by repeated management in cattle in the corral does not diminish antibody titers after vaccination against rabies.

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)