Gaussian basis sets by generator coordinate Hartree-Fock method to ab initio calculations of electron affinities of enolates

The Generator Coordinate Hartree-Fock (GCHF) method is employed to generate uncontracted 15s and 18s11p gaussian basis sets for the H, C and O atoms, respectively. These basis sets are then contracted to 3s and 4s H atom and 6s5p, for C and O atoms by a standard procedure. For quality evaluation of contracted basis sets in molecular calculations, we have accomplished calculations of total and orbital energies in the Hartree-Fock-Roothaaii (HFR) approach for CH, C(2) and CO molecules. The results obtained with the uncontracted basis sets are compared with values obtained with the standard D95, 6-311G basis sets and with values reported in the literature. The 4s and 6s5p basis sets are enriched with polarization and diffuse functions for atoms of the parent neutral systems and of the enolates anions (cycloheptanone enolate, 2,5-dimethyleyelopentanone enolate, 4-heptanone enolate, and di-isopropyl ketone enolate) from the literature, in order to assess their performance in ab initio molecular calculations, and applied for calculations of electron affinities of the enolates. The calculations were performed at the DFT (BLYP and B3LYP) and HF levels and compared with the corresponding experimental values and with those obtained by using other 6-3 1 + +G((*)) and 6-311 + +G((*)) basis sets from literature. For the enolates studied, the differences between the electron affinities obtained with GCHF basis sets, at the B3LYP level, and the experimental values are -0.001, -0,014, -0.001, and -0.001 eV. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Structural refinement and photoluminescence properties of irregular cube-like (Ca-1_Cu-x(x))TiO3 microcrystals synthesized by the microwave-hydrothermal method

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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.

SrSnO3:Nd obtained by the polymeric precursor method

In this work, the synthesis of Nd-doped SrSnO3 by the polymeric precursor method, with calcination between 250 and 700 A degrees C is reported. The powder precursors were characterized by TG/DTA and high temperature X-ray diffraction (HTXRD). After heat treatment, the material was characterized by XRD and infrared spectroscopy. Ester and carbonate amounts were strictly related to Nd-doping. According to XRD patterns, the orthorhombic perovskite was obtained at 700 A degrees C for SrSnO3 and SrSn0.99Nd0.01O3. For Sr0.99Nd0.01SnO3, the kinetics displayed an important hole in the crystallization process, as no peak was observed in HTXRD up to 700 A degrees C, while a XRD patterns showed a crystalline material after calcination at 250 A degrees C.

Is your vision consistent? A method for checking, based on scenario concepts

Common sense tells us that the future is an essential element in any strategy. In addition, there is a good deal of literature on scenario planning, which is an important tool in considering the future in terms of strategy. However, in many organizations there is serious resistance to the development of scenarios, and they are not broadly implemented by companies. But even organizations that do not rely heavily on the development of scenarios do, in fact, construct visions to guide their strategies. But it might be asked, what happens when this vision is not consistent with the future? To address this problem, the present article proposes a method for checking the content and consistency of an organization's vision of the future, no matter how it was conceived. The proposed method is grounded on theoretical concepts from the field of future studies, which are described in this article. This study was motivated by the search for developing new ways of improving and using scenario techniques as a method for making strategic decisions. The method was then tested on a company in the field of information technology in order to check its operational feasibility. The test showed that the proposed method is, in fact, operationally feasible and was capable of analyzing the vision of the company being studied, indicating both its shortcomings and points of inconsistency. (C) 2007 Elsevier Ltd. All rights reserved.

Yellow ZnxNi1-xWO4 pigments obtained using a polymeric precursor method

New tungstate-based ceramic pigments, displaying ZnxNi1-xWO4 stoichiometry, were obtained at low temperature using a polymeric precursor method. The powder precursors were milled in an attritor mill in an alcoholic rnedium and heat treated for 12 h. yielding homogeneous and crystalline powder pigments. Characterization (TG/DTA, XRD, IR and colorimetry) showed that mass loss increased with increasing Zn contents. Despite the presence of secondary phases and impurities, the wolframite phase was present in all samples. IR analysis revealed bands related to Me-O and [WO6](6-) group stretching was observed. The intensity of the yellow color of the pigments increased with increasing amount of nickel. (c) 2007 Elsevier Ltd. All fights reserved.

A device to improve the Schleger and Turner method for sweating rate measurements

The objective of this study was to test a device developed to improve the functionality, accuracy and precision of the original technique for sweating rate measurements proposed by Schleger and Turner [Schleger AV, Turner HG (1965) Aust J Agric Res 16:92-106]. A device was built for this purpose and tested against the original Schleger and Turner technique. Testing was performed by measuring sweating rates in an experiment involving six Mertolenga heifers subjected to four different thermal levels in a climatic chamber. The device exhibited no functional problems and the results obtained with its use were more consistent than with the Schleger and Turner technique. There was no difference in the reproducibility of the two techniques (same accuracy), but measurements performed with the new device had lower repeatability, corresponding to lower variability and, consequently, to higher precision. When utilizing this device, there is no need for physical contact between the operator and the animal to maintain the filter paper discs in position. This has important advantages: the animals stay quieter, and several animals can be evaluated simultaneously. This is a major advantage because it allows more measurements to be taken in a given period of time, increasing the precision of the observations and diminishing the error associated with temporal hiatus (e.g., the solar angle during field studies). The new device has higher functional versatility when taking measurements in large-scale studies (many animals) under field conditions. The results obtained in this study suggest that the technique using the device presented here could represent an advantageous alternative to the original technique described by Schleger and Turner.

Lanthanum-based perovskites obtained by the polymeric precursor method

Cobalt oxides, specially the ones with perovskite structure, are of a high technological interest, due to their interesting optical, electrical and magnetic properties. La(1 -x)Ca(x)CoO(3) powder samples were synthesized by the polymeric precursor method, with x varying from 0 to 0.4. The powder precursors were characterized by TG/DTA, XRD and IR. The TG curves showed several thermal decomposition steps; the first one is ascribed to the loss of water and the remaining steps are related to the combustion of the organic matter. The XRD patterns indicated only the presence of the perovskite phase. Moreover, the structure changes from rhombohedral to cubic, as calcium is added to the perovskite and the calcination temperature increases.

Nanometric Pb1-xLaxTiO3 (x=0, 0.13 and 0.27) powders obtained by the polymeric precursor method

PLT (Pb1-xLaxTiO3, in which x = 0, 0.13 and 0.27) powders were successfully synthesized using the polymeric precursor method, based on the Pechini method. The polymeric precursors were calcined at temperatures ranging from 350 to 500 degrees C for 4 h. X-ray diffraction (XRD) showed the evolution of the crystalline phase starting from the amorphous precursor. Thermogravimetric analyses (TG) and differential thermal analyses (DTA) of the powder precursors showed the influence of the pH on the elimination of organic material. PLT powders have a tendency to form agglomerates, what can be verified by comparing the values of the average particle sizes obtained by Brunauer-Emmett-Teller method, BET (D-BET) with the values of the average crystallite sizes obtained by XRD (D-XRD). (C) 2007 Elsevier Ltd. All fights reserved.

Luminescence properties of Eu(3+)- and Mg(2+)-doped LiTaO(3) obtained via the polymeric precursor method

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

Small-scale method for the determination of selected organochlorine pesticides in soil

A small-scale method was developed for the simultaneous determination of γ-HCH, heptachlor, aldrin, dicofol, mirex, endosulfan I, endosulfan II and endosulfan sulphate in soil. The extraction and clean-up steps were combined into one step by transferring soil samples to chromatographic columns prepacked with neutral alumina. The pesticides elution was processed with n-hexane : dichloromethane (7:3) and the concentrated eluate was analysed using gas-liquid chromatography with electron capture detection. Analyses of the in vitro fortified samples with the selected pesticides were performed at three different levels. Mean recoveries for aldrin, γ-HCH and heptachlor, at levels of 2, 10 and 20 ng/g, ranged from 71 to 87%; for dicofol, at levels of 8, 40 and 80 ng/g, ranged from 97 to 103%; for endosulfan I and II, at levels of 5, 25 and 50 ng/g, ranged from 88 to 96%; for mirex, at levels of 6, 30 and 60 ng/g, ranged from 86 to 110%; and for endosulfan sulphate, at levels of 15, 75 and 150 ng/g, ranged from 93 to 104%. The method can be used for rapid determination of these pesticides in soil. © Springer-Verlag 1996.

Fungus incidence on peanut grains as affected by drying method and Ca nutrition

An experiment was conducted to study the effects of liming and drying method on Ca nutrition, fungus infection and aflatoxin production potential on peanut (Arachis hypogea) grains. Peanut cv. Botutatu was grown in the absence or presence of liming to raise the base saturation of the soil from 20 to 56%. Calcium contents of the soil were increased from 5.5 to 14.6 mmol((c))kg-1 and pH from 4.2 to 4.9. After harvest, plants and pods were dried in (1) shade, (2) field down to 100 g water kg-1 (3) field down to 250 g water kg-1 and transferred to a forced-air oven at 30°C, (4) field down to 360 g water kg-1 and transferred to a forced-air oven at 30°C. Calcium contents were analyzed in the grains, pericarps and seed coats. The incidence of Aspergillus spp., Penicillium spp., Rhizopus spp. and potential aflatoxin production in vitro were evaluated, as well as the seed coat thickness. The seed coat was thicker when peanut was grown in the presence of lime, leading to a decrease in seed infection by Aspergillus spp. and Penicillium spp. When plants were dried in shade, the growth of aflatoxinogenic fungi was independent of liming. However, in plants dried in the field or field + oven, the development of these fungi was decreased and even suppressed when the Ca content of the seed coat was increased from 2.2 to 5.5 g kg-1.

Influence of barium and strontium addition on the ratio c/a of PZT obtained by the polymeric precursor method

Lead zirconate titanate powder, with Zr/Ti ratio of 50/50 was prepared by Pechini method after adding up to 10,0 mol% of Ba +2 and Sr +2 ions. Tetragonal phase is favored by the increase of barium and strontium concentration in the LiNbO 3 crystal lattice. The ratio c/a for tetragonal phase increases with the content of Ba +2 and Sr +2.