Estudo teórico QTAIM e DFT dos compostos de coordenação: efeito quelato, titanocenos e ligação química

This work is a study of coordination compounds by quantum theory of atoms in molecules (QTAIM), based on the topological analysis of the electron density of molecular systems, both theoretically and experimentally obtained. The coordination chemistry topics which were studied are the chelate effect, bent titanocene and chemical bond in coordination complexes. The chelate effect was investigated according to topological and thermodynamic parameters. The exchange of monodentate ligands on polydentate ligands from same transition metal increases the stability of the complex both from entropy and enthalpy contributions. In some cases, the latter had a higher contribution to the stability of the complex in comparison with entropy. This enthalpic contribution is explained according to topological analysis of the M-ligand bonds where polidentate complex had higher values of electron density of bond critical point, Laplacian of electron density of bond critical point and delocalization index (number of shared electrons between two atoms). In the second chapter, was studied bent titanocenes with bulky cyclopentadienyl derivative π-ligand. The topological study showed the presence of secondary interactions between the atoms of π-ligands or between atoms of π-ligand and -ligand. It was found that, in the case of titanocenes with small difference in point group symmetry and with bulky ligands, there was an nearly linear relationship between stability and delocalization index involving the ring carbon atoms (Cp) and the titanium. However, the titanocene stability is not only related to the interaction between Ti and C atoms of Cp ring, but secondary interactions also play important role on the stability of voluminous titanocenes. The third chapter deals with the chemical bond in coordination compounds by means of QTAIM. The quantum theory of atoms in molecules so far classifies bonds and chemical interactions in two categories: closed shell interaction (ionic bond, hydrogen bond, van der Waals interaction, etc) and shared interaction (covalent bond). Based on topological parameters such as electron density, Laplacian of electron density, delocalization index, among others, was classified the chemical bond in coordination compounds as an intermediate between closed shell and shared interactions

Adsorção dos gases NH3, NO e H2S em fosfato de vanadila, hidrogeno fosfato de vanadila e fosfatos de vanadila dopados por Al, Co, Mn e Cr

In this work were synthesized the materials called vanadyl phosphate, hydrogen vanadyl phosphate and vanadyl phosphate doped by transition metals with the aim in adsorption the following compounds: ammonia, hydrogen sulfide and nitrogen oxide. To characterize the starting compounds was used DRX, FTIR, FRX and TG analysis. After the characterization of substrates, proceeded de adsorption of NH3 and H2S gases in reactor, passing the gases with continuous flow for 30 min and room temperature. Gravimetric data indicate that the matrices of higher performance in adsorption of ammonia was those doped by aluminum and manganese, obtaining results of 216,77 mgNH3/g and 200,40 mgNH3/g of matrix, respectively. The matrice of higher performance in adsorption of hydrogen sulfide was that doped by manganese, obtaining results of 86,94 mgH2S/g of matrix. The synthesis of substrates VOPO4.2H2O and MnVOPO4.2H2O with nitrogen oxide was made in solution, aiming the final products VOPO4.G.nH2O and MnVOPO4.G.nH2O (G = NO and n = number of water molecules). The thermo analytical behavior and the infrared spectroscopy are indicative of formation of VOPO4.2,5NO.3H2O compound. Results of scanning electron microscopy (SEM) and Energy dispersive spectroscopy (EDS) of materials vanadyl phosphate and vanadyl phosphate modified after reaction in solid state or in solution with the gases show morphology changes in substrates, beyond the formation of orthorhombic sulfur crystals over their respective hosts when these adsorb hydrogen sulfide

Caracterização química e toxicológica da água produzida descartada em plataformas de óleo e gás na costa brasileira e seu comportamento dispersivo no mar

The production of oil and gas is usually accompanied by the production of water, also known as produced water. Studies were conducted in platforms that discharge produced water in the Atlantic Ocean due to oil and gas production by Petrobras from 1996 to 2006 in the following basins: Santos (Brazilian south region), Campos (Brazilian southeast region) and Ceara (Brazilian northeast region). This study encompasses chemical composition, toxicological effects, discharge volumes, and produced water behavior after releasing in the ocean, including dispersion plumes modeling and monitoring data of the marine environment. The concentration medians for a sampling of 50 samples were: ammonia (70 mg L-1), boron (1.3 mg L1), iron (7.4 mg L-1), BTEX (4.6 mg L-1), PAH (0.53 mg L-1), TPH (28 mg L-1); phenols (1.3 mg L-1) and radioisotopes (0.15 Bq L-1 for 226Ra and 0.09 Bq L-1 for 228Ra). The concentrations of the organic and inorganic parameters observed for the Brazilian platforms were similar to the international reference data for the produced water in the North Sea and in other regions of the world. It was found significant differences in concentrations of the following parameters: BTEX (p<0.0001), phenols (p=0.0212), boron (p<0.0001), iron (p<0.0001) and toxicological response in sea urchin Lytechinus variegatus (p<0.0001) when considering two distinguished groups, platforms from southeast and northeast Region (PCR-1). Significant differences were not observed among the other parameters. In platforms with large gas production, the monoaromatic concentrations (BTEX from 15.8 to 21.6 mg L-1) and phenols (from 2 to 83 mg L-1) were higher than in oil plataforms (median concentrations of BTEX were 4.6 mg L-1 for n=53, and of phenols were 1.3 mg L-1 for n=46). It was also conducted a study about the influence of dispersion plumes of produced water in the vicinity of six platforms of oil and gas production (P-26, PPG-1, PCR-1, P-32, SS-06), and in a hypothetical critical scenario using the chemical characteristics of each effluent. Through this study, using CORMIX and CHEMMAP models for dispersion plumes simulation of the produced water discharges, it was possible to obtain the dilution dimension in the ocean after those discharges. The dispersion plumes of the produced water modelling in field vicinity showed dilutions of 700 to 900 times for the first 30-40 meters from the platform PCR-1 discharge point; 100 times for the platform P-32, with 30 meters of distance; 150 times for the platform P-26, with 40 meters of distance; 100 times for the platform PPG-1, with 130 meters of distance; 280 to 350 times for the platform SS-06, with 130 meters of distance, 100 times for the hypothetical critical scenario, with the 130 meters of distance. The dilutions continue in the far field, and with the results of the simulations, it was possible to verify that all the parameters presented concentrations bellow the maximum values established by Brazilian legislation for seawater (CONAMA 357/05 - Class 1), before the 500 meters distance of the discharge point. These results were in agreement with the field measurements. Although, in general results for the Brazilian produced water presented toxicological effects for marine organisms, it was verified that dilutions of 100 times were sufficient for not causing toxicological responses. Field monitoring data of the seawater around the Pargo, Pampo and PCR-1 platforms did not demonstrate toxicity in the seawater close to these platforms. The results of environmental monitoring in seawater and sediments proved that alterations were not detected for environmental quality in areas under direct influence of the oil production activities in the Campos and Ceara Basin, as according to results obtained in the dispersion plume modelling for the produced water discharge

Caracterização química e toxicológica da água produzida descartada em plataformas de óleo e gás na costa brasileira e seu comportamento dispersivo no mar

The production of oil and gas is usually accompanied by the production of water, also known as produced water. Studies were conducted in platforms that discharge produced water in the Atlantic Ocean due to oil and gas production by Petrobras from 1996 to 2006 in the following basins: Santos (Brazilian south region), Campos (Brazilian southeast region) and Ceara (Brazilian northeast region). This study encompasses chemical composition, toxicological effects, discharge volumes, and produced water behavior after releasing in the ocean, including dispersion plumes modeling and monitoring data of the marine environment. The concentration medians for a sampling of 50 samples were: ammonia (70 mg L-1), boron (1.3 mg L1), iron (7.4 mg L-1), BTEX (4.6 mg L-1), PAH (0.53 mg L-1), TPH (28 mg L-1); phenols (1.3 mg L-1) and radioisotopes (0.15 Bq L-1 for 226Ra and 0.09 Bq L-1 for 228Ra). The concentrations of the organic and inorganic parameters observed for the Brazilian platforms were similar to the international reference data for the produced water in the North Sea and in other regions of the world. It was found significant differences in concentrations of the following parameters: BTEX (p<0.0001), phenols (p=0.0212), boron (p<0.0001), iron (p<0.0001) and toxicological response in sea urchin Lytechinus variegatus (p<0.0001) when considering two distinguished groups, platforms from southeast and northeast Region (PCR-1). Significant differences were not observed among the other parameters. In platforms with large gas production, the monoaromatic concentrations (BTEX from 15.8 to 21.6 mg L-1) and phenols (from 2 to 83 mg L-1) were higher than in oil plataforms (median concentrations of BTEX were 4.6 mg L-1 for n=53, and of phenols were 1.3 mg L-1 for n=46). It was also conducted a study about the influence of dispersion plumes of produced water in the vicinity of six platforms of oil and gas production (P-26, PPG-1, PCR-1, P-32, SS-06), and in a hypothetical critical scenario using the chemical characteristics of each effluent. Through this study, using CORMIX and CHEMMAP models for dispersion plumes simulation of the produced water discharges, it was possible to obtain the dilution dimension in the ocean after those discharges. The dispersion plumes of the produced water modelling in field vicinity showed dilutions of 700 to 900 times for the first 30-40 meters from the platform PCR-1 discharge point; 100 times for the platform P-32, with 30 meters of distance; 150 times for the platform P-26, with 40 meters of distance; 100 times for the platform PPG-1, with 130 meters of distance; 280 to 350 times for the platform SS-06, with 130 meters of distance, 100 times for the hypothetical critical scenario, with the 130 meters of distance. The dilutions continue in the far field, and with the results of the simulations, it was possible to verify that all the parameters presented concentrations bellow the maximum values established by Brazilian legislation for seawater (CONAMA 357/05 - Class 1), before the 500 meters distance of the discharge point. These results were in agreement with the field measurements. Although, in general results for the Brazilian produced water presented toxicological effects for marine organisms, it was verified that dilutions of 100 times were sufficient for not causing toxicological responses. Field monitoring data of the seawater around the Pargo, Pampo and PCR-1 platforms did not demonstrate toxicity in the seawater close to these platforms. The results of environmental monitoring in seawater and sediments proved that alterations were not detected for environmental quality in areas under direct influence of the oil production activities in the Campos and Ceara Basin, as according to results obtained in the dispersion plume modelling for the produced water discharge

Sobrevivência de Salmonella enteritidis em Ovos Contaminados Artificialmente, Após Desinfecção e Armazenados em Diferentes Temperaturas

Avaliou-se a contaminação da casca e do conteúdo interno de ovos inoculados com Salmonella enterica sorovar enteritidis fagotipo 4, lavados com água de torneira (AT) ou solução de amônia quaternária (AQ) e armazenados a 8ºC e 25ºC. Duzentos e cinqüenta e dois ovos foram divididos em três grupos. Os tratamentos de cada grupo consistiram de imersão em AT, AQ a 25ºC e a 43ºC. Após a secagem natural, todos os grupos foram contaminados com solução de S. enteritidis. Seguindo-se a contaminação, cada grupo tratado foi estocado a 8ºC ou 25ºC, e a presença de S. enteritidis na casca e no conteúdo interno foi avaliada após zero, 24, 96 e 168 horas. A sanitização com AQ mostrou-se eficiente na redução de S. enteritidis nas cascas dos ovos. O armazenamento dos ovos a 8ºC demonstrou ser preponderante na redução e na ausência de S. enteritidis na casca. Nos ovos lavados com AT, o armazenamento a 25ºC permitiu a permanência da bactéria nas cascas até 168 horas. Não se detectou S. enteritidis no conteúdo interno dos ovos em nenhum dos grupos.

Growth performance and metabolic response of Nile tilapia fed rations supplemented with autolized yeast and zinc

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

Performance of the constructed wetland system for the treatment of water from the corumbataí river

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

Dehydration and volatilization non isothermic kinetic of the solid state aluminium 8-hydroxyquinolinate

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

Processos diurnos e noturnos de remoção de NO2 e NH3 atmosféricos na região de Araraquara-SP

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

The importance of excretion by Chironomus larvae on the internal loads of nitrogen and phosphorus in a small eutrophic urban reservoir

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

Extração de amônio de filtros de amostragem, coleta e determinação pelo método da gota suspensa

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

Logistic regression to estimate the welfare of broiler breeders in relation to environmental and behavioral variables

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

Efeito de condicionadores químicos sobre a qualidade da cama de frango

Avaliou-se a qualidade química da cama de frango submetida, por três lotes consecutivos de criação, a diferentes condicionadores químicos. Foram utilizadas 1320 aves, 440 por lote, em delineamento experimental em blocos ao acaso, com cinco tratamentos (Trat. 1 - cama sem tratamento; Trat. 2 - cama tratada com sulfato de alumínio; Trat. 3 - cama tratada com gesso agrícola; Trat. 4 - cama tratada com superfosfato simples e Trat. 5 - cama tratada com cal hidratada) e quatro repetições. As amostras de cama foram coletadas no 42º dia de utilização. Não houve influência dos condicionadores (P>0,05) sobre a matéria seca. O sulfato de alumínio reduziu (P<0,002) o valor de pH (7,42; 7,07 e 6,00, respectivamente no primeiro, segundo e terceiro lotes) e reduziu (P<0,05) a quantidade de amônia volatilizada (3,14; 1,36 e 1,79mg/100g, respectivamente no primeiro, segundo e terceiro lotes), quando comparado aos outros tratamentos. Concluiu-se que o sulfato de alumínio pode ser adicionado à cama de frango para manter o pH baixo e inibir a volatilização da amônia.

Consumo, digestibilidade dos nutrientes e parâmetros ruminais em bovinos alimentados com silagem de capim-mombaça

Avaliaram-se o consumo, a digestibilidade aparente total e parcial dos nutrientes, o pH e a concentração de amônia ruminal em bovinos alimentados com silagem de capim-mombaça e concentrado nas seguintes proporções: 80:20, 65:35, 50:50 e 35:65, com base na matéria seca. Foram utilizados quatro animais Holandês x Zebu, com peso corporal médio inicial de 229kg, canulados no rúmen e abomaso, e distribuídos em quadrado latino 4x4. Os consumos de matéria seca (MS), matéria orgânica (MO), proteína bruta (PB), extrato etéreo (EE) e carboidratos totais (CHOT), expressos em kg/dia, e a digestibilidade parcial dos carboidratos não fibrosos (CNF) apresentaram comportamento linear crescente, com resposta platô nos níveis de concentrado de 54,1; 54,8; 52,9; 62,2; 55,2 e 52,7%. O consumo dos demais nutrientes, exceto da fibra em detergente neutro (FDN), e as digestibilidades aparente total de MS, MO e CNF e a parcial de MO aumentaram linearmente com o incremento do concentrado nas dietas. Não foram encontradas diferenças no consumo e nas digestibilidades aparente total e parcial da FDN. Para concentração de amônia e pH ruminal, observou-se efeito quadrático de tempo de amostragem, com valores máximos de 24,76mg/dL e 6,53 em 2,8 e 3,5 horas após a alimentação, respectivamente.

Utilização de probiótico e de lactulose no controle de hiperamonemia causada por desvio vascular portossistêmico congênito em um cão

O desvio vascular portossistêmico pode ser congênito ou adquirido nos cães. A enfermidade pode levar a alterações neurológicas decorrentes de encefalopatia hepática e a hiperamonenia é um dos mecanismos implicados na fisiopatologia deste quadro. O tratamento clínico visa a reduzir os níveis séricos de amônia com o uso de antibióticos e lactulose. em humanos com hepatopatias, os probióticos podem ser utilizados para reduzir a hiperamonemia. A resposta clínica e laboratorial de um cão com desvio vascular portossistêmico foi demonstrada com a utilização de lactulose e de probiótico, isoladamente e associados, sendo que a melhor evolução foi obtida na terapia conjunta.