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

Caracterização de resíduo sólido formado em biodiesel de sebo bovino

Biodiesel production has increased over the last decade because of the benefits associated with this fuel, including renewability, domestic feedstock, lower toxicity, and biodegradability. From 2008, the use of beef tallow as a feedstock for biodiesel production in Brazil has increased in significance, representing the second largest source of biodiesel, after soybeans. However, the performance of biodiesel in cold weather conditions is worse than diesel because of deposition of insoluble at low temperatures, accelerating the plugging of fuel filters and injectors of the vehicle engine. Studies have been conducted on beef tallow biodiesel, mostly related to the properties of thermal and oxidative stability. However, few studies have described the nature of the precipitate formed and its influence on product quality. Research suggests that the cause of deposition is related to the nature of saturated esters and monoacylglycerols as inducing agents. This study monitored the levels of mono-, diand triacylglycerols, the oxidation stability and the cold filter plugging point (CFPP) in beef tallow biodiesel samples from two commercial producers in Brazil for a period of twelve months. Filtered precipitates were analyzed by comparative techniques of GCFID, HPLC-UV/VIS, HPLC-MS-IT-TOF and TG to verify the nature, using monopalmitin and monostearin as reference standards. The formation of precipitate reduced the levels of monoacylglycerols in the beef tallow biodiesel. GC-FID and LCMS- IT-TOF results confirmed the nature of the deposit as saturated monoacylglycerols, predominantly monostearin and monopalmitin as the second major component. Moreover the TG analysis of the residue indicated similar thermal decomposition of the reference standards. The precipitate did not affect the oxidation stability of beef tallow biodiesel and the CFPP characteristic of blends up B60. However, the presence of iron reduced significantly the oxidation stability of biodiesel

Caracterização de resíduo sólido formado em biodiesel de sebo bovino

Biodiesel production has increased over the last decade because of the benefits associated with this fuel, including renewability, domestic feedstock, lower toxicity, and biodegradability. From 2008, the use of beef tallow as a feedstock for biodiesel production in Brazil has increased in significance, representing the second largest source of biodiesel, after soybeans. However, the performance of biodiesel in cold weather conditions is worse than diesel because of deposition of insoluble at low temperatures, accelerating the plugging of fuel filters and injectors of the vehicle engine. Studies have been conducted on beef tallow biodiesel, mostly related to the properties of thermal and oxidative stability. However, few studies have described the nature of the precipitate formed and its influence on product quality. Research suggests that the cause of deposition is related to the nature of saturated esters and monoacylglycerols as inducing agents. This study monitored the levels of mono-, diand triacylglycerols, the oxidation stability and the cold filter plugging point (CFPP) in beef tallow biodiesel samples from two commercial producers in Brazil for a period of twelve months. Filtered precipitates were analyzed by comparative techniques of GCFID, HPLC-UV/VIS, HPLC-MS-IT-TOF and TG to verify the nature, using monopalmitin and monostearin as reference standards. The formation of precipitate reduced the levels of monoacylglycerols in the beef tallow biodiesel. GC-FID and LCMS- IT-TOF results confirmed the nature of the deposit as saturated monoacylglycerols, predominantly monostearin and monopalmitin as the second major component. Moreover the TG analysis of the residue indicated similar thermal decomposition of the reference standards. The precipitate did not affect the oxidation stability of beef tallow biodiesel and the CFPP characteristic of blends up B60. However, the presence of iron reduced significantly the oxidation stability of biodiesel

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

The effects of intrathecal administration of betamethasone over the dogs' spinal cord and meninges

OBJETIVO: Determinar possíveis alterações clínicas e histológicas determinadas pela administração da betametasona no espaço subaracnóideo de cães. MÉTODOS: Vinte e um cães foram incluídos no estudo de forma aleatória e encoberta. Depois de anestesiados, os cães foram submetidos a punção subaracóidea com injeção de 1 ml da solução sorteada. Os animais receberam solução salina 0,9% em G1, betametasona na dose de 1,75 mg em G2 e betametasona na dose de 3,5 mg em G3. Todos os animais foram mantidos em observação clínica por 21 dias, sendo posteriormente sacrificados. Porções da medula espinhal e sacral foram removidas para análise histológica por microscopia óptica. RESULTADOS: Não foram detectadas alterações clínicas em quaisquer dos animais incluídos no estudo. da mesma forma, nenhum animal do G1 apresentou alterações histológicas. Infiltração inflamatória foi observada em dois cães, um do G2 e outro e G3. No cão do G2 onde a infiltração inflamatória foi observada ocorreu, conjuntamente, hemorragia e necrose. em dois cães, um de G2 e outro de G3, observou-se discreta fibrose e espessamento da aracnóide, sendo focal em um e difusa no outro. CONCLUSÃO: A administração subaracnóidea de betametasona determinou alterações histológicas em medula e meninges de alguns dos cães envolvidos no estudo.

Injeção intravascular acidental de ropivacaína a 0,5% durante a realização de anestesia peridural torácica: relato de casos

JUSTIFICATIVA E OBJETIVOS: A ropivacaína foi introduzida na prática clínica há pouco mais de dez anos, associando-se a baixo risco de complicações do sistema nervoso central e cardiovascular. O objetivo destes relatos é apresentar um caso de parada cardíaca e outro de toxicidade neurológica, após injeção intravascular acidental da ropivacaína, durante a realização de anestesias peridurais. RELATO DOS CASOS: Trata-se de duas pacientes submetidas a cirurgias plásticas estéticas sob anestesia peridural torácica com ropivacaína a 0,5%. Durante a realização da técnica, uma delas apresentou parada cardíaca em assistolia e a outra, toxicidade neurológica. Prontamente atendidas, ambas apresentaram rápida recuperação, tendo sido possível a realização dos respectivos atos cirúrgicos. CONCLUSÕES: O reconhecimento e o tratamento rápidos da injeção intravascular acidental, bem como as características farmacológicas da ropivacaína foram decisivos, em ambos os casos, na boa recuperação das pacientes.

Efeitos adversos do sufentanil associado ao anestésico local pelas vias subaracnóidea e peridural em pacientes submetidas à analgesia de parto

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

Revitalização do Rio Golandim (RN/Brasil) após décadas de contaminação por efluentes industriais e domésticos: este rio está recuperado?

Environmental pollution causes the loss of the quality of aquatic resources and also affects the health of human beings. The Golandim River is located in São Gonçalo do Amarante (RN Brazil) and had its water recovered seven years ago by measurements of parameters of the water s quality analyses physicochemistry, microbiological and heavy metals. However, it is not well established if this river is truly recovered, so this study provides a wide knowledge about the quality of these waters. Therefore, this investigation was accomplished by assays of ecotoxicology utilizing Ceriodaphnia dubia and of genotoxicity of the river s water using a biomarker Tradescantia Pallida (Trad-MCN). In set, it carried through a study of environmental perception through questionnaires that approached questions related to the profile of the interviewed one, knowledge on the environment and of the river Golandim with the community that lives in the neighborhoods of the river to diagnosis as they perceive the environment where live and its problems. The assays of the water had been carried out by collecting samples in three different sites of the Golandim River. They were collected between the periods of December 2010 (dry season in the northeast of Brazil) and July 2011 (rainy season in the northeast of). The analysis of the data allowed observing that the majority of the inhabitants are adult and presents a global vision of what it is part of the environment, the majority mentions the pollution of the river as one of the problems of the city, considering it serious. The ecotoxicology assay showed that there was not acute toxicity in all three samples collected. Meanwhile, all these three samples demonstrated significant chronic toxicity. The results from the Trad-MCN assay presented an increase in the frequency of micronucleus in one of the sites analyzed (S3) (p<0.01), in both seasons collected. On the other hand, the sites S1 and S2 did not presented a significant increase of micronucleus using this bioassay. The analyses of chemicals detected an increase in the levels of some metals, in different seasons and samples, which can be associates with some compounds found in urban and industrial areas. On the other hand, the physicochemistries parameters demonstrated that the Golandim River is recouped, when compared with the values presented at the CONAMA s legislation. However, these results indicate the presence of compounds capable of inducing chromosomal mutation in plants. On the other hand, the parameters physicistchemistries demonstrate that the river Golandim is if recouping, since when compares the values observed with the legislation of the CONAMA. All these results point to the fact that the Trad-MCN assay was sensitive and efficient biomarker for chromosomal instability and the C. dubia ecotoxicology assay was as though an efficient biomarker of toxicity of water s quality. The results from Trad-MCN associated with the ecotoxicology demonstrates that these analyses are important for environmental monitoring, once the first bioassay described above indicates alterations at the standards of cells and the other one indicates alterations at the standards of organisms. This study alerts for the necessity to carry out biological assays for the analyses of the water s quality

Avaliação do potencial mutagênico da água do açude de Lucrécia (RN- Brasil): um enfoque na relação saúde e ambiente

The water quality of many reservoirs in the world has been reduced due to percolation of contaminants to water, which can have natural or anthropogenic origin, increasing the level of genotoxic compounds in aquatic ecosystems. This fact has contributed to the reduction of environmental quality, and commitment the health of living beings that inhabit these ecosystems, including the human population. In this backdrop of reduced water quality, is the Lucrecia dam, which is a major surface water reservoirs by volume of semi-arid region of Rio Grande do Norte, and that has shown contamination by heavy metals, cyanobacteria toxic and the natural presence of Radon. The population that use this source has been showing high rates of cancer, popularly associated with the consumption of this water, with a prevalence about three times higher compared to the whole state of Rio Grande do Norte. Based on this, the present study aimed to evaluate the mutagenic potencial of surface water from the Lucrecia dam, using the Micronucleus Test in Tradescantia pallida (Trad-MN) and in human peripheral blood lymphocytes (CBMN) assay, as well as identify the concentrations of some heavy metals in this water. Water samples were collected on a dry season and a rainy season, in two distinct points. Moreover, in order to bring a completely view about the relationship of man-health-environment in this local, through the knowledge of knowing / acting environmental from residents of Lucrecia, and the use and perceptions they have about the dam of your city, a study of Environmental Perception was carried out with local residents. The results obtained for the both micronucleus test, showed significant results for the three points analyzed. The strongest mutagenic effect was observed in the dry season for both assays. Chemical analyses detected an increase of heavy metal levels in different points and season above the maximum allowed by legislation. Regarding the study of Environmental Perception with local residents, it was observed the knowledge of the environment that the residents have, as well as the strong ties and perceptions with the dam of the city. Thus, the combination of these two aspects (the genetic toxicity tests conducted in the dam together with analysis of environmental perception with the residents of Lucrecia) allowed to draw a more complete diagnosis on the local situation

Horticultura no baixo curso do Rio Doce, zona norte do Natal/RN: avaliação da qualidade da água por meio de ensaios ecotoxicológicos

The research is developed in areas of horticulture in the city of Natal, in the neighborhoods of Lagoa Azul, Pajuçara and Redinha, along the Doce River, border area with Extremoz city, Rio Grande do Norte State. The region of the fluvial plain of Doce River is located in an Environmental Protection Zone (ZPA-9). This is one of the ZPA which is not under the regulatory marks and there are several environmental problems caused by use and land occupation, featuring an evident disregard of environmental laws and whose protection is hindered by the lack of specific legal mechanisms. This study aims to provide an overview of the use of pesticides in the lower course of the Doce River, in Natal, Rio Grande do Norte, and to assess environmental degradation in the area through chronic toxicity tests using the microcrustaceous Ceriodaphnia dubia Richard 1894 (Cladocera, Crustacea) as test organism. Visits were made to the area in 2009 and 2010. To obtain information a diagnosis of the local situation was accomplished based on personal observation and non-participatory photographic record, with the aim of assessing the environmental characteristics, population diversity and work processes of horticulturists. During the visits four different points of the Doce River were chosen to collect water for ecotoxicological tests and survey of physico-chemical parameters (dissolved oxygen, pH, chloride, turbidity, conductivity and temperature), which were measured in the field using Multiparameter Probe (TROLL 9500). The adverse effects of pesticide use in the lower course of the Doce River is a major problem for both the environmental and human health, since many of the substances and active principles that enter in the composition of the products are synthesized molecules whose effects can only be evaluated through different studies on their actions and behavior at short, medium or long term

Avaliação do potencial tóxico de águas oriundas de irrigação agrícola no Baixo-Açu/RN: um problema socioambiental

For many decades the problematic raised about the indiscriminate use of pesticides in modern agriculture has incited the interest of many researchers to discover the effects caused by such products in the environment and consequently in the life of the ones which use that products (farmers) and those people who live in places next to the agricultural areas. Facing these facts, this research had the intention of comprehend the environmental perception of habitants of the Distrito Irrigado do Baixo-Açu (DIBA), located in the semiarid of Rio Grande do Norte, by using agro toxics and its possible environmental effects, as well as evaluate the levels of toxicity of waters from agricultural runoff in this region by using eco-toxicological exams with Ceriodaphnia silvestii. Were done 86 interviews with dwellers and farmers from DIBA. With the results reached in the evaluation of the interviews it was possible to identify that one of major problems is the inappropriate discard of empty packs of the pesticides used at that place. The samples collected for eco-toxicological evaluation showed a variation in its toxicity, once that the point of collect which receives waters from different cultures presented in four out of five samples toxicity for the tested species. Therefore, it concludes that the indiscriminate use of pesticides agricultural practice presented a potential to pollute to the irrigation waters, and the absence of elucidation by the farmers about the manipulation of these products contribute to the risk of environmental contamination and the possible decrease of the quality of life of the dwellers of the region

Metais pesados no caranguejo Ucides cordatus (Linnaeus, 1763) e ecotoxicologia de sedimentos do estuario dos Rios Jundiai e Potengi - RN

This study is conducted in the estuary of the rivers Jundiaí and Potengi, one of the most important estuaries of Rio Grande do Norte, which suffers a strong anthropogenic influence from neighboring cities. According to Resolution 344/2005 environments that have high concentrations of metals such as arsenic, cadmium, lead and mercury need ecotoxicological tests. This study aims to evaluate the heavy metals contamination in the estuary through analysis of sediment collected at four points distributed from Macaíba to Natal city, and in the crab Uçá, Ucides cordatus. The study aims also to evaluate the effects of sediment toxicity in the tests organisms Leptocheirus plumulosus. To obtain data about the concentrations of heavy metals in the environment, sediments were collected in January and May 2011 and crab Uçá was collected in June 2011. On the other hand the monitoring was carried out through toxicological tests with sediment collected from July to October 2011. During the collection of sediment samples the physico-chemical parameters of water (dissolved oxygen, pH, chloride, turbidity, conductivity and temperature) were measured by using multi-parametric probe (TROLL 9500). It was possible to identify contamination by metals such as lead, cadmium, arsenic and copper both in the sediment and in the Uçá crab, which characterizes that the consumption of this crustacean may be a risk to human health. Once the concentrations of metals were identified, toxicology tests were performed and revealed toxic effect to organisms in at least one of the four months studied. Point 2 was classified as toxic in three of the four months studied . The heavy metal contamination is a risk to the environment, to aquatic organisms and to the community which survives of resources taken from the environment

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.

Comparative study of the topical effectiveness of the andiroba oil (Carapa guianensis) and DEET 50% as repellent for Aedes sp

O DEET (N, N-dietil-3-metilbenzamida) é hoje o repelente mais efetivo disponível, porém, seu uso pode apresentar importantes efeitos colaterais tópicos e sistêmicos. Alguns compostos botânicos, como a Andiroba (Carapa guianensis), têm demonstrado propriedades repelentes a um baixo custo e baixa toxicidade. Quatro voluntários hígidos submeteram seus antebraços recobertos com óleo de Andiroba a 100%, DEET 50% (controle positivo), óleo de soja refinado, óleo de Andiroba 15% e na ausência de produtos (controles negativos), diretamente a picadas de fêmeas saudáveis de Aedes sp. Foram aferidos os tempos da primeira e terceira picadas. Os resultados mostraram que a mediana da primeira picada nos antebraços sem produto foi 17.5s e a terceira picada, 40.0s. No óleo de soja, as picadas ocorreram em 60.0s e 101.5s. No óleo de Andiroba 100%, em 56.0s e 142.5s. Com Andiroba 15%, em 63.0s e 97.5s. Usando DEET 50% não houve picadas após 3600s na maioria dos experimentos (p < 0.001 Wilcoxon). O óleo de Andiroba 100% comparado ao óleo de soja, antebraço sem produto e óleo de Andiroba 15%, mostrou discreta superioridade (p < 0.001 Wilcoxon). Concluímos que o óleo puro de Andiroba apresenta efeito repelente discreto contra picada de Aedes sp., sendo significativamente inferior ao DEET 50%.

O uso de implantes orbitários de polietileno granulado de ultra-alto peso molecular no reparo de cavidades anoftálmicas

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