Este trabalho apresenta o processo para obtenção de partículas de sílica amino-funcionalizadas contendo complexos de TR3+ utilizando os métodos de Stöber e por micro-ondas. Os espectros de absorção no infravermelho das partículas TR-BTC-Si preparadas pelo método de micro-ondas exibiram bandas de absorção atribuídas aos modos vibracionais dos complexos TR-BTC e da rede de sílica, indicando a incorporação destes complexos na matriz SiO2. Por outro lado, os complexos Eu-(β-dicetonatos) preparados pelo método Stöber mostraram apenas as bandas atribuídas à estrutura da rede de sílica, devido à dupla camada de revestimento de sílica. As morfologias das partículas de sílica amino-funcionalizadas contendo complexos de TR3+ foram visualizadas usando a técnica MEV. As diferenças nas morfologias entre o complexo precursor e o material amino-funcionalizado pode ser atribuído a presença da sílica na superfície do material. Além do mais, o método da ninidrina indicou a presença de grupos amina (-NH2) na superfície destes materiais. Os espectros de emissão dos materiais funcionalizados com os complexos de Eu3+ e Tb3+ apresentaram as bandas de emissão da transição intraconfiguracional dos íons Eu3+ (5D0→7FJ, J = 0-6) e Tb3+ (5D4→7FJ, J = 6-0), exibindo cores características de emissão vermelha e verde, respectivamente. É observado um decréscimo nos valores dos parâmetros Ω2 dos materiais Eu-(β-dicetonato)-Si e Eu-BTC-Si comparados com os respectivos complexos, devido a diminuição da intensidade da transição 5D0→7F2, indicando um maior caráter centrossimétrico. Conseqüentemente, os íons Eu3+ nos materiais com sílica estão em um ambiente químico menos polarizável do que nos complexos, sugerindo uma menor contribuição do mecanismo de acoplamento dinâmico. Os altos valores dos Ω4 para os sistemas com sílica Eu-(&#946-dicetonato)-Si e Eu-BTC-Si comparados com os valores de Ω2 reflete a intensidade extremamente alta da transição 5D0→7F4 observada nos espectros de emissão. Este resultado corrobora com o maior caráter centrossimétrico e evidencia a incorporação dos complexos de Eu3+ na rede de sílica. Foi realizado um fluoroimunoensaio usando os compostos amino-funcionalizados, que mostraram uma luminescência e propriedades físico-químicas eficientes para atuarem como marcadores biológicos. O marcador óptico foi conjugado com o anticorpo anti-oxLDL, que se liga a um suporte específico com o antígeno oxLDL. Portanto, estes materiais são candidatos promissores para conjugação molecular em clínicas de diagnóstico. / This work presents the process to obtain amino-functionalized silica particles containing complexes of trivalent rare earth ions (RE3+) using Stöber and microwave methods. Infrared spectra of the TR-BTC-Si particles prepared by microwave method exhibited absorption bands assigned to the vibrational modes of the TR-BTC complexes and silica network, indicating that the complexes have been incorporated in the SiO2 matrix. However, due to double coating of the silica network, the IR spectra of the Eu-(β-diketonates) complexes prepared by Stöber method showed only bands assigned to the silica structure. The morphologies of the amino-functionalized silica particles containing RE3+ complexes were examined using SEM technique. The difference in morphology between the complex precursor and amino-functionalized material can be attributed to the silica network on the material surface. Besides, the ninhydrin method confirmed the presence of amine groups (-NH2) in the functionalized materials. The emission spectra of the functionalized materials containing Eu3+ and Tb3+ complexes showed the emission bands originated from the intraconfigurational transitions of the Eu3+ (5D0→7FJ, J = 0-4) and Tb3+ (5D4→7FJ, J = 6-0), exhibiting red and green color emission, respectively. It is observed decreasing values of experimental intensity parameters (Ω2) of the Eu-(β-diketonate)-Si and Eu-BTC-Si materials when compared with the complex precursors, owing to the decreased intensity of the 5D0→7F2 transition, indicating a higher centrosymmetric character. As a result, the Eu3+ ions in silica materials are located in a chemical environment less polarizable than in the complexes, suggesting a smaller contribution of dynamic coupling mechanism. On the other hand, an abnormally high intensity of the 5D0→7F4 transition was observed, which is reflected by the high values of Ω4 of the silica systems, Eu-(β-diketonate)-Si and Eu-BTC-Si, compared with the Ω2 ones. These spectroscopic data corroborate with a higher centrosymmetric character, indicating the incorporation of the Eu3+ complexes in the silica network. A fluoroimmunoassay was developed using the amino-functionalized compounds that exhibit efficient luminescence and physical and chemical properties suitable for optical label. The biolabel was then chemically conjugated to anti-oxLDL antibody, which is linked in a specific support with oxLDL antigen. The result showed that it is a promising candidate for molecular conjugation in clinical diagnosis.

A indústria alimentícia utiliza variados materiais para embalagens, sendo o polietileno de baixa densidade linear (PELBD) um dos materiais de maior importância, por possuir características únicas e adequadas à produção de embalagens. A geração de espécies químicas em embalagens de alimentos vem sendo foco de estudos no mundo. Este controle de compostos é denominado como estudo de Substâncias Não Intencionalmente Adicionadas (NIAS) e tem sua importância justificada pela preocupação com a saúde humana devido à capacidade de contaminação do alimento embalado. Para este estudo foram escolhidas duas resinas PELBD amplamente aplicadas na produção de embalagens alimentícias, analisadas na forma de pellets. As amostras foram nomeadas como PELBD1 e PELBD2 e analisadas antes e após exposição natural e acelerada (estufa a 50°C) de um, dois e três meses. Ambas apresentaram grande aumento no número de NIAS detectadas por Cromatografia Gasosa com detecção de Massas (GC-MS) após envelhecimentos, quando comparadas à resina virgem, chegando a 1100% em PELBD1 e 100% em PELBD2, com surgimento de substâncias oxigenadas e tóxicas. O aditivo antioxidante ativo foi sendo consumido e analisado via Cromatografia Líquida de Alta Eficiência (HPLC) ao longo das exposições, confirmando os efeitos do envelhecimento. Através do Infravermelho por transformada de Fourier (FTIR) foi verificada degradação inicial em PELBD1 exposto por três meses à estufa. Porém, até mesmo em períodos menores de exposição natural, a formação de grupos cromóforos foi comprovada pela análise de cor, onde houve pequeno e gradual aumento do amarelecimento e diminuição da brancura principalmente em PELBD1. Por Cromatografia de Permeação à Gel (GPC), as amostras apresentaram pequena tendência para diminuição de M̅z. Já nas análises de Reometria Rotacional com variação de Frequência (DSR), Índice de Fluidez (IF) e Calorimetria Exploratória Diferencial (DSC), foram observadas mínimas tendências de degradação. Pode-se concluir a partir destes resultados que a maior degradação e produção de NIAS ocorreram em ambiente acelerado. Esta pesquisa trouxe grandes contribuições para futuros trabalhos que envolvam o estudo de NIAS e suas condições de formação. / The food industry uses various packaging materials being linear low density polyethylene (LLDPE) one of the most important materials, have unique features suitable for the production and packaging. The generation of chemical species in food packages has been the focus of research in the world. This control compounds is referred to as study Non-Intentionally Added Substances (NIAS) and has its importance justified by concern human health because of capacity contamination the food packaging. For this study it was chosen two LLDPE resins widely applied in the production of food packaging, analyzed in the form of pellets. The samples were named as PELBD1 and PELBD2 and analyzed before and after natural and accelerated exposure (oven at 50°C) of a two and three months. Both showed huge increase in the number of NIAS detected by Gas Chromatography with Mass detection (GC-MS) after ageing, when compared to virgin resin, reaching of 1100% in PELBD1 and 100% in PELBD2 with the appearance of oxygen substances and toxic substances. The active antioxidant additive was being consumed and analyzed via High-Performance Liquid Chromatography (HPLC), during the exposures, confirming the effects of ageing. For Fourier Transform Infrared (FTIR) was observed in initial degradation PELBD1 exposed for three months in an oven. However, even at under natural exposure periods, the formation of chromophoric groups were confirmed by analysis of color where there was a slight and gradual increase in yellowing and brightness decreased mainly PELBD1. For the Gel Permeation Chromatography (GPC), the samples showed a slight tendency to decrease M̅z. Already in the analysis of Rheometry Rotational Varying Frequency (DSR), Melt Flow Index (MFI) and Differential Scanning Calorimetry (DSC), were observed minimum trends of degradation. It can concluded from these results that the greatest degradation and NIAS production occurred in an accelerated environment. This research has brought great contributions to future work involving the study of NIAS and their conditions of training.

The effects of oxidatively modified low density lipoprotein (oxLDL) on atherogenesis may be partly mediated by alterations in nitric oxide (NO) production by macrophages. A major goal of this study was to identify the lipid components in oxLDL modulating NO production. The effect of a water soluble antioxidants (N-acetylcysteine) and lipid soluble antioxidant (alpha-tocopherol) on NO production in macrophages was also determined. A second goal was to determine if the effects of oxLDL occurred at the transcriptional level. Human LDL was oxidized using an azo-initiator 2,2$\sp\prime$-azobis (2-amidinopropane) HCI (ABAP). OxLDL markedly decreased the production of NO in LPS stimulated RAW264.7 macrophages. This inhibition depended on the levels of LOOH formed in oxLDL and was not due to oxLDL cytotoxicity. In contrast, acetylated LDL (AcLDL) and native LDL showed only minor inhibition. Lipid hydroperoxides (LOOH) and lysophosphatidylcholine (lysoPC) are the primary products formed during LDL oxidation. 13-Hydroperoxyl octadecadienoic acid (13-HPODE) markedly inhibited NO production, whereas lysoPC showed only slight inhibition. Furthermore, the effects of 13-HPODE and lysoPC did not require their uptake in an AcLDL carrier. Pre-treatment of macrophages with alpha-tocopherol attenuated the inhibition due to oxLDL. Similarly, pre-treatment with N-acetylcysteine attenuated the inhibition caused by oxLDL or 13-HPODE. OxLDL was found to decrease iNOS protein and mRNA levels in RAW264.7 macrophages induced by LPS. The activation of NF-$\kappa$B was slightly suppressed after 45 minutes of treatment. 13-HPODE showed much stronger reduction of iNOS protein levels than lysoPC. These results suggest that oxLDL may inhibit NO production in macrophages at transcriptional level. 13-HPODE is likely to be the most important lipid component in oxLDL for the inhibitory effect. Antioxidants were found to preserve NO production in macrophages treated with either oxLDL or 13-HPODE. The physiological consequences of decreased NO production in macrophages caused by oxLDL are discussed with respect to atherosclerosis.

The vector-borne protozoan Leishmania spp. cause the spectrum of disease known as leishmaniasis in human and animal hosts. The most common manifestations of leishmaniasis are the chronic, ulcerative skin disease cutaneous leishmaniasis (CL), and the more serious visceral leishmaniasis (VL) in which parasites take up residence in internal organs, causing death if not treated. The role of neutrophils (PMNs) in the immune response to CL and VL is unclear. It is s generally thought that PMNs are only a short-lived effector cell, and have been disregarded as playing a role in chronic Leishmania spp. infection. As both CL and VL are diseases characterized by increased inflammatory immune mediators, we hypothesized that PMNs from human or animal models of chronic leishmaniasis would display different properties from PMNs from healthy controls. We found in a subset of CL and VL patients circulating PMNs expressing HLA-DR, the human form of MHC class II, a molecule thought to be restricted primarily to professional antigen cells. When we examined PMNs recruited to CL skin lesions in human patients, or similar lesions in experimental murine model of CL, we found significantly increased MHC class II+ PMNs. Circulating HLA-DR+ PMNs also expressed the co-stimulatory molecules CD80, CD86 and CD40. While this suggested an antigen-presenting cell-like phenotype by these HLA-DR+ PMNs, compared to conventional HLA-DR- PMNs, HLA-DR+ PMNs showed not only a neutrophil-like appearance and function, but in fact increased activation, degranulation, intracellular MPO and phagocytosis of parasites and zymosan particles. Incubation of healthy control whole blood with inflammatory cytokines resulted in increased HLA-DR+ PMNs and the presence of hladrb1 mRNA, suggesting a connection between neutrophil “priming” and upregulation of HLA-DR. In addition to HLA-DR+ PMNs in CL patients, we also identified the presence of so-called “low-density” neutrophils (LD-PMNs). These neutrophils, which are enriched in low-density fractions following centrifugation of blood over a density gradient, are reported in numerous disease states, including cancer, HIV, and systemic lupus erythematosus. In some disease states, LD-PMN are reported to be immunosuppressive toward T cell activation and proliferation. However, LD-PMNs from leishmaniasis patients showed no evidence of immunosuppression. Additionally, we found that LD-PMNs show significantly increased surface expression of MHC class II, suggesting a heretofore unappreciated connection between these atypical neutrophil phenotypes. We also investigated the in vitro interactions with different Leishmania infantum life-stages, both those that cause acute infection (promastigotes) and amastigotes, which are found during chronic stages of the disease. We found that PMNs are readily infected by all L. infantum life-stages, but that amastigotes may have different methods of interacting with PMN surface receptors and are better equipped to avoid PMN anti-microbial responses. These data suggest that circulating PMNs in chronic leishmaniasis may have unique phenotypes and interact differently with the Leishmania spp. life-cycle present during chronic infection. Further investigation of the role of PMNs and atypical PMN phenotypes in chronic disease may help identify new immunomodulatory roles for this cell type.

Low-density parity-check (LDPC) codes provide excellent error correction performance and can approach the channel capacity, but their performance degrades significantly in the presence of burst noise. Bursts of errors occur in many common channels, including the magnetic recording and the wireless communications channels. Strategies such as interleaving have been developed to help compensate for bursts errors. These techniques do not exploit the correlations that can exist between the noise variance on observations in and out of the bursts. These differences can be exploited in calculations of prior probabilities to improve accuracy of soft information that is sent to the LDPC decoder. Effects of using different noise variances in the calculation of prior probabilities are investigated. Using the true variance of each observation improves performance. A novel burst detector utilizing the forward/backward algorithm is developed to determine the state of each observation, allowing the correct variance to be selected for each. Comparisons between this approach and existing techniques demonstrate improved performance. The approach is generalized and potential future research is discussed.

O desafio da gestão dos resíduos gerados pela produção e consumo de produtos sempre acompanhou a humanidade, revelando-se um problema quando se trata do seu descarte e destinação. No entanto, nos últimos anos verifica-se um agravamento deste problema, dado o volume e diversidade de resíduos gerados. Em especial, os resíduos poliméricos merecem bastante destaque pelo seu grande volume nos aterros sanitários e pela poluição causada em diversos ecossistemas. A reciclagem deste material é apontada como uma alternativa e auxílio na solução do problema. O presente estudo teve como objetivo o desenvolvimento de um método de reciclagem do polietileno de baixa densidade que envolve operações de processamento mecânico e tratamento térmico e químico do material. Para isto, blendas de resíduos de polietileno de baixa densidade (PEBD) e polipropileno (PP) com até 30 % em massa de PP foram preparadas com a incorporação de catalisadores do tipo zeólita ZSM-5 e Ziegler-Natta e submetidas ao tratamento térmico em condições controladas de temperatura e atmosfera de nitrogênio. Os resultados obtidos mostram a ação do catalisador zeólita ZSM- 5 como modificador da estrutura polimérica já na etapa de processamento termomecânico do material. Os catalisadores proporcionam mudanças consideráveis nas propriedades das blendas PEBD/PP, de acordo com as condições em que os ensaios são realizados. O tratamento de resíduos poliméricos em presença de catalisadores apresenta potencial para a reciclagem de resíduos poliméricos podendo gerar materiais reciclados com propriedades melhoradas. / The challenge for the waste management generated by the production and consume of products has always followed the Humankind, showing as a problem for discard and destination. However, in the last years an aggravation of this problem has been verified due to the volume and diversity of the waste produced. Particularly, the polymeric waste has a great prominence due to the large amount in landfills and pollution caused in several ecosystems. The polymeric recycling is indicated as an alternative for the problem. The aims of this study had been the development of a method for the recycling of the low-density polyethylene (LDPE) that involves mechanical processing operations and thermal-chemical treatment of the material. For this reason, blends of LDPE waste and polypropylene (PP) containing until 30 wt% of PP has been prepared with incorporation of zeolite ZSM-5 and Ziegler-Natta catalyst and submitted to thermal treatment under controlled conditions of temperature and nitrogen flow. The results presents the action of zeolite catalyst as modifier of the polymeric structure during step of the thermomechanical processing of the material. The catalysts have caused considerable changes on the properties of LDPE/PP blends, according to the experimental conditions. The treatment of polymeric waste in presence of catalyst shows potential for the recycling of polymeric materials and can generate recycled materials with improved properties.

The aim of this study was to investigate the distribution, density, health, condition, fertility, causes of mortality, home range size and tree preferences, of koalas in low density populations in the south of Sydney. This information was then used to make management recommendations; good management is needed because there is rapid human population growth and pressure for development of koala habitat in the Sydney region. State Environment Planning Policy 44(SEPP44) is New South Wales legislation that relates to developments affecting koala habitat. Problems in the application of SEPP44 in the Sydney region were found to exist, such as Sutherland Local Government Area (LGA) not being covered, and changes to this legislation are also recommended. / Doctor of Philosophy (PhD)

The aim of this study was to investigate the distribution, density, health, condition, fertility, causes of mortality, home range size and tree preferences, of koalas in low density populations in the south of Sydney. This information was then used to make management recommendations; good management is needed because there is rapid human population growth and pressure for development of koala habitat in the Sydney region. State Environment Planning Policy 44(SEPP44) is New South Wales legislation that relates to developments affecting koala habitat. Problems in the application of SEPP44 in the Sydney region were found to exist, such as Sutherland Local Government Area (LGA) not being covered, and changes to this legislation are also recommended. / Doctor of Philosophy (PhD)

Lysophosphatidic acid (LPA) is a potent bioactive lipid component of oxidized low density lipoproteins (oxLDL). High concentrations of LPA have been detected in human atherosclerotic plaques. Our data has shown that LPA highly induces smooth muscle cell (SMC) migration. Cyr61, a matricellular protein, which also accumulates in human atherosclerotic plaques, has been implicated in the injury-induced neointimal formation. Smooth muscle cell migration is a key event in the development of atherosclerosis, and it contributes to the progressive growth of atherosclerotic lesions. Data generated by this study demonstrate that LPA markedly induces Cyr61 expression in mouse aortic smooth muscle cells (MASMC). We hypothesized that LPA-induced matricellular Cyr61 mediates LPA-induced MASMC migration. To date, little is known about the relationship between LPA and Cyr61 in smooth muscle cells; the signaling pathway leading to LPA-induced Cyr61 is unknown. Furthermore, whether Cyr61 contributes to LPA-induced cell migration is unrevealed. Our study demonstrates that LPA, by binding to LPA1 receptor, activates the intracellular signaling pathway leading to the activation of PKCdelta which in turn contributes to the increased expression of Cyr61 in MASMCs. Interestingly, we found that after LPA-induced Cyr61 mRNA has been translated into its protein intracellularly, the de novo synthesized proteins promptly accumulate in the Golgi apparatus and then translocalize to the extracellular matrix. Importantly, our data reveal a novel LPA/Cyr61 pathway in controlling MASMC migration. Understanding the mechanism underlying LPA induction of Cyr61 provides new insight into pathogenesis of atherosclerosis.

This thesis presents a novel VLSI design of multi-code rate Low-Density Parity-Check code (LDPC) decoder for IEEE 802.16e standard. In order to support the different code rates adopted by the standard, this thesis proposes a programmable LDPC decoder architecture based on the edge-serial approach. This edge-serial architecture can perform the sequential check-node computation according to the internal sequence update commands. Any complex and irregular parity-check matrix can all be realized in the proposed architecture if the number of bit-nodes each check node connects does not exceed a certain bound. In addition to the high flexibility, this thesis also proposes several design optimization techniques suitable for the LDPC decoder. First, the designs of the LDPC decoders in the past all put more emphasis on the realization of check node function. This thesis instead applies a novel bit-node major approach which can lead to more compact design. Secondly, a fine-grain message update method is used which allows more rapid message passing such that the decoder can converge in less cycles. In addition, almost half of the message memory can be reduced. Furthermore, based on the bit-node major decoder design, the early termination scheme can be utilized to partially terminate the function of some bit nodes to reduce the decoding cycles. The other salient features also include the rescheduling of the message update order to allow the overlap of different decoding iterations in order to reduce effect of the possible message update hazard due to the long internal pipeline latency. Based on the proposed optimization methods, our experimental results show that the hardware cost can be reduced by 23.1% while the decoding cycles can be reduced by 27.4%. The proposed LDPC decoder architecture has been realized by using 0.18 µm technology with the total gate count of 316k. Our experimental shows that the proposed LDPC decoder can run up to 235 MHz and deliver the average of 116 Mbps throughput.