La thèse a soulevé deux défis dans l’analyse des métaux dans le riz : (i) un dosage multiélémentaire dans le but de la classification du riz selon l’origine géographique, et (ii) la spéciation du sélénium, élément essentiel dans la nutrition, dans le but de l’identification des cibles moléculaires de son assimilation et stockage. Une méthode d’analyse multiélémentaire par l’ICP MS combinée avec des techniques chimiométriques a été proposée comme outil pour la discrimination des riz selon leurs origines géographiques. Les concentrations des 21 éléments ont été analysées par le diagramme en radar, l’analyse en composantes principales, et l’analyse discriminante linéaire. Le riz thaï (riz jasmin) a pu être discriminé des riz étrangers. De plus, l’analyse discriminante a permis de de différencier les riz produits dans les différentes régions de Thaïlande. L’approche de protéomique assistée par l’ICP MS a permis l’identification d’une douzaine de protéines accumulant préférentiellement le sélénium sous forme de sélénomethionine et de sélénocystéine (en proportion 2:1). / The PhD work is focused on two major analytical chemistry challenges concerning rice characterization: (i) the geographical origin classification of rice based on multi-element fingerprinting and (ii) speciation of selenium with the goal of the identification of molecular target of it assimilation and storage in rice. The methods based on the multi-element fingerprinting by inductively coupled plasma mass spectrometry (ICP-MS) in combination with multivariate statistical techniques were developed and validated as tools for authentication of rice. Twenty-one key variables were assessed by a radar plot technique and multivariate data analysis, including principal component analysis (PCA) and discriminant analysis (DA) enabling classification according to geographical origin. Thai jasmine rice could be clearly differentiated from foreign rice samples. In addition, the DA could be used to classify Thai jasmine rice obtained from different regions in Thailand. In the second part of the project, an analytical ICP-MS-assisted proteomic method was developed for the identification of Se-containing proteins in rice. Selenium was found to be present as both selenomethionine (SeMet) and selenocysteine (SeCys) in a dozen of rice proteins with the Se/S substitution ratio two times higher for SeMet than that for SeCys.

Orientador: Joel Mesa Hormaza / Resumo: A úlcera péptica é provocada pelo desequilíbrio entre fatores lesivos e protetores das mucosas gástrica e duodenal, em consequência a fatores endógenos ou exógenos aos tecidos. Para seu tratamento, algumas plantas são popularmente empregadas e demonstram eficácia semelhante ou superior aos fármacos geralmente utilizados, ocasionando menores efeitos adversos. Apesar de várias pesquisas na área, a compreensão do mecanismo gastroprotetor dos compostos fitoterápicos ainda não é completa. Assim, com o objetivo de contribuir para a compreensão da ação farmacológica dos extratos de três plantas medicinais (Alchornea glandulosa, Davilla elliptica e Davilla nitida), foi realizada uma análise da distribuição elementar dos constituintes das amostras de mucosas gástricas de ratos tratados com os extratos vegetais e que tiveram úlceras gástricas induzidas por álcool ou por droga anti-inflamatória não-esteroidal (DAINE). O experimento foi realizado no Laboratório Nacional de Luz Síncrotron (LNLS) e permitiu a análise dos elementos Cl, Ca, Mn, Fe, Cu e Zn que contem relação com a formação ou neutralização das úlceras pépticas. De acordo com os mapas da distribuição dos elementos, foi possível detectar alta concentração de Fe, Cu e Zn no interior da lesão das amostras de úlcera induzida por DAINE, e de Cu, Zn e Cl no interior da lesão das amostras induzidas por álcool. Nas amostras de úlcera induzida por DAINE e tratadas com Alchornea glandulosa, as concentrações de Ca, Cu e Fe aumentaram. N... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The peptic ulcer is caused by the imbalance between harmful and protective factors of the gastric and duodenal mucosa, as a consequence of factors endogenous or exogenous to the tissues. For its treatment, some plants are popularly employed and demonstrate efficacy akin or superior to the drugs normally used, leading to less adverse effects. Although much research has been conducted in the field, the understanding of the gastroprotective mechanism of phytotherapic compounds is still not complete. Therefore, aiming to advance the understanding of the pharmacological action of the extracts of three medicinal plants (Alchornea glandulosa, Davilla elliptica e Davilla nitida), we conducted an analysis of the elemental distribution of constituents within samples of gastric mucosa from rats treated with phytoterapic extracts and affected with peptic ulcers induced by alcohol or nonsteroidal anti-inflammatory drugs (NSAIDs). The experiment was performed at the Brazilian Synchrotron Light Laboratory (LNLS) and allowed for the analysis of the elements Cl, Ca, Mn, Fe, Cu and Zn that are connected to peptic ulcers development or inhibition. According to the elemental distribution maps, it was possible to detect high concentrations of Fe, Cu and Zn inside the lesion from the NSAID-induced ulcer samples, and of Cu, Zn and Cl inside the lesion from the alcohol-induced ulcer samples. In NSAID-induced ulcer samples treated with Alchornea glandulosa, Ca, Cu and Fe concentrations were augmented... (Complete abstract click electronic access below) / Doutor

Made available in DSpace on 2016-08-10T10:55:44Z (GMT). No. of bitstreams: 1 Aurelio de Melo Barbosa.pdf: 8372928 bytes, checksum: 34ed59e6bd218f99a1d12f2d2abdaa9e (MD5) Previous issue date: 2009-03-30 / Water, essential for life, has a direct influence on health, quality of life and development of mankind. However, due to natural and human causes, water may suffer contamination from various species, especially for chemical elements. Thus, this paper appears the results of a study of multi-elemental chemical analysis of samples of treated water collected in Water Treatment Plants of twenty-two cities of South Region of Goias State. It was also exposes data on sanitation and hospital morbidity and mortality of the study area. It was found two geochemical associations (SO4-Cl-Zn-Mn and Ca-Sr-Mg), that were presented in maps of distribution of each element geochemistry. Also it was found anomalous concentrations above the maximum permitted values of nitrate in samples of Quirinópolis and Morrinhos, and lead in the sample of Cromínia, with possible impact on the morbidity and mortality of these municipalities. / A água, essencial para a vida, tem influência direta sobre a saúde, qualidade de vida e desenvolvimento do ser humano. Entretanto, devido a causas naturais e antrópicas, a água pode sofrer contaminação de várias espécies, especialmente por elementos químicos. Assim, realizou-se um estudo de análise química multielementar de amostras de água tratada colhidas em Estações de Tratamento de Água de vinte e dois municípios da Mesorregião Sul Goiano. Também foram coletados dados sobre saneamento básico e morbidade hospitalar e mortalidade da área de estudo. Como resultado foram encontradas duas associações geoquímicas (Cl-Zn-SO4-Mn e Ca-Sr-Mg), sendo apresentados os mapas de distribuição geoquímica de cada elemento. Também descobriu-se concentrações anômalas, acima dos Valores Máximos Permitidos, de nitrato nas amostras de Quirinópolis e Morrinhos, e de chumbo na amostra de Cromínia, com possível impacto sobre a morbimortalidade dos referidos municípios.

[pt] A busca de níveis superiores de qualidade, tempo e competitividade é uma preocupação constante das agências econômicas e no setor agro - alimentar não poderia ser diferente. Um crescente número de pesquisas tem sido publicado detalhando o uso de técnicas analíticas para a determinação do conteúdo mineral, razões isotópicas ou de ambos como descritores geográficos de diferentes produtos agrícolas desde alimentos frescos até produtos processados. A pesquisa de vinhos no Brasil ainda é muito restrita aos pólos produtores de vinhos do país. E, a maior parte dos trabalhos tem como o objetivo a análise de parâmetros clássicos de controle de qualidade, sendo recente em nosso país a pesquisa envolvendo o desenvolvimento e/ou aplicações de metodologias que possam caracterizar o vinho e sua região produtora. Técnicas espectrométricas, como a ICP-OES, ICP-MS, são as mais utilizadas para este propósito e, foram utilizadas neste trabalho. Pela primeira vez o estudo das razões isotópicas de boro e chumbo foi aplicado aos vinhos brasileiros. A análise e classificação dos componentes principais (PCCA) e a análise de agrupamentos (CA), foram utilizadas no processamento dos dados. As regiões Sul e Nordeste puderam ser definidas utilizando tanto os dados da caracterização inorgânica quanto os isotópicos, mas não o suficiente para se definir as regiões produtoras de vinhos do Rio Grande do Sul, em especial o Vale dos Vinhedos. Ficou claro neste trabalho que o emprego da estatística multivariada aos dados obtidos através das determinações inorgânicas e isotópicas é uma poderosa ferramenta analítica. / [en] The search for higher levels of quality, time and competitiveness is a constant concern of economic agencies and agro - food could not be different. A growing body of research has been published detailing the use of analytical techniques for determining the mineral content, isotopic ratios or both as geographical descriptors of different agricultural products from fresh food to processed products. A search of wines in Brazil is still very restricted to the poles wine producers in the country. And, most of the work has as objective the analysis of classical parameters of quality control, and recent research in our country involving the development and / or application of methodologies that characterize the wine and its producing region. Spectrometric techniques such as ICP-OES, ICP-MS, are the most used for this purpose and were used in this study. For the first time the study of the isotopic ratios of lead and boron was applied to the Brazilian wines. The analysis and classification of the major components (PCCA) and cluster analysis (CA) were used for data processing. The South and Northeast could be identified using data from both inorganic as the isotopic characterization, but not enough to define the wine producing regions of Rio Grande do Sul, particularly the Valley of the Vineyards. It became clear in this study that the use of multivariate statistical data obtained through the inorganic and isotopic determinations is a powerful analytical tool.

In this thesis natural science is combined with environmental psychology in order to determine how deforestation and subsequent agricultural expansion in the Peruvian highland jungle has affected the natural environment and rural livelihoods. This region is part of one of the most biodiverse areas on Earth and is also exposed to high pressure from deforestation that threatens the ecosystems as well as the well-being of local populations. The problem stretches beyond the upper Amazon since the region constitutes headwaters to theAmazon Riverand is part of the most important forest ecosystem of the world. This study evaluates the relative controls of human induced land-cover change and natural factors on the chemical status of soils, stream waters, and sediments, mainly through a spatial sampling design. The field work was located to two adjacent river basins underlain by sedimentary rocks. Streams of 48 independent sub-basins, the two main rivers, 80 upland soil sites (weakly developed soils on sandstone and siltstone) and four vertical profiles of floodplain sediments were sampled and analysed for major and trace elements, including nutrients and potentially toxic metals. Further, perceptions of environmental changes were investigated through a combination of quantitative and qualitative interview data collected from 51 smallholder farmers. Soils of primary forests were found to be chemically similar to those of regenerated forests and agricultural land-covers (pastures and coffee plantations), and differences in chemical concentrations between streams draining areas to varying degrees covered by forest were assigned to natural variability. In addition, the chemical composition of alluvial deposits was similar in the two drainage basins despite a substantial difference in exploitation degree (30 % versus 70 % cleared from forest). Thus, no evidence was found of long-term changes in the geochemistry of the Subandean river basins as a result of the conversion of primary forest to agricultural land-uses. The farmers, however, perceived an overall increase in environmental degradation as well as a change towards drier and warmer climatic conditions. The climate change was reported to be the main factor responsible for a negative trend in life quality (rural livelihoods). The results may be used in the work of identifying priorities and key factors necessary for environmental and socioeconomic sustainability in the upper Amazon. / En esta tesis se combina la ciencia natural con la psicología ambiental con el fin de determinar como la ampliación de la frontera agrícola ha afectado el medio ambiente y los medios de vida en la selva alta del Perú. Esta región forma parte de una de las zonas con mayor biodiversidad en el planeta y a su vez está expuesta a una alta presión de la deforestación que amenaza a los ecosistemas, así como el bienestar de la población en esta zona. Así mismo, este problema se hace sentir mas allá de la selva alta ya que esta zona forma parte de las cabeceras del río Amazonas y pertenece al ecosistema forestal más importante del mundo. Este estudio evalúa los efectos de la agricultura de tala y quema, en comparación con los factores naturales, sobre las propiedades químicas de los suelos, las quebradas, y los sedimentos, principalmente a través de un diseño de muestreo espacial. El trabajo de campo se realizó en dos cuencas fluviales adyacentes que están compuestas por rocas sedimentarias. Quebradas de 48 sub-cuencas independientes, dos ríos principales, 80 localidades de suelo (poco desarrollados sobre areniscas y limolitas) y cuatro perfiles verticales de sedimentos fluviales fueron muestreados y analizados para los elementos mayores y menores, incluyendo nutrientes y metales potencialmente tóxicos. También se han investigado las percepciones sobre los cambios ambientales usando una combinación de datos cuantitativos y cualitativos, recopilados a través de entrevistas a 51 agricultores. Según los resultados no hubo diferencias significativas entre la química de suelos de bosques primarios y tierras agrícolas (pastos, plantaciones de café y de bosques secundarios). En cuanto a las quebradas, las diferencias en las concentraciones de sustancias químicas entre sub-cuencas afectadas por la deforestación en diferentes grados fueron asignados a una variabilidad natural. Además, la composición química de los depósitos aluviales fue similar en las dos cuencas a pesar de una diferencia sustancial en el grado de explotación (30 % en comparación con 70 % deforestado). Por lo tanto, no se encontró evidencia de cambios persistentes en la geoquímica de las cuencas Subandinas como resultado de la conversión de bosques a tierras agrícolas. Sin embargo los agricultores percibieron una tendencia general de aumento de la degradación del medio ambiente, así como un cambio en el clima a condiciones más secas y cálidas, lo cual fue reportado como el principal factor responsable de un cambio negativo en la calidad de vida. Estos resultados pueden ser utilizados en el trabajo de identificación de prioridades y factores claves para la sostenibilidad ambiental y socioeconómica en la selva alta.