In this work we study properties of spacetimes with a high degree of symme- try. Particularly, we focus on geometries related to higher-dimensional rotating black-hole spacetimes described by the Kerr-NUT-(A)dS metric. In the first part, we examine spacetimes admitting a separable Klein-Gordon equation. Motivated by Carter's work in four dimensions, we introduce a separable met- ric ansatz in higher dimensions. Analyzing Einstein's equations, we obtain the Kerr-NUT-(A)dS and specific Einstein-K¨ahler metrics. Then we consider a metric ansatz in the form of warped geometries of two Klein-Gordon separable metrics and classify the corresponding solutions. In the second part, we in- vestigate a class of limits of the Kerr-NUT-(A)dS spacetimes where particular roots of metric functions degenerate. Our limiting procedure results in various NUT-like and near-horizon geometries such as the higher-dimensional Taub- NUT-(A)dS spacetime. We demonstrate that the symmetries of the resulting geometries are enhanced, which is manifested by decomposition of Killing ten- sors into Killing vectors. The third part of this work deals with generalized symmetry axes of the Kerr-NUT-(A)dS spacetimes that are formed by fixed points of isometries. We show that some parts of the symmetry axes are sin- gular for nonzero NUT charges....

Brazil nuts (Bertholletia excelsa, H.B.K.) are seeds of high nutritional value collected from South American rainforests and its productive chain is one of the most important non-timber economic activities in Brazilian amazon. The main objectives of this research were: 1) characterize the occurrence of chemical changes in Brazil nut kernels (BNK), cold-pressed Brazil nut oil (BNO) and Brazil nut flour obtained by water extraction (BNF); and 2) investigate strategies of control and monitoring these changes during storage. For this, consolidated techniques, such as spectrophotometry and chromatography, and a relatively new analytical technique, the electron spin resonance (ESR) spectroscopy, were employed. As major results, it was found that different combinations of storage temperatures and atmosphere packages have differently affected the tendency of radical formation and off-flavor volatile aroma compounds generation in BNK, and that the combination of refrigeration with vacuum packing was able to keep BNK at their best. It was demonstrated that a spin-trapping ESR spectroscopy method would be suitable to monitor oxidative changes in BNO with known history stored either in clear or in brown glass bottles under retail conditions. For BNF, it was demonstrated that minor variations on water activity (aw) might significantly affect the rates of both lipid oxidation and nonenzymatic browning reactions during storage. There was indication that for BNF with initial aw of 0.196, but not for BNF with initial aw of 0.101, under the studied conditions, secondary products from lipid oxidation might be substrates for nonenzymatic browning products formation. As a conclusion, these results may help to better understand chemical deteriorative processes in BNK and its co-products, according to the storage conditions, and that the use of less sample-demanding, fast and solvent-free analytical method to monitor these changes in BNO is feasible. / A castanha do Brasil (Bertholletia excelsa, H.B.K.) é uma semente de boa qualidade nutricional coletada em florestas tropicais da América do Sul, cuja cadeia produtiva é uma das mais importantes atividades econômicas não madeireiras da Amazônia brasileira. Os principais objetivos desta pesquisa foram: 1) caracterizar a ocorrência de alterações químicas em castanhas do Brasil (CB), óleo de castanha do Brasil obtido por prensagem a frio (OCB) e farinha de castanha do Brasil obtida por extração aquosa (FCB); e 2) investigar estratégias para controlar e monitorar essas alterações ao longo do armazenamento. Para isso, técnicas consolidadas como a espectrofotometria e a cromatografia, e uma técnica relativamente recente, a espectroscopia de ressonância de spin eletrônico (RSE), foram empregadas. Dentre os principais resultados obtidos, foi possível constatar o efeito de diferentes combinações de temperaturas e atmosferas de embalagem sobre a tendência de formação de radicais e sobre a geração de compostos voláteis de aroma relacionados a odor indesejável em CB, e que a temperatura de refrigeração combinada com a embalagem a vácuo foi a mais eficiente na preservação da qualidade da CB. Demonstrou-se que o uso de um método de aprisionamento de spins de RSE pode ser eficiente para monitorar alterações químicas em OCB com histórico conhecido embalado em frascos de vidro transparente ou marrons sob condições de armazenamento comercial. Para FCB, foi demonstrado que pequenas variações na atividade de água (aw) podem afetar significativamente as taxas de oxidação lipídica e de reações de escurecimento não enzimático durante armazenamento. Obteve-se indicação de que para FCB com aw inicial de 0,196, mas não para FCB com aw inicial de 0,101, produtos secundários da oxidação lipídica podem ser substratos para a formação de produtos do escurecimento não enzimático. Como conclusão geral, os resultados obtidos podem ajudar a explicar melhor os processos de deterioração química em CB e seus coprodutos, conforme as condições de armazenamento, e que o uso de um método que requer menor quantidade de amostras, é rápido e não usa solventes é viável para o monitoramento da qualidade de OCB.

STUDENT NUMBER: 0516082G Master of Science in Resource Conservation Biology Faculty of Science / The aim was to determine the availability of marula (Sclerocarya birrea) (A.Rich.) Hochst. Subsp.cafra (Sond.) Kokwaro trees for the harvesting of nut oils, through determining abundance, population structure and regeneration capacity, within the context of the socioeconomic and biophysical dimensions of villages in Zvishavane, Zimbabwe. Both arable and non arable lands in the study area were sampled within four randomly selected villages to measure species abundance, regeneration and population dynamics of the trees. The socioeconomic factors influencing marula commercialisation were determined through participatory rural appraisal (PRA) and household questionnaire survey techniques. Vegetation characteristics were assessed through the point centre quarter (PCQ) method by placement of transects across sampled villages. All households (100%) collected marula fruit for their household use, mainly for brewing marula beer, making jam and selling kernels for snacks or oil pressing. In 2005, the mass of marula harvest per household averaged 160 ± 18 (SD) kg, with a range of 50-800 kg within the study area. A linear regression analysis indicates no increase in mass of marula harvest with larger sizes of household (r2 = 0.0089, d.f = 50, p = 0.4048). In addition, household interviews revealed that there was no association between level of household wealth status and the household’s use of traditional medicine from marula trees (χ2 = 0.2233, d.f = 2, p = 0.8944). The vegetation survey indicated a elatively high density of marula within the study area of 8.03 ± 3.19 stems ha-1. There was a significant difference in marula densities between arable and non arable land uses (F1, 197 = 11.92, p=0.001). The arable land had 6.40 ± 5.29 stems ha-1 while non arable land had three times more at 19.63 ± 11.82 stems ha-1. However there was no significant difference in densities between the villages in the study area (F 3, 195 =1.063, p= 0.366). There was a significant difference between marula tree diameters between arable and non arable land (t 92, 107 = 1.69, p = 0.0401). The arable land had generally bigger tree diameters (31.2 ± 25.3 cm) than non arable land (26.5 ± 20.8 cm), suggesting a form of domestication through allowing marula to grow around homesteads and crop fields. The investigation of marula size class profiles shows a large proportion of smaller diameter trees and this indicates ongoing recruitment of trees into the population. A closer analysis of the smallest diameter class shows a higher proportion of saplings (> 6cm diameter) than of seedlings (< 4cm diameter). Fruit harvesting seems to have a low potential for any negative impact, compared to other uses of marula trees. However fruits have the highest economic return and therefore should be targeted for the commercialisation activities. The management of some destructive forms of marula tree use (such as harvesting for bark, firewood, and carving wood) however, do need to be monitored to limit negative impacts on the population. There is also a need to determine the annual quantity of harvestable marula fruits and also the sex ratio of marula trees (a dioecious species) on this particular site, as a prelude to developing sustainable harvesting quotas, so that harvesting rates do not exceed the capacity of populations to replace the individuals extracted. There are some non governmental organisations (NGOs) and local institutions that are working towards natural resources conservation in the area. Zvishavane water project (ZWP) and Phytotrade Africa are assisting the rural producers in marula commercialisation activities through providing information on processing, packaging and marketing. At a current value of US$1 kg-1of fruit, the 3200 ha study area is estimated to yield a total harvest of 1 120 000 kg of marula fruit per year, and this should translate to an approximate total value of $1 120 000 per year for the whole area. There is still a need to expand the supply of processed goods with added value to wider markets locally, nationally, and internationally. There is therefore an indication that marula products offer a promising economic alternative for the people in the rural areas of Zvishavane area and southern Africa as a whole. The cash injection earned from selling fresh marula products comes at a particularly crucial time of the year, when money is required for school fees, uniforms and books. However there is a need for long-term monitoring and evaluation of socio-economic and environmental impacts of marula commercialisation so as to achieve sustainable resource utilisation in the region.

Ao longo da história da humanidade duas características se destacam: a crescente capacidade de captar energia e informação por parte das populações humanas, especialmente exponencial nos últimos 300 anos, e o aumento da complexidade na organização das suas sociedades em razão notadamente do crescimento das teias de interdependência humana. As pressões políticas e econômicas por satisfazer as necessidades do mercado mundial colocam em risco a reprodução social das populações amazônicas com seus meios tradicionais de sobrevivência, o que implica em ameaça à estabilidade política do país. O olhar investigativo deste trabalho se volta para os contextos sócio-históricos como base de uma análise das instituições em torno do uso de um recurso de acesso comum, considerando as múltiplas funções (sociais, ambientais, culturais) destas práticas sociais, particularmente relacionadas ao manejo e exploração coletiva da castanha do Brasil (Bertholletia excelsa). Neste quadro, este estudo teve como objetivo examinar em que medida o uso deste recurso de acesso comum, a castanha do Brasil, regido por normas locais, é afetado por medidas governamentais. As instituições relacionadas aos recursos de acesso comum participam e se desenvolvem na propriedade comunal, num processo de longo tempo. Elas podem se reforçar ou se fragilizar em razão de medidas governamentais. Estas últimas serão o objeto de análise, constituindo parte do quebra-cabeça necessário para nos aproximar de uma realidade complexa. Os resultados deste trabalho visam também contribuir com a reflexão sobre o papel do Estado na promoção e reconhecimento ou, ao contrário, na erosão - de funções associadas às atividades extrativas florestais, neste caso em torno da exploração comunitária da castanha do Brasil em Tres Islas. Para desenvolver este objetivo, procura-se resgatar e analisar a história da Amazônia peruana, destacando processos socioculturais da comunidade de Tres Islas. Ademais, procura-se caracterizar o sistema de exploração da castanha em seu ecossistema específico e identificar as múltiplas funções associadas a esta atividade extrativa. Posteriormente, são analisadas as políticas públicas que afetam o manejo da castanha do Brasil na comunidade de Tres Islas, análise fundada nos referenciais que orientam a ação do Estado. A abordagem metodológica desta pesquisa se fundamenta, sobretudo, na análise de entrevistas com coletores de castanha, o que permite apresentar as características de manejo coletivo da terra, discutir como as políticas, em escala regional e nacional, e como padrões culturais ou forças sócio-econômicas se relacionam com a tomada de decisões dos atores individuais e coletivos sobre suas estratégias de reprodução social. Como conclusão observou-se que as regras usadas na comunidade de Tres Islas para a atividade castanheira configuram, em grande medida, um sistema de gestão robusto, favorável a preservação da auto-gestão comunitária da atividade extrativa florestal, com benefício econômico às famílias de Tres Islas e fortalecimento das relações sociais ao interior da comunidade. Ao mesmo tempo, este sistema rege uma exploração extrativista que contribui com conservação da floresta, quando comparada com outras atividades. No entanto, este sistema de manejo autogestionário encontra-se sob risco: as medidas governamentais são concebidas e implementadas sem um maior reconhecimento das múltiplas funções associadas a esta atividade extrativa. / There are two remarkable characteristics during mankind history: the increasing capacity of human populations, exponentially in the last 300 years, to obtain energy and information and the increase in the complexity of the organization of their societies based especially on human interdependence. Economical and political pressures to satisfy the needs of the worldwide market put at risk the social reproduction of the Amazonian populations with their traditional ways of survival. This implies a threat to the political stability of the country. The research approach of this project focuses on the social-historical context to analyze institutions regarding the use of a common-pool resource. We have considered multiple functions (social, environmental, cultural) of these social practices, particularly, regarding the management and collective exploration of the Brazil nut (Bertholletia excelsa). In this scenario, the purpose of the study was to evaluate the extent of use of the commonpool resource, the Brazil nut, governed by local laws and affected by governmental measures. The institutions related with the common-pool resources participate in the common property in a very long process. They can become stronger or more fragile depending on the governmental measures. These measures will be analyzed, constituting part of the puzzle necessary to be closer to a complex reality. The results of this project also propose to contribute with a reflection about the role of the State in the promotion and acknowledgment, or on the contrary, in the erosion on associated functions to forest extraction activities. In this particular case, about the communal exploration of the Brazil nut in Tres Islas. To develop the objective, we pursued to rescue and analyze the history of the Peruvian Amazon. We emphasized social-cultural processes of the community Tres Islas. Also, we pursued to characterize the exploration system of the Brazil nut in its specific ecosystem and identify the multiple functions associated to this extractive activity. After the analysis of the public policies affecting the management of the Brazil nut, in the community Tres Islas, it reported that everything is dependent on a States action. The methodological approximation of this research focuses, overall, in the analysis of interviews with harvesters of Brazil nuts. This allows us to present the characteristics of collective management of the land, discuss policies at regional and national level, and how cultural patterns or social-economical forces are related with decisions taken by individual and collective stakeholders about their social reproduction strategies. In conclusion, we observed that the rules used in the community Tres Islas for the activity of Brazil nut harvest, lead to a strong management system favorable to the preservation of the self-community management in forest activities. This also brings an economical advantage to the families and the strengthening of the social relations inside the community. At the same time, this system guides an extractive exploration contributing with the forest preservation in comparison with other activities. However, this self-managed system is under risk, governmental measures are thought and implemented without the corresponding acknowledgment of the multiple functions associated to this extractive activity.

Existe ampla evidência do nível de seletividade exibido por macacos-prego (Sapajus sp) em situações de escolha de ferramentas para a quebra de frutos encapsulados; indicando que as características dos martelos (material, peso e distância de transporte), assim como as características físicas próprias dos indivíduos, afetam a eficiência do na quebra e determinam o processo individual de tomada de decisões no uso de ferramentas. Considerando a predição de que também é provável que a eficiência na quebra seja dependente do controle do macaco sobre a pedra e do ângulo de impacto; o presente trabalho teve como objetivo avaliar experimentalmente se a forma das ferramentas afeta a eficiência na quebra e é levada em consideração pelos macacos-prego, na hora de escolher as ferramentas a serem usadas. Para tal, testamos a escolha de pedras por cinco macacos-prego semilivres usuários de ferramentas - fazendo uso de pedras artificiais e realizando tentativas discretas de escolha com participação livre dos indivíduos - através de um delineamento fatorial de medidas repetidas com oito condições experimentais, correspondentes às possíveis combinações de três variáveis independentes em dois níveis: forma dos martelos (possibilidades de pegada e superfície potencial de contato), peso (leve e pesado) e distância de transporte exigida (perto e longe das bigornas). Avaliamos a seletividade exibida, os comportamentos manipulativos exploratórios e a proficiência natural de quebra de cada sujeito, visando elucidar os fatores determinantes do processo de escolha de ferramentas para a quebra de frutos. Os resultados apontam preferência dos macacos-prego pelos martelos que fornecem maior eficiência, pedras com maior possibilidade de pegada e maior superfície potencial de contato no golpe, aumentando os benefícios e diminuindo os custos do uso. Não encontramos um efeito evidente das variáveis de custo (peso e distância de transporte) sobre a preferência pelas características da forma, nem foi encontrada uma relação entre a preferência exibida em condições experimentais com o engajamento e proficiência natural dos indivíduos na quebra de cocos. Finalmente, verificamos que os macacos-prego baseiam suas escolhas principalmente a partir das dicas visuais, não obstante exibirem comportamentos manipulativos exploratórios que possivelmente permitem ganhar informação adicional sobre as propriedades da forma das ferramentas para realizar a escolha / Evidences point out that capuchin monkeys select stone tools for nut cracking based on the physical characteristics of tools (material, weight, transporting distance) in relation to their own physical characteristics (size, weight), and that selectivity seems to affect the efficiency of nut cracking, determining individual decision making in tool use. Considering the prediction that nut crack efficiency is affected by individual control, the stone and the impact angle; this study aimed to evaluate experimentally if the tools shape affect nut crack efficiency, and if this is considered in individual tool selection. We tested the choices of five semi-free individuals using artificial designed tools in eight different experimental conditions, manipulating hammers weight, shape and distance to the anvil, to determine the factors involved in tool selection process for nut cracking. The results shows the monkeys prefer hammers that increase cracking nut efficiency, with more holding possibility, and higher potential contact surface in the bites. There was no evidence for effect of variables related with costs (hammer weight and transporting distance) on the shape preference, and there was no relation between preferences in experimental conditions and engage or efficiency in baseline. We found that the capuchin monkeys based their tool choices in visual characteristics and exhibit manipulative exploratory behaviors that allow them to gain information about the tools shape to make choices

M. Tech. (Chemistry, Faculty of Applied and Computer Science), Vaal University of Technology / The abundance of agricultural waste materials has led to its use as adsorbents for trace metal adsorption. The raw Macadamia nutshell (RMN) powder was treated with a hydrochloric acid solution to obtain acid modified Macadamia nutshells (AMM), and with sodium hydroxide solution to obtain base modified Macadamia nutshells (BMM). Then, the AMM and BMM materials were grafted with 0.5 M, 1 M, and 2 M acrylic acid. The different AMM grafted materials were labelled 0.5 GAM, 1 GAM and 2 GAM representing the different grafting ratios. The same naming order was followed for the BMM grafted materials, that is, 0.5 GBM, 1 GBM and 2 GBM corresponding to different concentrations used. The prepared Macadamia based adsorbents were characterized using Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), carbon, hydrogen, nitrogen and sulphur (CHNS) analysis, powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) analysis. The determination of surface properties such as the point of zero charge (pHPZC), bulk density and the surface negative charge was accomplished with appropriate wet chemistry methods. The adsorption of selected trace metals (Cu(II), Cd(II), Co(II), and Cr(VI)) was done in batch experiments. Atomic absorption spectroscopy (AAS) was used for the determination of metal ions concentrations and total Cr. The ultraviolet-visible (UV–Vis) spectroscopy was used for the determination of Cr(VI) concentration remaining in solution after adsorption. The RMN, AMM, and BMM adsorbents showed potential in removing more than 45% Cu(II) ions, but less than 30% for both Cd(II) and Co(II) ions. However, more than 90% removal of Cr(VI) ions was achieved with the same adsorbents. Consequently, only the adsorption of Cr(VI) was further investigated in the study due to the higher removal efficiency displayed by the Macadamia based biosorbents. The optimum adsorption conditions for the RMN, AMM, and BMM materials were found to be pH 2, 100 mg/L initial concentration of Cr(VI), 600 min contact time and 0.2 g adsorbent mass. The ideal conditions for the 0.5 GAM and 0.5 GBM were found to be pH 2, 25 mg/L initial concentration of Cr(VI), 180 min contact time, and 0.15 g adsorbent mass. The optimum temperature was found to be 40℃ for all materials. A volume of 20 mL was used for all batch experiments. The RMN, AMM, BMM, 0.5 GBM, and 0.5 GAM adsorption mechanisms were better described by the Langmuir isotherm which predicted a monolayer sorption process. The kinetic data fitted better to the pseudo second-order rate model which signified a chemisorption type of interaction. The thermodynamic parameters showed that the adsorption reaction was feasible, spontaneous and endothermic. The Macadamia based materials showed greater potential as adsorbents for the adsorption of Cr(VI) ions from aqueous solution compared to the other selected trace metal ions [Cd(II), Cu(II) and Co(II)].

Observações feitas pelo próprio autor sugerem potencial ação do Líquido da Castanha de Caju (LCC) na pigmentação da pele, ação esta semelhante a da hidroquinona. O LCC é um líquido contido na casca da castanha de caju, possui característica de resina líquida, bastante viscosa e de odor forte, sua coloração varia de marrom claro, escuro a preto, dependendo do método de extração utilizado, podendo ser denominado de Natural ou Técnico. Este estudo propôs cultivar melanócitos e queratinócitos em cocultura e posteriormente tratálos com LCC. A L-DOPA, agente estimulador da melanogênese, via da produção de melanina, responsável pela pigmentação da pele, foi utilizada na cocultura para avaliar a ação do LCC. A hidroquinona, conhecido inibidor desta via, foi utilizada na cocultura como controle positivo para o LCC, visto que este poderia apresentar ação semelhante a da hidroquinona. Para a utilização do LCC na cocultura, testes de solubilidade do mesmo para posterior dispersão no meio de cultura, foram necessários, bem como a identificação de seu potencial cito e fototóxico in vitro. Para a realização do teste de fototoxicidade foi construída uma câmara específica, atendendo as normas exigidas pelos guias ©ECVAM DB-ALM: INVITTOX protocol e OECD TG-432, sendo esta qualificada por método validado. Os testes realizados com o LCC (natural e técnico) indicaram potencial ação destes na pigmentação da pele, estimulando a proliferação de melanócitos em cocultura. Este perfil apresentado, pelos extratos de LCC, é contrário ao da hidroquinona, e ao esperado inicialmente, sendo necessário aprofundar estes estudos. No entanto, estes resultados são promissores, sugerindo a descoberta de um novo tratamento para hipocromias. / Observations, made by the author, suggest potential action of Cashew Nut Shell Liquid (CNSL) in skin pigmentation, action similar to hydroquinone. The CNSL is a liquid contained inside the shell of the cashew nut, it has features of liquid resin, quite viscous and strong smell. Its color varies from clear or dark brown, to black, depending on the extraction method used, which may be called Natural or Technical. This study aimed to cultivate melanocytes and keratinocytes in co-culture and thus treat them with CNSL. The L-DOPA, stimulating agent of melanogenesis, melanin production pathway, responsible for skin pigmentation, was used to assess the CNSL action in the co-culture. Hydroquinone, known inhibitor of this pathway, was used as positive control for CNSL in the co-culture, since this could provide a similar action to hydroquinone. For use of CNSL in the co-culture, solubility tests, for subsequent dispersion in the culture medium, were necessary, as well as the identification of its cytototoxic and phototoxic potential in vitro. To achievement of the phototoxicity tests a specific chamber was built according to the standards required by the guides ©ECVAM DB-ALM: INVITTOX protocol and OECD TG-432, being qualified by validated method. Tests conducted with the CNSL (natural and technical) indicated their potential actions in skin pigmentation, stimulating the proliferation of melanocytes in co-culture. This behavior presented by the CNSL extracts, is opposite to the hydroquinone, and to the initially expected, being required further studies. However, these results are promising, suggesting the discovery of a new treatment for hypochromia.

Este trabalho apresenta os estudos decorrentes da identificação de espécies moleculares associadas aos elementos Ca, Cu, Fe, Mg e Zn em amostras de castanha de caju (Anacardium Ocidentale), os quais foram realizados por: (1) digestão total da amostra, (2) digestão simulada in vitro, (3) extração de metais e proteínas empregando água, NaOH e Tampão Tris-HCl, (4) precipitação de proteínas com HCl ou acetona, (5) avaliação da associação entre espécies elementares e moleculares presentes nos diferentes meios extratores utilizando o acoplamento entre SEC-UV-SIMAAS e SEC-UV-ICP OES e (6) especiação de Fe em amostra de água de diálise empregando método espectrofotométrico. As determinações elementares nas amostras de castanha de caju demonstraram que os teores de Ca foram de (0,031 ± 0,001)%; Cu (19,1 ± 0,1) mg kg-1; Fe (53,5 ± 0,2) mg kg-1; Mg (0,22 ± 0,01) % e Zn (40 ± 3) mg kg-1, respectivamente. O emprego de soluções gástrica e intestinal simuladas revelou que 10% de Ca, 29% de Zn, 44% de Mg, 80% de Fe e 90% de Cu são extraídos durante a digestão. Após o processo de diálise, verificou-se que 100% do Zn e 90% do Ca, Fe e Mg passaram através da membrana de ester de celulose (tamanho de poro = 12 kDa). Porém, o cobre apresentou uma porcentagem de diálise de 70%. O processo de extração de proteínas indicou que a solução alcalina possui elevada capacidade de solubilização dos analitos, quando comparada com os demais extratos. A análise molecular das soluções extratoras demonstrou que em meio alcalino e tamponado há uma maior solubilização de compostos de alto peso molecular e o meio aquoso solubiliza espécies de baixo peso molecular. A precipitação realizada a partir dos extratos proteícos utilizando HCl propiciou uma alteração no perfil de distribuição molecular dos compostos presentes nos extratos aquoso e tamponado. Porém, o uso da precipitação em meio de acetona revela um perfil de separação diferente, pois em meio orgânico ocorre a seleção de compostos de baixo peso molecular (< 6,5 kDa). As análises por SEC-UV-ICP OES em soluções gastrointestinais revelou que os elementos estão distribuidos entre proteínas de alto e baixo peso molecular. Mas o processo de diálise demonstrou que algumas interações elementares e moleculares foram desfeitas após esta etapa de precipitação com HCl ou acetona. Porém, estes dados podem fornecer o primeiro indício da presença de metaloproteínas em amostras de castanha de caju. O monitoramento das espécies de ferro em amostras de água de diálise demonstra que apenas o íon trivalente (Fe3+) foi identificado. Sendo que, ao realizar a quantificação desta espécie, verifica-se que o teor de ferro livre presente na solução foi de 15%. Portanto, esta solução continha, aproximadamente, 85% de espécies químicas de ferro presentes no extrato gastrointestinal, as quais estão associadas a outros compostos presentes na amostra / In this work studies were done for the identification of molecular species associated to Ca, Cu, Fe, Mg and Zn in cashew nuts (Anacardium Occidental) using the following procedures: (1) sample acid digestion for total element determination; (2) in vitro digestion; (3) metals and proteins extraction using water, NaOH and Tris-HCl; (4) protein precipitation with HCl or acetone; (5) evaluation of association between elemental and molecular species in different extractors using SEC-UV-SIMAAS and SEC-UV-ICP OES and (6) iron speciation analysis in dialysis water using a spectrophotometric method. The elemental analysis showed that in cashew nuts there is a great quantity of Ca (0.031 ± 0.001) % and Mg (0.22 ± 0.01) %, but minor quantity of Cu (19.1 ± 0.1) mg kg-1, Fe (53.5 ± 0.2) mg kg-1 and Zn (40 ± 3) mg kg-1. The bioavailability studies reveal that Ca (10%), Zn (29%), Mg (44%), Fe (80%) and Cu (90%) were extracted during the in vitro digestion. After dialysis, 100% of Zn and 90% of Ca, Fe and Mg passed through the membrane, however, only 70% of Cu was dialysed in this step. The protein extraction procedures indicate that alkaline media has a great capacity for solubilization of analytes, if compared with other extracts. The molecular analysis of extracts showed that in alkaline and buffered media there is a presence of high molecular weight compounds and water extracted low molecular weight compounds. The HCl precipitation in water and buffered extractors change the molecular distribution profile and acetone precipitation selected low molecular weight compounds (< 6.5 kDa) for all extractors. The SEC-UV-ICP OES analysis in gastric intestinal solutions showed that the elements were distributed between high and low molecular weight compounds, but the dialysis procedure revealed the elemental and molecular correlations disappear to some metals. The monitoring of iron species by spectrophotometric method demonstrated that only 15% of trivalent iron was identified in the water dialysis. Therefore, this solution contain approximately 85% of iron species present in the gastrointestinal extract which are associated with others compounds in the sample.

Este trabalho apresenta os estudos decorrentes da identificação de espécies moleculares associadas aos elementos Ca, Cu, Fe, Mg e Zn em amostras de castanha de caju (Anacardium Ocidentale), os quais foram realizados por: (1) digestão total da amostra, (2) digestão simulada in vitro, (3) extração de metais e proteínas empregando água, NaOH e Tampão Tris-HCl, (4) precipitação de proteínas com HCl ou acetona, (5) avaliação da associação entre espécies elementares e moleculares presentes nos diferentes meios extratores utilizando o acoplamento entre SEC-UV-SIMAAS e SEC-UV-ICP OES e (6) especiação de Fe em amostra de água de diálise empregando método espectrofotométrico. As determinações elementares nas amostras de castanha de caju demonstraram que os teores de Ca foram de (0,031 ± 0,001)%; Cu (19,1 ± 0,1) mg kg-1; Fe (53,5 ± 0,2) mg kg-1; Mg (0,22 ± 0,01) % e Zn (40 ± 3) mg kg-1, respectivamente. O emprego de soluções gástrica e intestinal simuladas revelou que 10% de Ca, 29% de Zn, 44% de Mg, 80% de Fe e 90% de Cu são extraídos durante a digestão. Após o processo de diálise, verificou-se que 100% do Zn e 90% do Ca, Fe e Mg passaram através da membrana de ester de celulose (tamanho de poro = 12 kDa). Porém, o cobre apresentou uma porcentagem de diálise de 70%. O processo de extração de proteínas indicou que a solução alcalina possui elevada capacidade de solubilização dos analitos, quando comparada com os demais extratos. A análise molecular das soluções extratoras demonstrou que em meio alcalino e tamponado há uma maior solubilização de compostos de alto peso molecular e o meio aquoso solubiliza espécies de baixo peso molecular. A precipitação realizada a partir dos extratos proteícos utilizando HCl propiciou uma alteração no perfil de distribuição molecular dos compostos presentes nos extratos aquoso e tamponado. Porém, o uso da precipitação em meio de acetona revela um perfil de separação diferente, pois em meio orgânico ocorre a seleção de compostos de baixo peso molecular (< 6,5 kDa). As análises por SEC-UV-ICP OES em soluções gastrointestinais revelou que os elementos estão distribuidos entre proteínas de alto e baixo peso molecular. Mas o processo de diálise demonstrou que algumas interações elementares e moleculares foram desfeitas após esta etapa de precipitação com HCl ou acetona. Porém, estes dados podem fornecer o primeiro indício da presença de metaloproteínas em amostras de castanha de caju. O monitoramento das espécies de ferro em amostras de água de diálise demonstra que apenas o íon trivalente (Fe3+) foi identificado. Sendo que, ao realizar a quantificação desta espécie, verifica-se que o teor de ferro livre presente na solução foi de 15%. Portanto, esta solução continha, aproximadamente, 85% de espécies químicas de ferro presentes no extrato gastrointestinal, as quais estão associadas a outros compostos presentes na amostra / In this work studies were done for the identification of molecular species associated to Ca, Cu, Fe, Mg and Zn in cashew nuts (Anacardium Occidental) using the following procedures: (1) sample acid digestion for total element determination; (2) in vitro digestion; (3) metals and proteins extraction using water, NaOH and Tris-HCl; (4) protein precipitation with HCl or acetone; (5) evaluation of association between elemental and molecular species in different extractors using SEC-UV-SIMAAS and SEC-UV-ICP OES and (6) iron speciation analysis in dialysis water using a spectrophotometric method. The elemental analysis showed that in cashew nuts there is a great quantity of Ca (0.031 ± 0.001) % and Mg (0.22 ± 0.01) %, but minor quantity of Cu (19.1 ± 0.1) mg kg-1, Fe (53.5 ± 0.2) mg kg-1 and Zn (40 ± 3) mg kg-1. The bioavailability studies reveal that Ca (10%), Zn (29%), Mg (44%), Fe (80%) and Cu (90%) were extracted during the in vitro digestion. After dialysis, 100% of Zn and 90% of Ca, Fe and Mg passed through the membrane, however, only 70% of Cu was dialysed in this step. The protein extraction procedures indicate that alkaline media has a great capacity for solubilization of analytes, if compared with other extracts. The molecular analysis of extracts showed that in alkaline and buffered media there is a presence of high molecular weight compounds and water extracted low molecular weight compounds. The HCl precipitation in water and buffered extractors change the molecular distribution profile and acetone precipitation selected low molecular weight compounds (< 6.5 kDa) for all extractors. The SEC-UV-ICP OES analysis in gastric intestinal solutions showed that the elements were distributed between high and low molecular weight compounds, but the dialysis procedure revealed the elemental and molecular correlations disappear to some metals. The monitoring of iron species by spectrophotometric method demonstrated that only 15% of trivalent iron was identified in the water dialysis. Therefore, this solution contain approximately 85% of iron species present in the gastrointestinal extract which are associated with others compounds in the sample.

Avec la globalisation des échanges et la nécessité de répondre à de nouveaux enjeux liés au changement climatique et à la crise énergétique, les agricultures africaines sont sollicitées pour produire de nouvelles cultures. L‘introduction de ces dernières dans les espaces productifs a connu des succès, comme le cas de l‘anacarde (noix de cajou) en Afrique de l‘Ouest ou des déconvenues, comme c‘est actuellement le cas du jatropha dans toute cette région. Ces résultats ont des intensités, des rationalités, des formes, des trajectoires diverses en fonction des espaces dans lesquels ils ont lieu. Ainsi au sein d‘un même pays, certaines régions s‘empareront de ces cultures alors que d‘autres les rejetteront plus ou moins rapidement. Comprendre les raisons de ces succès et échecs en relation avec leur localisation est un enjeu majeur pour accompagner au mieux ces changements. Ainsi, cette thèse questionne la forme et la dynamique d‘une innovation agricole au regard de son ancrage territorial. Actuellement, le concept de Système d‘Innovation (SI) offre un cadre d‘analyse systémique des processus d‘innovations. Mais ce dernier est généralement appliqué à des échelles nationales ou sectorielles ; la dimension territoriale n‘y est que rarement prise en compte. L‘objectif de cette thèse est de construire un cadre d‘analyse territorial de l‘innovation selon une approche fonctionnaliste, permettant d‘identifier les fonctions que le SI et le territoire doivent activer conjointement pour que l‘innovation puisse se diffuser. Ce cadre a été construit à partir de la littérature et d‘observations de terrain avant d‘être appliqué aux cas de l‘anacarde et du jatropha dans le sud-ouest du Burkina Faso. La démarche mise en place, allie des enquêtes, une analyse spatiale de l‘innovation et une grille d‘évaluation des relations entre fonctionnement du SI et fonctionnement des territoires. Les résultats mettent en évidence des facteurs de blocage et les synergies expliquant le degré d‘adoption de l‘innovation, tels que l‘accessibilité du territoire, sa capacité d‘échange, son système productif, la légitimité de ses institutions, etc. Ils permettent de comprendre la dynamique de l‘innovation agricole comme un processus d‘interactions successives avec le territoire et mettent également en lumière le rôle de l‘innovation dans les changements territoriaux en cours. La grille d‘analyse offre aussi des perspectives d‘utilisation prédictive pour évaluer le développement d‘une innovation selon les caractéristiques des territoires. Enfin, des recommandations sont formulées en faveur d‘actions localisées et priorisées afin d‘améliorer l‘efficacité des systèmes d‘innovation agricoles. / Due to globalization of trade and the need to fulfill the challenges raised by climate change and the energy crisis, African agricultures are required to grow new crops. Their insertion in productive spaces has been successful like the cashew nut in West Africa, or has encountered some setbacks as it is currently the case of jatropha across the region. These results have intensities, rationalities, forms and various trajectories, depending on the spaces in which they take place. Thus, within a country, some regions will be able to take hold of these crops whereas others won‘t and will reject it more or less rapidly. Understand the inner workings of success or failures in connection with their localization is a major issue to provide the best support to these changes. So, this PhD thesis questions the shapes and dynamics of agricultural innovation in terms of its territorial integration. Currently, the Innovation System (IS) concept provides a systematic analytical frame for innovation processes. But it is usually applied to national or sectorial levels; territorial dimension is rarely taken into account. The objective of this thesis is to build a territorial analysis of the innovation in a functionalist framework, identifying the functions that the IS and the territory must activate jointly for innovation to diffuse. This analytical framework has been built on the literature and on field observations, then it has been implemented on the cases of cashew nut and jatropha in the south-west region of Burkina Faso. The developed approach combines surveys, a spatial analysis of innovation and evaluation of the relations between IS and territories functioning. Results highlight synergies and blocking factors explaining the degree of adoption of innovation, such as the accessibility of the territory, its ability to exchange, its productive system, the legitimacy of its institutions, etc. They provide a means for understanding the dynamics of agricultural innovation as a process of successive interactions with the territory, and also highlighting the role of innovation in current territorial changes. The analytical framework provides also perspectives for a predictive approach to assess the future development of an innovation according to the characteristics of the territories. Finally, recommendations are made for localized and prioritized actions in order to improve the efficiency of agricultural innovation systems.