Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2017-04-04T10:15:18Z No. of bitstreams: 2 Dissertação - André Luiz Borges Machado - 2017.pdf: 4018960 bytes, checksum: 0f752eee89eafe0cb8606742dc6901b7 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2017-04-04T10:15:52Z (GMT) No. of bitstreams: 2 Dissertação - André Luiz Borges Machado - 2017.pdf: 4018960 bytes, checksum: 0f752eee89eafe0cb8606742dc6901b7 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2017-04-04T10:15:52Z (GMT). No. of bitstreams: 2 Dissertação - André Luiz Borges Machado - 2017.pdf: 4018960 bytes, checksum: 0f752eee89eafe0cb8606742dc6901b7 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2017-02-23 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Brazil nut (Bertholletia excelsa) and Macadamia (Macadamia integrifolia) are rich feeds with excellent nutrients with higher quality. The main form of consumption of these nuts and almonds are in natura, but there are products which can be elaborated using these raw materials with high nutritional value and pleasant flavor. Water-soluble extracts are an alternative to consume them, which consist of fluid food of plant origin, that can be produced by nuts, oleaginous and even some grasses and they have great commercial appeal since they are free of animal’s fats, “lac free” (free of lactose) and have high rate of minerals. Thus, this research aimed to determine the best formulation, to accompany physical and microbiological stability, proximal composition, to estimate the shelf life and to determine the rheological behavior of a water-soluble extract made of Brazil nut and Macadamia. For the construction of mathematical models, with the purpose of knowing the effect of the variation of water, Brazil nut and Macadamia concentrations, basic components in the elaboration of the product on the proximal composition and physical aspects such as pH, titratable acidity and colorimetry, a simplex centroid design for mixtures was used and provided quadratic and cubic models showing excellent adjustment of experimental data. The Global Acceptance and Purchase Intention tests were performed for each experiment proposed by simplex centroid design and the Tukey test was used in order to determine the best proportion among the components of the ternary mixture. The formulation of water-soluble extract composed of 70% (w/w) water, 15% (w / w) Brazilian nut and 15% (w/w) Macadamia was considered to be the most preferred by tasters submitted to the sensory evaluations. In order to improve the product’s flavor, 10% (w/v) of sugar, expressed as sucrose, was added and the concentration of preservatives citric acid, potassium sorbate and sodium benzoate was reduced. The product was processed technologically under hygienic conditions and filled in 220 ml transparent glass bottles, hermetically sealed with metal crown cork, pasteurized at 80 °C/25 min, stored under refrigeration at 4 ° C and had its stability evaluated during 28 days. Growth of Thermotolerant Coliforms, Positive Coagulase Staphylococci, Salmonella sp, Molds and Yeasts during the evaluation period was not detected. There was a significant variation (p < 0.05) in pH in the first two weeks of storage, and remained without significant variation (p > 0.05) for the other weeks analyzed. The acidity remained constant throughout the lifetime. The product showed a yellowish-white color throughout the study, determined by the coordinates of the colorimetry. Sensory analysis scores for odor, color, taste and global impression averaged around 6, thus, concluding that the product has a 28 days of shelf life. The rheological profile of the beverage was evaluated at three different temperatures, at 25 °C (room temperature), at 45 °C (temperature of the disintegration stage of Brazil nut and Macadamia with water in blender), and at 80 °C, (pasteurization temperature). The Ostwald-de-Waele model was considered the best to describe the beverage flow and since the calculated flow rate of the model, was less than 1 at the temperatures studied, it had concluded that the beverage behaved as a fluid Non-Newtonian pseudoplastic. The apparent viscosity curves of the mixed drink were plotted and showed that the apparent viscosity decreased significantly (p < 0.05) with the increasing of temperature. / A Castanha-do-Brasil (Bertholletia excelsa) e a Macadâmia (Macadamia integrifolia) são alimentos ricos em nutrientes de excelente qualidade. A principal forma de consumo de nozes e amêndoas é in natura, porém existem produtos que podem ser elaborados a partir destas matérias-primas com alto valor nutricional e também de sabor agradável. Uma alternativa ao consumo desses alimentos são os extratos hidrossolúveis, que consistem em alimentos fluidos de origem vegetal que podem ser produzidos a partir de castanhas, oleaginosas e até mesmo algumas gramíneas e possuem grande apelo comercial, uma vez que são isentos de gorduras animais, não possuem lactose e apresentam alto teor de minerais. Sendo assim, esta pesquisa objetivou determinar a melhor formulação, acompanhar a estabilidade física e microbiológica, composição proximal, estimar a vida útil e determinar o comportamento reológico de um extrato hidrossolúvel a base de Castanha-do-Brasil e Macadâmia. Para a construção de modelos matemáticos, com a finalidade de se conhecer o efeito da variação das concentrações de água, Castanha-do-Brasil e Macadâmia, dos componentes básicos na elaboração do produto sobre a composição proximal e aspectos físicos como pH, acidez titulável e colorimetria, utilizou-se o planejamento experimental para misturas tipo simplex centroide que forneceu modelos quadráticos e cúbicos com excelente ajuste frente aos dados experimentais. Os Testes de Aceitação Global e Intenção de Compra foram realizados para cada experimento proposto pelo planejamento simplex centroide e o teste de Tukey foi utilizado a fim de determinar a melhor proporção entre os componentes da mistura ternária. A formulação de extrato hidrossolúvel composta por 70% (p/p) de água, 15% (p/p) de Castanha-do-Brasil e 15% (p/p) de Macadâmia, foi considerada como a mais preferida pelos provadores submetidos as avaliações sensoriais. Com a finalidade de melhorar o sabor do produto, adicionou-se 10% (p/v) de açúcar, expressos em sacarose, e reduziu-se a concentração dos conservantes ácido cítrico, sorbato de potássio e benzoato de sódio. O produto foi processado tecnologicamente sob condições higiênicas, sendo envasado em garrafas de vidro transparente de 220 mL, fechado hermeticamente com tampas metálicas do tipo coroa, pasteurizado a 80 °C/25 min, armazenado sob refrigeração a 4 °C e teve sua estabilidade avaliada por 28 dias. Não foi detectado o crescimento de Coliformes Termotolerantes, Estafilococos Coagulase Positiva, Salmonella sp, Bolores e Leveduras durante o período de avaliação. Houve variação significativa (p < 0,05) do pH nas duas primeiras semanas de estocagem, estabilizando-se para as demais semanas analisadas. A acidez se manteve constante durante todo o período de vida útil. O produto apresentou coloração branco-amarelada durante todo o estudo, determinada pelas coordenadas da colorimetria. As notas das análises sensoriais para Odor, Cor, Sabor e Impressão Global tiveram média em torno de 6, concluindo assim que o produto tem vida útil de, pelo menos, 28 dias. Foi avaliado o perfil reológico da bebida em três temperaturas distintas, a 25 ºC (temperatura ambiente), a 45 ºC, (temperatura da etapa de desintegração da Castanha-do-Brasil e Macadâmia com a água em liquidificador), e a 80 ºC, (temperatura de pasteurização). O modelo de Ostwald-de-Waele foi considerado o melhor para descrever o escoamento da bebida e uma vez que o índice de escoamento calculado do modelo foi menor que 1, nas temperaturas estudadas, conclui-se que a bebida comportou-se como um fluido não newtoniano pseudoplástico. As curvas de viscosidade aparente da bebida mista foram plotadas e mostram que a viscosidade aparente diminuiu significativamente (p < 0,05) com o aumento da temperatura.

MENVSC / Department of Ecology and Resource Management / See the attached abstract below

M. Tech (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology. / Activated carbons have been produced from various carbonaceous source materials including nutshells, peat, wood, coir, lignite, coal and petroleum pitch and the produced carbons have been used for adsorption of inorganic and organic compounds from numerous matrices. Activated carbons are characterized by large surface area and high degree of microporosity. The ability of activated carbon to adsorb gold from solutions, which is present in very low concentrations while loading to fairly high concentrations, has made it an attractive material for the concentration of gold from dilute solutions. Consequently, the use of activated carbons for the recovery of gold from cyanide-leached liquors has gained wide acceptance in the mining industry. However, the price of commercially prepared carbons, the time taken for them to arrive, the breakage of the carbon during transportation and the interest in utilization of various local wastes for the generation of adsorbents has led to a search of more cost effective and time friendly source for the activated carbons. The focus of this research was to conduct a study in which a comparison was conducted between untreated coconut shell derived activated carbon (CAC) and Macadamia nutshell derived activated carbon (MAC) for the adsorption of gold. These activated carbons were modified with HNO3 and H3PO4 to increase their surface adsorption properties. This was done in order to explore if these activated carbons prepared from Macadamia shells could be an attractive alternative or a complementary supplement to the coconut shell based carbons that are currently being used in the gold extraction industry. The modification of the commercially prepared Macadamia activated carbons was done with 3 different concentrations for both nitric acid and phosphoric acid. The modified activated carbons were labelled MACP20%, MACP40% and MACP60%, to signify the materials prepared from 20% (v/v) H3PO4, 40% (v/v) H3PO4 and 60% (v/v) H3PO4 , respectively . Same labelling was used for 20% (v/v) HNO3, 40% (v/v) HNO3 and 55% (v/v) HNO3 modifications to correspond to MACN20%, MACN40% and MACN55%, respectively. Also, untreated coconut shell derived activated carbon (CAC) and Macadamia nutshell derived activated carbon (MAC) were investigated for gold adsorption for comparison purposes. All the activated carbons prepared in the iii | P a g e study were characterized with Brunauer-Emmet-Teller (BET), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), Thermo gravimetric analysis (TGA), elemental analysis (EL) and X-ray diffraction spectroscopy (XRD). The physical properties of the activated carbons were done by determining attrition, ash content, volatile matter, and moisture content of all the activated carbons. Various parameters that affect selective adsorption such as the effect of initial concentration, time, agitation speed, interfering species, and dose of the adsorbent were investigated. Optimal parameters for gold ion adsorption were as follows: solution pH, 10; contact time, 6 h; agitation speed 150 rpm; sorbent amount 4 g and 5.5 ppm for initial concentration of gold. The observed selectivity order was not the same for all the adsorbents but the adsorption of gold was found to be mostly influenced by the presence of nickel and least influenced by copper. The MACP60% was found to be the most effective from the three concentrations investigated for the phosphoric acid modified activated carbons yet proved to have lower adsorption capabilities compared to CAC. The MACN55% was found to be the most efficient and displayed similar adsorption capabilities to those of CAC.

As embalagens ativas têm ganhado destaque no mercado mundial, pois possibilitam a interação do alimento com o material da embalagem, permitindo a incorporação de compostos ativos. Dentre os compostos ativos, o extrato etanólico de cúrcuma (EEC) tem chamado atenção, devido suas propriedades antioxidante, antimicrobiana, dentre outras. Assim, os objetivos deste trabalho foram desenvolvimento, caracterização e aplicação de filmes à base de gelatina aditivados com EEC. Os filmes foram produzidos pela técnica de casting (2 g de gelatina/100 g de solução filmogênica (SF), 30 g de sorbitol/100 g de gelatina) e o EEC foi incorporado na SF, nas concentrações de 0, 5, 50, 100, 150 e 200 g EEC/100 g de gelatina. Os filmes foram caracterizados em relação às propriedades mecânicas, conteúdo de água, matéria solúvel, permeabilidade ao vapor de água, parâmetros de cor, opacidade, brilho, microestrutura, espectroscopia de infravermelho com transformada de Fourier (FTIR), barreira UV/Vis, transparência, teor de curcumina, atividade antioxidante e atividade antimicrobiana. O filme com os melhores resultados para as propriedades mecânicas, barreira UV/Vis e atividade antioxidante foi utilizado para embalar noz macadâmia e, as propriedades da noz foram avaliadas em função do tempo de estocagem. A incorporação do EEC melhorou as propriedades mecânicas dos filmes, a tensão de ruptura aumentou de 27,7 MPa (filme controle) para 35,1 MPa (filme com 200 g de EEC/100 g de gelatina) e a elongação na ruptura aumentou de 22,3 % (filme controle) para 36,5 % (filme com 200 g de EEC/100 g de gelatina). O conteúdo de água não foi influenciado pela adição do EEC, porém a matéria solúvel reduziu em relação ao filme controle. A permeabilidade ao vapor de água também reduziu em média 24,1 % para os filmes aditivados. Os parâmetros de cor, opacidade e brilho foram afetados pela incorporação do EEC. As análises de microestrutura indicaram alterações na rugosidade da superfície e um aumento na rugosidade da estrutura interna, em função do aumento da concentração de EEC nos filmes. A análise de FTIR mostrou deslocame ntos dos picos associados às amidas A, I e II para os filmes aditivados. Os filmes com EEC apresentaram reduzida transmitância na região UV/Vis e aumento da transparência. O teor de curcumina aumentou linearmente (y=0,6115x+6,6629, R2=0,9817) com o aumento da concentração do extrato. A capacidade antioxidante aumentou em função do aumento da concentração do EEC e a atividade antimicrobiana (Staphylococcus aureus) foi verificada para concentrações acima de 5 g de EEC/100 g de gelatina. Assim, o filme com concentração de EEC de 200 g de EEC/100 g de gelatina foi utilizado para embalar noz macadâmia. Em relação ao conteúdo de água da noz macadâmia foram observadas diferenças significativas em função do tipo de filme utilizado (com e sem ad ição de EEC) nos primeiros 30 dias de estocagem. Entretanto, para a atividade de água não foram observadas diferenças. Após 60 dias a dureza da noz macadâmia embalada com o filme aditivado foi superior e as substâncias reativas (ácido tiobarbitúrico) fora m inferiores. Pode-se concluir que é possível a utilização desse sistema como embalagem ativa para a noz macadâmia. / Active packaging has been receiving growing attention in the world market because it allows interaction between food and packaging material, thus enabling the incorporation of active compounds. Among active compounds, curcuma ethanol extract (CEE) has been highlighted mainly because its antioxidant and antimicrobial properties. The objectives of this study were the development, characterization and application of gelatin-based films added with CEE. The films were produced by casting technique (2 g gelatin/100 g filmogenic solution (FS), 30 g sorbitol/100 g gelatin) and CEE was added to FS at 6 concentrations (0, 5, 50, 100, 150 and 200 g CEE/100 g gelatin). The films were characterized regarding mechanical properties, water content, soluble matter, water vapor permeability, color parameters, opacity, gloss, microstructure, Fourier transform infrared spectroscopy (FTIR), light transmission, transparency, curcumin content, antioxidant activity, and antimicrobial activity. The film with the best results concerning mechanical properties, light transmission and antioxidant activity was selected to package macadamia nut, whose properties were evaluated during the storage time. The addition of CEE improved mechanical properties of the films: tensile strength increased fro m 27.7 MPa (control film) to 35.1 MPa (film with 200 g CEE/100 g gelatin) and the elongation at break increased from 22.3 % (control film) to 36.5 % (film with 200 g CEE/100 g gelatin). Water content was not affected by the addition of CEE, however soluble matter reduced compared to control film. The water vapor permeability for added films also reduced on average 24.1 %. Color parameters, opacity and gloss were affected by the incorporation of CEE. Microstructure analysis indicated changes in surface roughness and increase in roughness regarding the internal structure due to the growing concentration of CEE in the films. FTIR analysis showed peaks displacements associated to amides A, I and II for the added films. Films added CEE showed reduced transmittance for the UV/Vis region and increased transparency. The curcumin content increased linearly (y=0.6115x+6.6629, R2=0.9817) with increasing extract concentration. The antioxidant capacity increased was improved with the increase of extract concentration and antimicrobial activity (Staphylococcus aureus) was verified at concentrations above 5g CEE/100g gelatin. Thus, the film with CEE concentration of 200 g CEE/100 g gelatin was used for macadamia nut packaging. Regarding water content in the macadamia nut, significant differences in the first 30 day of storage were found according to the film (with or without CEE). However, no significant difference concerning water activity was found. After 60 days of storage nuts packaged with added film had their hardness increased and lower reactive substances (thiobarbituric acid). It can be concluded that the utilization of this system as active packaging for macadamia nut is possible.

As embalagens ativas têm ganhado destaque no mercado mundial, pois possibilitam a interação do alimento com o material da embalagem, permitindo a incorporação de compostos ativos. Dentre os compostos ativos, o extrato etanólico de cúrcuma (EEC) tem chamado atenção, devido suas propriedades antioxidante, antimicrobiana, dentre outras. Assim, os objetivos deste trabalho foram desenvolvimento, caracterização e aplicação de filmes à base de gelatina aditivados com EEC. Os filmes foram produzidos pela técnica de casting (2 g de gelatina/100 g de solução filmogênica (SF), 30 g de sorbitol/100 g de gelatina) e o EEC foi incorporado na SF, nas concentrações de 0, 5, 50, 100, 150 e 200 g EEC/100 g de gelatina. Os filmes foram caracterizados em relação às propriedades mecânicas, conteúdo de água, matéria solúvel, permeabilidade ao vapor de água, parâmetros de cor, opacidade, brilho, microestrutura, espectroscopia de infravermelho com transformada de Fourier (FTIR), barreira UV/Vis, transparência, teor de curcumina, atividade antioxidante e atividade antimicrobiana. O filme com os melhores resultados para as propriedades mecânicas, barreira UV/Vis e atividade antioxidante foi utilizado para embalar noz macadâmia e, as propriedades da noz foram avaliadas em função do tempo de estocagem. A incorporação do EEC melhorou as propriedades mecânicas dos filmes, a tensão de ruptura aumentou de 27,7 MPa (filme controle) para 35,1 MPa (filme com 200 g de EEC/100 g de gelatina) e a elongação na ruptura aumentou de 22,3 % (filme controle) para 36,5 % (filme com 200 g de EEC/100 g de gelatina). O conteúdo de água não foi influenciado pela adição do EEC, porém a matéria solúvel reduziu em relação ao filme controle. A permeabilidade ao vapor de água também reduziu em média 24,1 % para os filmes aditivados. Os parâmetros de cor, opacidade e brilho foram afetados pela incorporação do EEC. As análises de microestrutura indicaram alterações na rugosidade da superfície e um aumento na rugosidade da estrutura interna, em função do aumento da concentração de EEC nos filmes. A análise de FTIR mostrou deslocame ntos dos picos associados às amidas A, I e II para os filmes aditivados. Os filmes com EEC apresentaram reduzida transmitância na região UV/Vis e aumento da transparência. O teor de curcumina aumentou linearmente (y=0,6115x+6,6629, R2=0,9817) com o aumento da concentração do extrato. A capacidade antioxidante aumentou em função do aumento da concentração do EEC e a atividade antimicrobiana (Staphylococcus aureus) foi verificada para concentrações acima de 5 g de EEC/100 g de gelatina. Assim, o filme com concentração de EEC de 200 g de EEC/100 g de gelatina foi utilizado para embalar noz macadâmia. Em relação ao conteúdo de água da noz macadâmia foram observadas diferenças significativas em função do tipo de filme utilizado (com e sem ad ição de EEC) nos primeiros 30 dias de estocagem. Entretanto, para a atividade de água não foram observadas diferenças. Após 60 dias a dureza da noz macadâmia embalada com o filme aditivado foi superior e as substâncias reativas (ácido tiobarbitúrico) fora m inferiores. Pode-se concluir que é possível a utilização desse sistema como embalagem ativa para a noz macadâmia. / Active packaging has been receiving growing attention in the world market because it allows interaction between food and packaging material, thus enabling the incorporation of active compounds. Among active compounds, curcuma ethanol extract (CEE) has been highlighted mainly because its antioxidant and antimicrobial properties. The objectives of this study were the development, characterization and application of gelatin-based films added with CEE. The films were produced by casting technique (2 g gelatin/100 g filmogenic solution (FS), 30 g sorbitol/100 g gelatin) and CEE was added to FS at 6 concentrations (0, 5, 50, 100, 150 and 200 g CEE/100 g gelatin). The films were characterized regarding mechanical properties, water content, soluble matter, water vapor permeability, color parameters, opacity, gloss, microstructure, Fourier transform infrared spectroscopy (FTIR), light transmission, transparency, curcumin content, antioxidant activity, and antimicrobial activity. The film with the best results concerning mechanical properties, light transmission and antioxidant activity was selected to package macadamia nut, whose properties were evaluated during the storage time. The addition of CEE improved mechanical properties of the films: tensile strength increased fro m 27.7 MPa (control film) to 35.1 MPa (film with 200 g CEE/100 g gelatin) and the elongation at break increased from 22.3 % (control film) to 36.5 % (film with 200 g CEE/100 g gelatin). Water content was not affected by the addition of CEE, however soluble matter reduced compared to control film. The water vapor permeability for added films also reduced on average 24.1 %. Color parameters, opacity and gloss were affected by the incorporation of CEE. Microstructure analysis indicated changes in surface roughness and increase in roughness regarding the internal structure due to the growing concentration of CEE in the films. FTIR analysis showed peaks displacements associated to amides A, I and II for the added films. Films added CEE showed reduced transmittance for the UV/Vis region and increased transparency. The curcumin content increased linearly (y=0.6115x+6.6629, R2=0.9817) with increasing extract concentration. The antioxidant capacity increased was improved with the increase of extract concentration and antimicrobial activity (Staphylococcus aureus) was verified at concentrations above 5g CEE/100g gelatin. Thus, the film with CEE concentration of 200 g CEE/100 g gelatin was used for macadamia nut packaging. Regarding water content in the macadamia nut, significant differences in the first 30 day of storage were found according to the film (with or without CEE). However, no significant difference concerning water activity was found. After 60 days of storage nuts packaged with added film had their hardness increased and lower reactive substances (thiobarbituric acid). It can be concluded that the utilization of this system as active packaging for macadamia nut is possible.

M. Tech (Department of Chemistry, Faculty of Applied and Computer Sciences) Vaal University of Technology. / In this study, analytical method for determining the chlorinated phenols in water was developed using High Performance Liquid Chromatography. The following four compounds which are 2, 4, 6- Trichlorophenol (2, 4, 6 TCP), 3-chlorophenol (3CP), 2, 4- Dichlorophenol (2, 4 DCP) and 4-chloro-3-methylphenol (4C3MP) were identified and quantified with a High Performance Liquid Chromatography (HPLC). The validation parameters tested were,: linearity, trueness, precision, detection limit of quantitation, sensitivity, specificity, selectivity. The linear calibration ranges of five standard solution from 1-10 ppm. The linearity ranges between 0.9298-0.9813. The activated carbon based on the waste macadamia nutshell activated carbon (MAC) was investigated for its potential uses as an adsorbent for chlorinated phenols removal and compared with grafted macadamia nutshell activated carbon (GMAC). The adsorbent was characterized with Fourier transform infrared spectrophotometer (FTIR), scanning electron microscope (SEM) and thermo gravimetric analysis (TGA). The parameters such as pH, temperature, contact time, concentration and adsorbent were investigated by adsorption technique. The strata C18E has been used before for the same reason and therefore the research was based on mimic the functional group of solid phase extraction (SPE) into macadamia activated carbon (MAC). The functional groups in SPE C18E are benzene and octadecyl. MAC was grafted with strata C18E functional groups to compare its potential with the SPE. The pseudo-first-order and pseudo-second-order kinetic models were applied to verify the experimental data. The pseudo-second order exhibited the best fit for the kinetic studies for MAC adsorption. Chemical removal of chlorinated phenols from wastewater is necessary to reduce harmful products on the environment and human health. Chlorinated phenols have been previously listed as some of the highest priority contaminants and as well as mainly important capability carcinogenic toxins released from chemical plants. Their availability in water supplies was perceived by their bad taste and smell. The acceptable chlorinated phenols concentration in portable water is 1 (mg/l) base on the approval of world health organization. The permanent checking of chlorinated phenols in environmental samples has a greater significance and stresses highly effectiveness, common selectively and great sensitively methods. The maximum uptake of Phenol using weighed mass of MAC was found to be 78 % and for GMAC was 84% for both 2,4,6TCP. t=250 min, pH=5, Co=1mg/l, T = 25 oC and m = 0.3 g/l were the optimum condition for Phenol-MAC system and GMAC system. Over all analysis of equilibrium model analysis indicates the fitness of Langmuir isotherm model to Phenol MAC adsorption system, suggesting a monolayer adsorption of phenol on the surface of MAC. Phenol adsorption capacity of MAC was found to be decreasing with increase in temperature suggesting that the adsorption process was exothermic in nature, which was further supported by the negative values of change in enthalpy. Characterization of MAC and GMAC confirmed the mesoporous texture, highly carbonaceous nature and a higher effective surface area of 912 m2/g. The highest phenol uptake capacity of GMAC was found to be 8.0049 mg/g. The optimal conditions for various process parameters are t = 250 min, pH=5, Co=1mg/l, T = 25 oC and m = 0.3 g/l were the optimum condition for Phenol-GMAC system. Like Phenol-MAC system, the kinetics studies confirmed that Phenol-GMAC adsorption system can be described by pseudo- second-order kinetics model. Equilibrium model analysis indicates the fitness of Langmuir isotherm model to Phenol-MAC adsorption system, suggesting a monolayer adsorption of phenol on the surface of GMAC. Phenol adsorption capacity of GMAC was found to be decreasing with increase in temperature suggesting that the adsorption process was exothermic in nature, which was further supported by the negative values of change in enthalpy. The negative values of Gibb’s free energy suggested that adsorption of phenol onto GMAC was a spontaneous process.

Ph. D. (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology. / Driven by the need for sustainably sourced catalysts and the use of reaction systems that generate environmentally benign by-products, the present study aimed to deposit stable, dispersed palladium (Pd) nanoparticles on the modified surfaces of granular macadamia nutshell (MNS) biomass for catalytic reduction of hexavalent chromium [Cr(VI)] to trivalent chromium [Cr(III)]. Through wet impregnation with Pd(II) ions and subsequent hydrazinemediated reduction to Pd(0), Pd nanoparticles were embedded in a scaffold of polyethyleneimine grafted on bleached MNS previously coated with a chemically bound layer of polyglycidyl methacrylate. Visualization and imagery from scanning electron microscopy showed the formation of different layers of the polymeric coating and dispersed palladium resulting from surface modification and palladium nanoparticle synthesis, respectively. X-ray diffraction, energy-dispersive X-ray spectroscopic, and X-ray photoelectron spectroscopic analysis confirmed the formation of Pd on the modified MNS surface. An estimate of 5.0 nm for crystallite size was calculated by application of the Scherrer equation. The composite material, denoted Pd@PEI-MNS, exhibited catalytic activity in formic acidmediated Cr(VI) reduction. Through a one-factor-at-a-time experimental design, the activity of the Pd@PEI-MNS was illustrated to be dependent on solution pH; initial Cr(VI) concentration, initial formic acid concentration, and presence of competing anions; Pd@PEI-MNS dose; and temperature. Subsequent modeling of the Cr(VI) removal process by response surface methodology revealed that the most influential factor was Pd@PEI-MNS dose followed by temperature and formic acid concentration. The influence of initial Cr(VI) concentration, was surpassed by the dose-temperature and dose-formic acid concentration interactive effects. Elucidation of the Cr(VI) removal mechanism by XPS and FTIR demonstrated the active participation of surface –CH2OH functional groups, the bulk of which originated from the reduction of esters of the grafted ligands. Replacement of formic acid with hydrochloric acid in the reaction medium limited the Cr(VI) removal process to adsorption with non-extensive redox reaction with –CH2OH groups. Where the redox reactions converted formic acid to carbon dioxide, the –CH2OH groups were converted to –COO– groups.

A macadâmia (Macadamia integrifolia Maiden & Betche) é uma nogueira arbórea originária das florestas tropicais australianas. Sua distribuição natural ocorre por quase toda a costa leste da Austrália. No Brasil, foi introduzida em 1931, mas sua expansão aconteceu a partir da década de 70. As variedades comerciais são originadas de duas espécies, Macadamia integrifolia e M. tetraphylla, e seus híbridos. As informações sobre pedigree são geralmente incompletas e a identificação das variedades algumas vezes não é clara. O uso de técnicas moleculares auxilia em diversas fases dos programas de melhoramento, inclusive na caracterização do material genético e seleção de parentais envolvidos nos cruzamentos. A partir do uso de técnicas moleculares (microssatélites e diversity array technology), as 28 variedades que compõe o germoplasma brasileiro foram genotipadas com a finalidade de investigar a estrutura e a divergência genética entre estas. Foram utilizados 29 primers flanqueadores de locos microssatélites e 462 marcas de diversity array technology. A análise pelo programa Structure apresentou a formação de duas subpopulações: uma com a maioria das variedades desenvolvidas no Havaí/USA e Brasil, e outra composta pelas variedades desenvolvidas na Austrália e três variedades brasileiras. A análise da diversidade genética detectou valores medianos de heterozigosidade para o conjunto de variedades ( = 0,46 e = 0,43), com indicação de um pequeno excesso de homozigoto em relação ao esperado sob Equilíbrio de Hardy-Weinberg. A estimativa do índice de fixação (F = 0,067) para o conjunto de subpopulações apresentou grande variação, porém na média, foi baixo e não diferente de zero. Os resultados também mostram que a maior parte da diversidade genética do germoplasma está dentro de subpopulações ( q = 0,041). O índice de fixação devido ao sistema reprodutivo também variou entre os locos analisados, mas na média foi igualmente baixo e não diferente de zero ( f = 0,027). Os valores das Distâncias de Jaccard variaram entre 0,00 e 0,787 enquanto que as Distâncias de Roger Modificada variaram entre 0,227 e 0,671. O dendrograma UPGMA formado pelas Distâncias de Jaccard formou três grupos enquanto que pelas Distâncias de Roger Modificada formou dois grupos, sendo possível distinguir somente o grupo externo formado pelas duas espécies de grevílea. A falta de divergência entre alguns pares de variedades foi inesperada, assim como o não agrupamento entre variedades identificadas com o mesmo nome ou que apresentam histórico de parentesco. Da mesma forma, as duas subpopulações discriminadas pelo programa Structure não formaram agrupamento específico em ambos os dendrogramas. Os resultados das análises dos Componentes Principais foram coerentes aos obtidos nos dendrogramas formando os mesmos agrupamentos. / Macadamia (Macadamia integrifolia Maiden and Betche) is a nut crop tree widespread across eastern Australia. Although has been introduced in Brazil in 1931, just in the past 20 years its cultivated area has expanded more significantly. Commercial varieties are originated from Macadamia integrifolia and M. tetraphylla, as well as its hybrids. The information on pedigree is generally incomplete and the identification of varieties is sometimes not so clear. Molecular techniques could provide genetic information useful for breeding programs, such as, the kinship (relatedness) between individuals. Molecular techniques (microsatellites and diversity array technology) was used to genotype all 28 varieties that composes Brazils germoplasma with the purpose to investigate the structure and the genetic divergence between these varieties. Twenty nine microsatellites locus and 462 markers of diversity array was used. Analysis using the Structure software showed evidence of two subpopulations: one with the majority of the varieties developed in the Hawaii/USA and Brazil, and another with varieties developed in Australia and three in Brazil. The analysis of genetic diversity detected medium values of heterozigosis ( = 0.46 and = 0.43), with indication of a small excess of homozygotes in relation the expected value under Hardy- Weinberg equilibrium. The estimate of inbreeding coefficient showed great variation (from - 0.522 to 0.558), however in the average (F = 0.067) it was low and statistically not different from zero. The results also showed that most of the genetic diversity is within subpopulations ( q = 0.041). The inbreeding due to the reproductive system varied between analyzed loci, but on average it was low and statistically not different from zero ( f = 0.027). Values of Jaccard distances ranged from 0 to 0.787, whereas the modified Rogers distances ranged from 0.227 to 0.671. UPGMA Cluster analysis from Jaccard distances formed three groups, whereas modified Rogers distances of formed two groups. In the latter, it is possible to distinguish only the external group formed by the two species from Grevilea spp. For some varieties that we expected to be clustered together were unexpected assigned to different clusters. On the other hand, for some varieties that we expected to be placed in different clusters were unexpected clustered together. Unexpected, the two subpopulations discriminated in the analysis (Structure) did not form specific groups when using both Jaccard and modified Rogers distances. The results of Principal Coordinate Analysis were coherent with the UPGMA analyses.

A macadâmia (Macadamia integrifolia Maiden & Betche) é uma nogueira arbórea originária das florestas tropicais australianas. Sua distribuição natural ocorre por quase toda a costa leste da Austrália. No Brasil, foi introduzida em 1931, mas sua expansão aconteceu a partir da década de 70. As variedades comerciais são originadas de duas espécies, Macadamia integrifolia e M. tetraphylla, e seus híbridos. As informações sobre pedigree são geralmente incompletas e a identificação das variedades algumas vezes não é clara. O uso de técnicas moleculares auxilia em diversas fases dos programas de melhoramento, inclusive na caracterização do material genético e seleção de parentais envolvidos nos cruzamentos. A partir do uso de técnicas moleculares (microssatélites e diversity array technology), as 28 variedades que compõe o germoplasma brasileiro foram genotipadas com a finalidade de investigar a estrutura e a divergência genética entre estas. Foram utilizados 29 primers flanqueadores de locos microssatélites e 462 marcas de diversity array technology. A análise pelo programa Structure apresentou a formação de duas subpopulações: uma com a maioria das variedades desenvolvidas no Havaí/USA e Brasil, e outra composta pelas variedades desenvolvidas na Austrália e três variedades brasileiras. A análise da diversidade genética detectou valores medianos de heterozigosidade para o conjunto de variedades ( = 0,46 e = 0,43), com indicação de um pequeno excesso de homozigoto em relação ao esperado sob Equilíbrio de Hardy-Weinberg. A estimativa do índice de fixação (F = 0,067) para o conjunto de subpopulações apresentou grande variação, porém na média, foi baixo e não diferente de zero. Os resultados também mostram que a maior parte da diversidade genética do germoplasma está dentro de subpopulações ( q = 0,041). O índice de fixação devido ao sistema reprodutivo também variou entre os locos analisados, mas na média foi igualmente baixo e não diferente de zero ( f = 0,027). Os valores das Distâncias de Jaccard variaram entre 0,00 e 0,787 enquanto que as Distâncias de Roger Modificada variaram entre 0,227 e 0,671. O dendrograma UPGMA formado pelas Distâncias de Jaccard formou três grupos enquanto que pelas Distâncias de Roger Modificada formou dois grupos, sendo possível distinguir somente o grupo externo formado pelas duas espécies de grevílea. A falta de divergência entre alguns pares de variedades foi inesperada, assim como o não agrupamento entre variedades identificadas com o mesmo nome ou que apresentam histórico de parentesco. Da mesma forma, as duas subpopulações discriminadas pelo programa Structure não formaram agrupamento específico em ambos os dendrogramas. Os resultados das análises dos Componentes Principais foram coerentes aos obtidos nos dendrogramas formando os mesmos agrupamentos. / Macadamia (Macadamia integrifolia Maiden and Betche) is a nut crop tree widespread across eastern Australia. Although has been introduced in Brazil in 1931, just in the past 20 years its cultivated area has expanded more significantly. Commercial varieties are originated from Macadamia integrifolia and M. tetraphylla, as well as its hybrids. The information on pedigree is generally incomplete and the identification of varieties is sometimes not so clear. Molecular techniques could provide genetic information useful for breeding programs, such as, the kinship (relatedness) between individuals. Molecular techniques (microsatellites and diversity array technology) was used to genotype all 28 varieties that composes Brazils germoplasma with the purpose to investigate the structure and the genetic divergence between these varieties. Twenty nine microsatellites locus and 462 markers of diversity array was used. Analysis using the Structure software showed evidence of two subpopulations: one with the majority of the varieties developed in the Hawaii/USA and Brazil, and another with varieties developed in Australia and three in Brazil. The analysis of genetic diversity detected medium values of heterozigosis ( = 0.46 and = 0.43), with indication of a small excess of homozygotes in relation the expected value under Hardy- Weinberg equilibrium. The estimate of inbreeding coefficient showed great variation (from - 0.522 to 0.558), however in the average (F = 0.067) it was low and statistically not different from zero. The results also showed that most of the genetic diversity is within subpopulations ( q = 0.041). The inbreeding due to the reproductive system varied between analyzed loci, but on average it was low and statistically not different from zero ( f = 0.027). Values of Jaccard distances ranged from 0 to 0.787, whereas the modified Rogers distances ranged from 0.227 to 0.671. UPGMA Cluster analysis from Jaccard distances formed three groups, whereas modified Rogers distances of formed two groups. In the latter, it is possible to distinguish only the external group formed by the two species from Grevilea spp. For some varieties that we expected to be clustered together were unexpected assigned to different clusters. On the other hand, for some varieties that we expected to be placed in different clusters were unexpected clustered together. Unexpected, the two subpopulations discriminated in the analysis (Structure) did not form specific groups when using both Jaccard and modified Rogers distances. The results of Principal Coordinate Analysis were coherent with the UPGMA analyses.

MSc (Zoology) / Department of Zoology / See the attached abstract below