O objetivo do presente estudo foi medir experimentalmente a solubilidade do óleo de café verde em dióxido de carbono supercrítico em condições preestabelecidas de pressão (P) e temperatura (T), e a partir dos dados experimentais estabelecer ajustes em modelos termodinâmicos que empregam a equação de estado (EDE) de Peng-Robinson com a regra de mistura clássica de van der Waals para predição do equilíbrio de fases. Foi obtido óleo a partir de grãos de café verde (Coffea arabica), cultivar (cv.) Catuaí Amarelo moído (dm de 0,8409 mm) usando CO2 supercrítico, nas condições de 40, 50, 60, 70, 80 °C e nas pressões de 300 e 350 bar. A solubilidade foi medida pelos métodos dinâmico e estático nas mesmas condições. Foi determinado o perfil de ácidos graxos por cromatografia gasosa acoplada à espectrometria de massas (CG/EM) e, a partir destes resultados, a composição em triacilgliceróis (TAGs) foi estimada. Foram determinadas as propriedades físico-químicas dos TAGs pelo método de contribuição de grupos. Nas condições de P e T estudadas, os maiores rendimentos do óleo de grãos de café verde, 7,58% e 7,60%, foram obtidos nas condições de 70 °C e 300 bar e 80 °C e 350 bar, respectivamente. Normalmente o rendimento do óleo aumentou com o aumento da temperatura, com exceção das condições de 80 °C e 300 bar e 70 °C e 350 bar. O aumento do rendimento com a temperatura reflete nos dados experimentais da solubilidade (0,0099 a 0,026 g/gCO2) que aumentou com a temperatura a 300 e 350 bar para o método estático e para o método dinâmico a 350 bar (0,0058 a 0,0065 g/gCO2). Um comportamento distinto ocorreu com a medida de solubilidade pelo método dinâmico a 300 bar. Neste caso a solubilidade diminuiu com o aumento da temperatura. Para a maioria das condições de P e T estudadas, o comportamento da solubilidade foi semelhante em função destas variáveis, o mesmo para os métodos estático e dinâmico, no entanto com ordens de grandezas distintas. As condições de extração não influenciaram na composição dos ácidos graxos no óleo nem na predição dos TAGs presentes. Os TAGs apresentaram variações entre número de carbonos (C50 a C58). As propriedades físico-químicas dos seis principais TAGs presentes no óleo de grãos de café verde (PSL, PLL, PLP, PLO, PLA e POP), temperatura do ponto de ebulição normal (Tb), temperatura crítica (Tc), pressão crítica (Pc) e fator acêntrico (ω) foram estimadas por métodos de contribuição de grupos. Estas variáveis são dados de entrada para a predição do equilíbrio de fases entre o óleo de grãos de café verde, representado pela mistura dos seis TAGs em maior concentração neste óleo, e o CO2 supercrítico. Os valores de Tb dos TAGs variaram de 821,52 a 844,50 K, os valores de Tc de 909,12 a 930,02 K, os valores de Pc de 5,0115 a 4,7221 bar e o ω de 1,5704 a 1,7452. Os dados de propriedades físicas e da solubilidade convertida em fração molar foram usados para predizer os parâmetros de interação binária da regra de mistura clássica de van der Waals entre cada TAG e o CO2 supercrítico, já que estes parâmetros também são dados de entrada para a modelagem termodinâmica que emprega a EDE de Peng-Robinson. No entanto, o programa não rodou, não sendo possível este cálculo, nem tão pouco a predição do equilíbrio de fases. Os dados experimentais da solubilidade do óleo de grãos de café verde em CO2 supercrítico determinados pelos métodos estático e dinâmico indicou que àqueles determinados pelo método estático são mais precisos e confiáveis. / The objective of this study was to experimentally measure the solubility of green coffee oil in supercritical carbon dioxide under predetermined pressure (P) and temperature (T) conditions and, from the experimental data, establish thermodynamic models that use the Peng-Robinson equation of state (EOS) and the classic mixing rule of van der Waals to predict phase equilibrium. The oil was obtained from ground green coffee beans (Coffea arabica L.) cultivar (cv.) Yellow Catuaí (dm of 0.8409 mm) using supercritical CO2 under temperatures of 40, 50, 60, 70 and 80 °C and pressures of 300 and 350 bar. The solubility was measured by dynamic and static methods under the same conditions. The fatty acid profile was determined by gas chromatography-mass spectrometry (GC/MS) and, from these results, the composition of triacylglycerols (TAGs) was estimated. Physicochemical properties of TAGs were determined by the group contribution method. In the studied conditions of P and T, higher yields of green coffee beans oil, 7.58% and 7.60%, were obtained at 70 °C and 300 bar and 80 °C and 350 bar, respectively. Normally, the oil yield increased with increasing temperatures, except for the conditions of 80 °C and 300 bar and 70 °C and 350 bar. The increase of yield with temperature reflects in the experimental solubility data (from 0.0099 to 0.026 g/g CO2), which, also increased with T at 300 and 350 bar for the static method and, for the dynamic method, at 350 bar (from 0.0058 to 0.0065 g/g CO2). A different behavior occurred with the solubility measured by dynamic method at 300 bar. In this case, the solubility decreased with increasing temperature. For most of the P and T conditions studied, the solubility behavior was similar in function of these variables, the same for static and dynamic methods, but with different magnitude orders. The extraction conditions did not affect the composition of fatty acids in the oil and nor the TAGs prediction. The TAGs showed variations between carbon numbers (from C50 to C58). The physicochemical properties of the six major TAGs present in green coffee bean oil (PSL, PLL, PLP, PLO, PLA and POP), boiling temperature (Tb), critical temperature (Tc), critical pressure (Pc) and acentric factor (ω) were estimated by group contribution methods. These are input variables for the prediction for the phase equilibrium between the green coffee oil, represented by the mixture of the six TAGs in higher concentration in this oil, and supercritical CO2. The Tb values of TAG ranged from 821.52 to 844.50 K, Tc values from 909.12 to 930.02 K, Pc values from 5.0115 to 4.7221 bar and ω from 1, 5704 to 1.7452. The data of physical properties and solubility converted to mole fraction were used to predict the binary interaction parameters of the classic mixing rule of van der Waals between each TAG and supercritical CO2, since these are also input parameters for the thermodynamic modeling that use Peng-Robinson EOS. However, the program did not run and this calculation was not possible, nor the prediction for the phase equilibrium. The experimental data on the solubility of the green coffee beans oil in supercritical CO2 determined by static and dynamic methods indicated that those determined by the static method are more accurate and reliable.

O pólen apícola, produto da aglutinação do pólen das flores com néctar e substâncias salivares das abelhas, tem sido promovido como suplemento da dieta humana por apresentar propriedades nutricionais e bioativas. Sessenta e duas amostras de pólen apícola desidratado foram avaliadas para as análises de compostos fenólicos, flavonoides, atividade antioxidante por três métodos (DPPH, sistema β-caroteno e ORAC), origem botânica, qualidade comercial (umidade, cinzas, lipídeos, proteínas e carboidratos) e sanitária (bolores e leveduras, aeróbios mesófilos, coliformes totais, E.coli, clostrídios sulfito redutores e S.aureus.), além da atividade antimicrobiana (Candida albicans, Escherichia coli, Staphylococcus aureus). Os valores obtidos para compostos fenólicos e flavonoides totais variaram de 12,60 a 84,22 mg GAE/g de pólen apícola (GAE: equivalentes em ácido gálico) e 1,90 a 36,85 mg de quercetina/g de pólen apícola respectivamente. O EC50, determinado pelo método do DPPH, variou de 0,35 a 13,42 mg pólen apícola/mL de extrato. Os extratos de pólen apícola apresentaram valores entre 52,58 e 98,37 % para o método do β-caroteno. Quando quantificada por ORAC, a atividade antioxidante medida ficou entre 132,98 e 575,85 µmol eq. trolox/g pólen apícola. Na avaliação da qualidade comercial foram obtidos os valores de 3,06% a 8,12% para umidade, de 1,94 a 4,61%, para cinzas, de 3,35 a 10,96% para lipídeos; de 17,73 a 34,73% para as proteínas, de 11,86 a 25,71% e de 2,77 a 15,87% para os açúcares frutose e glicose, respectivamente. Verificou-se que a presença do pólen apícola inibiu o crescimento de todos os microrganismos estudados. Candida albicans foi a mais resistente e o Staphylococcus epidermides foi o mais sensível. Observou-se 36 tipos polínicos diferentes, destacando-se: Cocos nucifera sp., Mimosa scabrella (Benth.), Mimosa caesalpiniaefolia sp., Eucalyptus sp., Myrcia sp., Asteraceae, Poaceae., Euphorbiaceae e Brassica que ocorreram com maior frequência entre as amostras estudadas. Foram observadas somente correlações moderadas e fracas entre os tipos polínicos presentes e os parâmetros avaliados para as amostras desidratadas de pólen apícola. / Bee pollen, a product of agglutination of flower pollen with nectar and bee salivary substances, has been promoted as a dietary supplement for human because of its nutritional and bioactive properties. Sixty-two samples of dehydrated bee pollen were analyzed for phenolics, flavonoids, antioxidant activity using three methods (DPPH, βcarotene and ORAC), botanical composition, commercial quality (moisture, ashes, lipids, proteins, carbohydrates), hygiene (aerobic mesophiles, yeasts and moulds, coliforms, Escherichia coli, Staphylococcus aureus and sulfite-reducing Clostridium), and antimicrobial activity (Candida albicans, Escherichia coli, Staphylococcus aureus). The obtained values for total phenolics ranged from 12.60 to 84.22 mg GAE/g bee pollen (GAE: gallic acid equivalents) while for total flavonoids ranged from 1.90 and 36.85 mg quercetin/g bee pollen. The EC50, determined by the DPPH method, ranged from 0.35 to 13.42 mg bee pollen/ml of extract. The bee pollen extracts showed values between 52.58 and 98.37% by β- carotene method. When measured by ORAC, antioxidant activity was between 132.98 and 575.85 µmols eq. trolox/g bee pollen. In the evaluation of commercial quality, the following results were achieved: 3.06% to 8.12% for moisture, 1.94 to 4.61% for ashes, 3.35 to 10.96% for lipids, 17.73 to 34.73% for proteins, from 11.86 to 25.71% and 2.77 to 15.87% for the carbohydrates glucose and fructose respectively. It was verified that the presence of the bee pollen inhibited the growth of all microorganisms studied. Candida albicans was the more resistant and Staphylococcus epidermides the more sensitive. Thirty-three pollen-types were identified mainly Cocos nucifera sp., Mimosa scabrella (Benth.) sp., Mimosa caesalpiniaefolia sp., Eucalyptus sp., Myrcia sp., Asteraceae sp., Poaceae sp., Euphorbiaceae sp. and Brassica sp. that occurred more frequently among the samples studied. It was observed only moderate and weak correlations between the pollen types present and the evaluated parameters for dehydrated samples of bee pollen

Parmi les méthodologies d’appréciation du danger ayant connu une forte croissance ces dernières décennies figurent le Control Banding (CB). Selon une estimée du NIOSH (National Institute for Occupational Safety and Health), cette approche qualitative a été développé dans l’industrie pharmaceutique dans un but concret de protéger près de 90% de travailleurs n’ayant pas accès à des services de santé, de sécurité et d’hygiène au travail. Actuellement, cette approche peut être adaptée aux spécificités des nanomatériaux (NMs) pour lesquelles peu de connaissances scientifiques sont disponibles sur les risques potentiels pour la santé et pour la sécurité des travailleurs. Au cours des dernières années, différentes études ont porté sur l’application de l’approche CB et plusieurs pays ont développé leur propre méthode adaptée aux NMs. Par contre, tous les modèles développés sont basés sur des critères qualitatifs du danger et de l’exposition. Une approche semi-quantitative permettrait de mieux gérer les dangers liés à la manipulation des NMs. L’objectif de ce mémoire était de développer une approche semi-quantitative d’évaluation des dangers sur la base d’une approche de CB. Pour ce faire, une analyse systématique de la littérature scientifique des 20 dernières années sur l’approche de CB a été effectué. Les bases de données Toxline, Pubmed et Google Scholar ont été consultées, couvrant la période de janvier 1996 à novembre 2016, en utilisant 4 mots-clés: control banding, nanomaterials, physicochemical, biological characteristics. Cette recherche a permis d’identifier 982 articles, dont 11% (91) furent retenus en première intention pour au final en garder 6 % (51/982). Il ressort de cette revue que le CB est une approche complémentaire aux méthodes d’évaluation quantitative et que les outils CB développés pour les NMs sont tous de nature qualitative, en réponse à une exposition. Une approche semi-quantitative où il y a maillage entre la caractérisation biologique avec les tests in vitro et la caractérisation physicochimique par des analyses chimiques pour mieux caractériser le niveau de dangérosité des NMs tel que présenté dans le présent mémoire permettrait une utilisation plus judicieuse du CB. Cette approche novatrice du CB dépasse largement l’utilisation que l’on en fait actuellement en hygiène du travail, devrait accroître la confiance dans le jugement des experts en santé au travail, afin d’orienter les travailleurs et la population générale vers une utilisation sécuritaire des NMs. / Among the hazards assessment methodology that has grown exponentially during the last decade, mention Control Banding (CB). According to the National Institute for Occupational Safety and Health (NIOSH), this qualitative approach originally developed in the pharmaceutical industry, aims to protect approximately 90% or 2.7 billion workers that do not have access to occupational safety, health, and hygiene. Currently, this approach can be adapted to the specificities of nanomaterials (NMs), considering the significant lack of scientific knowledge about their potential health and safety risks to workers. In recent years, several CB models have been developed, and many countries have created their own nano-specific CB instruments. However, a semi-quantitative approach would better managing the hazards of handling nanomaterials in the workplace. This thesis aimed to perform a systematic literature review over the past 20 years about the CB approach and then to suggest a semi-quantitative hazard assessment. The official Web pages of the databases Toxline, Pubmed and Google Scholar were used, covering the literature from January 1996 to November 2016, with use of the 4 keywords to locate relevant articles: Control Banding, nanomaterials, physico-chemical, biological characteristics. These searches yielded a total of 982 articles, 11% (91) were retained to eventually retain 6% (51/982). This review shows that the CB approach is an interesting and complementary methodology to quantitative evaluation methods and the CB tools developed for NMs are all qualitative in nature, in response to an exposure and adapted to different work environments. It is possible to make better use by proposing a semi-quantitative approach based on physicochemical and toxicity parameters of NMs to better characterize their degree of dangerousness. We propose here an original methodology proposing the interaction of in vitro tests and chemical analyzes. This innovative Control Banding approach should increase confidence in the judgment of experts and industry, as well as to guide both exposed workers and the uses of NMs in this industry.

Stárnutí teplonosných kapalin na organické bázi je dlouhodobým problémem, který je znám od počátku jejich používání. První část této disertační práce je tak věnována případové studii funkčního experimentálního systému, který byl jako nový naplněn teplonosnou kapalinou na bázi propan-1,2-diol a pozorován po období 7 let. Pro analýzu stárnutí kapaliny v tomto systému byly sledovány základní provozní vlastnosti kapaliny jako jsou hustota, viskozita, teplota tuhnutí, pH a obsah kovů. Skrze tyto vlastnosti tak bylo sledováno stárnutí kapaliny nepřímo. Přímé sledování stárnutí bylo posléze provedeno analýzou degradačních produktů, jako jsou organické kyseliny a změny ve složení směsi pomocí izotachoforézy a hmotnostní spektrometrie. Pro srovnání byly taktéž analyzovány vybrané vzorky z několik dalších systémů plněných identickou kapalinou s prokazatelně pokročilou formou degradace. V druhé části práce jsou představeny základní fyzikálně-chemické vlastnosti směsí propan-1,3-diolu s vodou a jejich analytické hodnocení a matematické modelování pro universální použití jakožto nového základu pro nemrznoucí teplonosné kapaliny. Na základě dostupných informací je pak hodnocena použitelnost této směsi. Výhoda propan-1,3-diolu je spatřována především ve výrobě z obnovitelných zdrojů a v některých fyzikálních a chemických vlastnostech, které dle dosavadních poznatků předčívají doposud používané glykolové směsi.

PhD (Agric) (Food Science and Technology) / Department Food Science and Technology / In recent years, there has been a lot of interest in orange fleshed sweet potato (OFSP) [Ipomoea batatas (L.) Lam] cultivar, as a cheaper source of vitamin A. In Southern Africa, reports have shown that one in every three children has deficiency in vitamin A. This study investigated the variations in β-carotene (vitamin A precursor) content among selected OFSP cultivars grown in Limpopo Province, South Africa. In addition, the study investigated the effects of location on functional properties, total carotenoids and antioxidant profile of the sweet potato flour as well as their physicochemical, functional and nutritional properties. Four (4) sweet potato cultivars [Dagga, Bophelo, Impilo (orange fleshed) and Mvuvhelo (cream fleshed)] were obtained from two locations, namely, University of Venda (Univen) agricultural experimental farm and Tshiombo irrigation scheme (Tshiombo) and analysed for pasting, functional, physicochemical and nutritional properties. The sweet potato flours from these two locations were also analysed by computed tomographic (CT) scans for flour particle density. Mineral and microstructure of OFSP flours were analysed by scanning electron microscope (SEM). All measurements, except the tristimulus L* a* b* and other colour parameters from five replicates, were performed in triplicate. Statistical analysis was performed using a one-way analysis of variance and means were separated using Duncan’s multiple range test; P < 0.05 was considered to be statistically significant. Pearson’s correlation coefficients were used to determine the correlation among functional, physicochemical, nutritional and pasting properties of sweet potato flour. β-carotene content varied significantly between the two locations from 70.98 ± 0.8 μg/g (Tshiombo) to 86.09 ± 2.0 μg/g (Univen), among cultivars from 1.71 ± 0.0 μg/g (Mvuvhelo) to 201.50 ± 1.0 μg/g (Dagga) and among orange fleshed (Dagga, Bophelo and Impilo) flours from 28.38 ± 0.2 μg/g (Impilo) to 201.50 ± 1.0 μg/g (Dagga). There was a similar trend in the contents of α-carotene to that of β-carotene from the two locations, which ranged from 0.63 ± 0.0 mol/L (Tshiombo) to 1.01 ± 0.0 mol/L (Univen). Mvuvhelo had significantly the lowest α-carotene content (0.50 ± 0.0 mol/L) and Impilo the highest (1.28 ± 0.0 mol/L). The total carotenoids was highest for Impilo (7.56 μg/g) and lowest for Mvuvhelo (1.33 ± 0.1 μg/g) but did not vary significantly (P > 0.05) between ii the locations. The antioxidant activity, based on 2, 2-diphenyl-1picrylhydrazyl (DPPH) free radical scavenging activity, was significantly highest in Bophelo (63.37 ± 0.8 mMAAE ml-1) and lowest in Dagga (26.93 ± 1.4 mMAAE ml-1) flours. The ferric reducing antioxidant power (FRAP) varied significantly across the locations and among the cultivars and ranged from 14.45 ± 0.3 μMTE ml-1 (Tshiombo) to 17.40 ± 1.1 μMTE ml-1 (Univen). FRAP was significantly highest in Impilo (21.12 ± 2.1 μMTE ml-1) and lowest in Mvuvhelo (8.16 ± 2.0 μMTE ml-1). Total carotenoid content positively correlated with DPPH (0.486*), FRAP (0.830**), β-carotene (0.370*), and α-carotene (0.424*). The antioxidant content and the radical scavenging activity were significantly correlated (0.563**). Vitamin A content was significantly lowest (6.88 ± 0.38 μg/g retinol) in Dagga flour and highest (7.97 ± 0.25 μg/g) in Impilo flour. Protein content varied significantly across the two locations and ranged from 4.23% (Tshiombo) to 7.16% (Univen). Dagga had significantly the lowest (3.47%) protein content while Impilo had the highest (7.53%). The fat content of the flours varied significantly between the two locations ranging from 0.63% (Tshiombo) to 1.01% (Univen). The protein content was positively correlated 0.594** and 0.421* to vitamin A and fat contents respectively. The Bophelo colour luminosity was significantly lower (L* 76.2) than the other two OFSP, Dagga (L* 83.51) and Impilo (L* 82.07). Bophelo a* (14.09) also differed significantly across all sweet potato cultivars. All cultivars differed significantly in b* values. Colour intensity (ΔE*) ranged from 15.87 to 38.48 for Mvuvhelo and Bophelo, respectively. Chroma ranged from 87.52 to 84.95 for Dagga and Mvuvhelo respectively. Total starch content was significantly different in all sweet potato cultivars and ranged from 244.07 μg/100 g (Bophelo) to 325.04 mg/g (Dagga). Resistant starch differed significantly in all sweet potato cultivars ranging from 1.21 μg/100 g dwb (Bophelo) to 7.07 μg/100 g dwb (Impilo). Ash content was significantly different in all cultivars and ranged from 3.17% (Dagga) to 3.79% (Bophelo). Water holding capacity (WHC) varied significantly across the two locations and ranged from 1.44 g H2O/g DM (Tshiombo) to 1.72 g H2O/g DM (Univen). Bophelo had significantly the lowest (1.27 g H2O/g DM) WHC and Impilo the highest (1.99 g H2O/g DM). The ash content negatively correlated to total starch (-0.928**) but positively iii correlated to WHC (0.654**). Peak viscosity differed significantly across all cultivars under study and ranged from 126.54 RVU (Bophelo) to 302.36 RVU. (Dagga). There was significant difference in trough viscosity across all cultivars ranging from 55.97 RVU (Impilo) to 280.78 RVU (Dagga). There were significant differences in the final viscosity across all cultivars ranging from 78.99 RVU (Impilo) to 319.26 (Dagga). Peak time viscosity varied significantly across all cultivars ranging from 3.87 min (Impilo) to 8.47 min. (Bophelo). Dagga cultivar had significantly the highest pasting temperature (94.16oC) and Bophelo the lowest (77.75oC). The setback viscosity was significantly highest 51.10 RVU (Mvuvhelo) and lowest 23.01 RVU (Impilo). All cultivars from the two locations consistently showed high potassium content ranging from 0.46% (Impilo) to 1.38% (Dagga) as compared to other minerals such as magnesium, calcium and chlorine which ranged from 0.16% (Impilo) to 0.34%. (Dagga). The CT scans revealed that there was a possibility of evaluating the effect of location on the density of granules of sweet potato flour and also the inherent differences in granular distribution of various sweet potato cultivars. SEM revealed high amounts of potassium, magnesium and chlorine. A profile of physicochemical and functional properties of flour of some of the OFSP cultivars produced in Limpopo province, South Africa has been drawn. This study also highlights the nutritional quality of the flour from four sweet potato cultivars and provides a ranking of flour to help the producers in the selection process. Bophelo flour was ranked the highest in terms of β- and, α-carotenes, total carotenoids and antioxidant capacity while Impilo was ranked highest in terms of functional properties and ash content. This study has highlighted significant differences in a number of parameters measured among the sweet potato cultivars. Therefore, in order to derive the maximum benefit from aIn recent years, there has been a lot of interest in orange fleshed sweet potato (OFSP) [Ipomoea batatas (L.) Lam] cultivar, as a cheaper source of vitamin A. In Southern Africa, reports have shown that one in every three children has deficiency in vitamin A. This study investigated the variations in β-carotene (vitamin A precursor) content among selected OFSP cultivars grown in Limpopo Province, South Africa. In addition, the study investigated the effects of location on functional properties, total carotenoids and antioxidant profile of the sweet potato flour as well as their physicochemical, functional and nutritional properties. Four (4) sweet potato cultivars [Dagga, Bophelo, Impilo (orange fleshed) and Mvuvhelo (cream fleshed)] were obtained from two locations, namely, University of Venda (Univen) agricultural experimental farm and Tshiombo irrigation scheme (Tshiombo) and analysed for pasting, functional, physicochemical and nutritional properties. The sweet potato flours from these two locations were also analysed by computed tomographic (CT) scans for flour particle density. Mineral and microstructure of OFSP flours were analysed by scanning electron microscope (SEM). All measurements, except the tristimulus L* a* b* and other colour parameters from five replicates, were performed in triplicate. Statistical analysis was performed using a one-way analysis of variance and means were separated using Duncan’s multiple range test; P < 0.05 was considered to be statistically significant. Pearson’s correlation coefficients were used to determine the correlation among functional, physicochemical, nutritional and pasting properties of sweet potato flour. β-carotene content varied significantly between the two locations from 70.98 ± 0.8 μg/g (Tshiombo) to 86.09 ± 2.0 μg/g (Univen), among cultivars from 1.71 ± 0.0 μg/g (Mvuvhelo) to 201.50 ± 1.0 μg/g (Dagga) and among orange fleshed (Dagga, Bophelo and Impilo) flours from 28.38 ± 0.2 μg/g (Impilo) to 201.50 ± 1.0 μg/g (Dagga). There was a similar trend in the contents of α-carotene to that of β-carotene from the two locations, which ranged from 0.63 ± 0.0 mol/L (Tshiombo) to 1.01 ± 0.0 mol/L (Univen). Mvuvhelo had significantly the lowest α-carotene content (0.50 ± 0.0 mol/L) and Impilo the highest (1.28 ± 0.0 mol/L). The total carotenoids was highest for Impilo (7.56 μg/g) and lowest for Mvuvhelo (1.33 ± 0.1 μg/g) but did not vary significantly (P > 0.05) between ii the locations. The antioxidant activity, based on 2, 2-diphenyl-1picrylhydrazyl (DPPH) free radical scavenging activity, was significantly highest in Bophelo (63.37 ± 0.8 mMAAE ml-1) and lowest in Dagga (26.93 ± 1.4 mMAAE ml-1) flours. The ferric reducing antioxidant power (FRAP) varied significantly across the locations and among the cultivars and ranged from 14.45 ± 0.3 μMTE ml-1 (Tshiombo) to 17.40 ± 1.1 μMTE ml-1 (Univen). FRAP was significantly highest in Impilo (21.12 ± 2.1 μMTE ml-1) and lowest in Mvuvhelo (8.16 ± 2.0 μMTE ml-1). Total carotenoid content positively correlated with DPPH (0.486*), FRAP (0.830**), β-carotene (0.370*), and α-carotene (0.424*). The antioxidant content and the radical scavenging activity were significantly correlated (0.563**). Vitamin A content was significantly lowest (6.88 ± 0.38 μg/g retinol) in Dagga flour and highest (7.97 ± 0.25 μg/g) in Impilo flour. Protein content varied significantly across the two locations and ranged from 4.23% (Tshiombo) to 7.16% (Univen). Dagga had significantly the lowest (3.47%) protein content while Impilo had the highest (7.53%). The fat content of the flours varied significantly between the two locations ranging from 0.63% (Tshiombo) to 1.01% (Univen). The protein content was positively correlated 0.594** and 0.421* to vitamin A and fat contents respectively. The Bophelo colour luminosity was significantly lower (L* 76.2) than the other two OFSP, Dagga (L* 83.51) and Impilo (L* 82.07). Bophelo a* (14.09) also differed significantly across all sweet potato cultivars. All cultivars differed significantly in b* values. Colour intensity (ΔE*) ranged from 15.87 to 38.48 for Mvuvhelo and Bophelo, respectively. Chroma ranged from 87.52 to 84.95 for Dagga and Mvuvhelo respectively. Total starch content was significantly different in all sweet potato cultivars and ranged from 244.07 μg/100 g (Bophelo) to 325.04 mg/g (Dagga). Resistant starch differed significantly in all sweet potato cultivars ranging from 1.21 μg/100 g dwb (Bophelo) to 7.07 μg/100 g dwb (Impilo). Ash content was significantly different in all cultivars and ranged from 3.17% (Dagga) to 3.79% (Bophelo). Water holding capacity (WHC) varied significantly across the two locations and ranged from 1.44 g H2O/g DM (Tshiombo) to 1.72 g H2O/g DM (Univen). Bophelo had significantly the lowest (1.27 g H2O/g DM) WHC and Impilo the highest (1.99 g H2O/g DM). The ash content negatively correlated to total starch (-0.928**) but positively iii correlated to WHC (0.654**). Peak viscosity differed significantly across all cultivars under study and ranged from 126.54 RVU (Bophelo) to 302.36 RVU. (Dagga). There was significant difference in trough viscosity across all cultivars ranging from 55.97 RVU (Impilo) to 280.78 RVU (Dagga). There were significant differences in the final viscosity across all cultivars ranging from 78.99 RVU (Impilo) to 319.26 (Dagga). Peak time viscosity varied significantly across all cultivars ranging from 3.87 min (Impilo) to 8.47 min. (Bophelo). Dagga cultivar had significantly the highest pasting temperature (94.16oC) and Bophelo the lowest (77.75oC). The setback viscosity was significantly highest 51.10 RVU (Mvuvhelo) and lowest 23.01 RVU (Impilo). All cultivars from the two locations consistently showed high potassium content ranging from 0.46% (Impilo) to 1.38% (Dagga) as compared to other minerals such as magnesium, calcium and chlorine which ranged from 0.16% (Impilo) to 0.34%. (Dagga). The CT scans revealed that there was a possibility of evaluating the effect of location on the density of granules of sweet potato flour and also the inherent differences in granular distribution of various sweet potato cultivars. SEM revealed high amounts of potassium, magnesium and chlorine. A profile of physicochemical and functional properties of flour of some of the OFSP cultivars produced in Limpopo province, South Africa has been drawn. This study also highlights the nutritional quality of the flour from four sweet potato cultivars and provides a ranking of flour to help the producers in the selection process. Bophelo flour was ranked the highest in terms of β- and, α-carotenes, total carotenoids and antioxidant capacity while Impilo was ranked highest in terms of functional properties and ash content. This study has highlighted significant differences in a number of parameters measured among the sweet potato cultivars. Therefore, in order to derive the maximum benefit from a given cultivar careful selection of sweet potato cultivars would be necessary.

Surface engineering of tailored materials with adjustable characteristics in relation to biological environment, is one of the main prerequisites for biotechnological applications. In recent years, advanced surface coatings in the nanometer range have drawn big attention. A special category of this group are stimuli responsive polymers tethered by one functional end to the surface. When the surface grafting density is big enough, the polymer chains are forced to stretch away from the interface due to excluded volume effects, creating a so called polymer brush. Nano-scaled polymer brushes are advantageous due to their nanostructure, which can be comparable to biological species, and their collaborative response to external stimuli. Moreover, the material design parameters such as chemistry, surface topography, charge, and surface wettability can be adjusted by using the appropriate polymer, or a combination of polymers with respect to the desired material performance. In case of binary polymer brushes, the materials' properties are switched between the properties of two constituent polymers. Besides, upon switching of external stimuli, biomodified binary polymer brushes can hide or expose biofunctionalities, on demand. Hence, they are classified as smart biomaterials' surface coatings.

The cytochrome bc1 complex of the mitochondrial electron transport chain accomplishes the enzymatic reaction known as the modified Q-cycle. In the Q-cycle the bc1 complex transports protons from the matrix to the intermembrane space of the mitochondria, creating the proton gradient used to make ATP. The energy to move these protons is obtained by shuttling electrons from the coenzyme ubiquinol (QH2) to coenzyme ubiquinone (Q) and the mobile cytochrome c. This well studied complex is ideal for examining molecular adaptation because it consists of ten different subunits, it functions as a dimer, and it includes at least five different active sites. The program TreeSAAP was used to characterize molecular adaptation in the bc1 complex and identify specific amino acid sites that experienced positive destabilizing (radical) selection. Using this information and three-dimensional structures of the protein complex, selection was characterized in terms of coevolution and coadaptation. Coevolution is described as reciprocal local biochemical shifts based on phylogenetic location and results in overall maintenance. Coadaptation, on the other hand, is more dynamic and is described as coordinated local biochemical shifts based on phylogenetic location which results in overall adaptation. In this study both coevolution and coadaptation were identified in various locations on the protein complex near the active sites. Sites in the pore region of cyt c1 were shown to exhibit coevolution, in other words maintenance, of many biochemical properties, whereas sites on helix H of cyt b, which flanks the active sites Qo and Qi, were shown to exhibit coadaptation, in other words coordinated shifts in the specific properties equilibrium constant and solvent accessible reduction ratio. Also, different domains of the protein exhibited significant shifts in drastically different amino acid properties: the protein imbedded in the membrane demonstrated shifts in mainly functional properties, while the part of the complex in the intermembrane space demonstrated shifts in conformational, structural, and energetic properties.

Fort McMurray has experienced significant environmental disruptions, raising concerns about chemical releases that affect the environment, particularly berries. This thesis explores the relationship between environmental factors and the nutritional quality of pin cherry (Prunus pensylvanica L.F.) and common blueberry (Vaccinium myrtilloides Michx) fruits and soil in Fort McMurray (reclaimed and natural lands). Samples were collected in August 2022 and analyzed for chemicals and quality variables. The results revealed concentration variations among samples, with hydrocarbons higher in reclaimed areas and blueberries than others and soil surpassing those in fruits. Copper and iron in fruits exceeded regulatory limits. A strong association between soil chemicals and alkylated hydrocarbons in fruits explained most differences. Soil trace elements and properties were primary environmental drivers, while hydrocarbons were secondary influencers, evident mainly in reclaimed berry environments. Antioxidant-focused nutritional quality in reclaimed berries was predominantly influenced by these key drivers in soil, requiring consistent monitoring.

Thesis (M.Sc. (Microbiology)) -- University of Limpopo, 2016 / Access to safe drinking water is a major problem globally and it mostly affects people living in low-income countries. The lack of potable water leads to the use of raw water from surface or ground water sources for drinking and other household purposes. A water filtration unit was designed and constructed using fabric, gravel and sand, which were wet-packaged into a 20 L bucket. The efficiency of the filter unit to improve the bio-physicochemical properties of contaminated water was tested using surface waters from rivers in the Sekhukhune area. Physico-chemical parameters tested included turbidity, colour, total suspended solids (TSS), total dissolved solids (TDS), total hardness and pH. Turbidity and colour were the most improved characteristics, where turbidity improved by 69% and colour by 80%. Other parameters such as total hardness, TSS and TDS were non-significantly reduced following treatment with the filtration unit. The amount of soluble solids in raw water was well within allowable limits by WHO standards. Microbiological tests included heterotrophic bacteria, total coliform and faecal coliform counts. The bacterial load was too numerous to count for the untreated water, however, after treatment with the filtration unit, heterotrophic bacterial load decreased to 15 x 10103 CFU/ml, total coliforms to 14 x 10 2 CFU/100ml and faecal coliforms to 11 x 10 2 CFU/100ml. Further treatment with UV sterilization unit resulted in undetectable amount of bacteria. The unit designed in this study can be beneficial in those rural communities were clean water is not available, it is easy to construct and simple to operate and most importantly it reduced contaminants in surface water. The UV unit incorporated in this study is not cost effective, therefore, other household treatment options such as chlorination and boiling which are easily accessible to most communities can be used to further eliminate remaining microorganisms after filtration. The effective shortest boiling time and minimum dosage of Na(OCl2) have been previously tested in our laboratory and total elimination of bacteria was achieved within 2 minutes of rolling boil and after 30 minutes following addition of 5ml/20L of liquid chlorine.

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