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No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) TESE_ANDRÉ LUIZ RADÜNZ.pdf: 551392 bytes, checksum: 8bb5bdffe88549767cc66638c91ddda1 (MD5) Previous issue date: 2014-02-07 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / Na fruticultura estudos que comtemplem o conhecimento sobre o hábito de frutificação, a fenologia e o manejo da poda tem a finalidade de fornecer informações e dados científicos a cadeia produtiva. Em especial aos agricultores, proporcionando condições destes melhorarem o manejo de seu pomar a fim de obter melhores resultados produtivos e qualitativos dos frutos. Neste sentido, o mirtileiro, espécie exótica para as condições Brasileiras, possui características que tornam seu cultivo atrativo para a inserção nas propriedades da região sul do Brasil. Diante desta possibilidade de difusão do cultivo do mirtileiro, bem como a necessidade de conhecer o comportamento da espécie para as condições climáticas do sul do Brasil. Objetivou-se avaliar o hábito produtivo, o desenvolvimento fenológico das plantas e o manejo da poda sobre as características produtivas das plantas e nos atributos qualitativos dos frutos, para as condições da mesorregião de Pelotas, RS. Para a realização da pesquisa, executou-se o experimento em uma propriedade comercial conduzida em sistema de produção de base ecológica, localizada no munícipio de Morro Redondo, RS. Foram utilizadas plantas da cultivar Climax, Bluegem e Powderblue, pertencentes ao grupo Rabbiteye, de baixa exigência em frio. As avaliações realizadas foram, comportamento fenológico, caracterização da cultura quanto ao hábito de frutificação, bem como, a aplicação dos tratamentos com diferentes épocas e intensidades de poda seca. Sendo avaliados durante a colheita, o número de frutos, teor de sólidos solúveis, o pH, a acidez, cor, a relação entre sólidos solúveis e acidez titulável total, antocianinas, fenóis totais, atividade antioxidante e a produção por planta. Os resultados demonstram que o comportamento fenológico das plantas segue um padrão de necessidade térmica para completar o ciclo (em média, 1911, 1927,4 e 2026,5 GD e 176, 177 e 184, respectivamente, para as cultivares Climax, Bluegem e Powderblue). Quanto ao hábito de frutificação foi verificado semelhança entre as cultivares e comprimentos de ramos, no que tange a proporção de gemas vegetativas por floríferas. Em média, para os longos há 10,27 gemas floríferas e para os curtos 6,33 gemas floríferas. O comportamento produtivo do ramos demonstra que quanto mais apical for a gema, maior será o número e a qualidade dos frutos. Quanto ao efeito da intensidade de poda sobre a produção das plantas, verificou-se que a poda leve causou aumento na produção comparado a poda média e normal, para as três cultivares avaliadas. Os atributos de qualidade físico-química foram, em geral, superiores na época de poda normal para as cultivares Clímax e Powderblue. De maneira geral, os dados fenológicos, de caracterização das plantas, quanto ao número e distribuição das gemas, e o efeito desta sobre os frutos, bem como o manejo da poda, associam-se para a determinação de datas mais apropriadas de realização das práticas culturais, podendo servir com indicador para otimizar a utilização da mão de obra na propriedade. Convergindo ainda, para melhorar a produção, sob os aspectos quantitativos e qualitativos dos frutos. / In the fruit growing activity, studies which contemplate knowledge about the habit of fructification, phenology and the handling of pruning have the objective of providing information and scientific data to the productive chain, particularly to fruit growers, providing them with conditions to improve the handling of their orchards with the objective of obtaining better production and quality of fruits. In this context, the blueberry plant, an exotic species for Brazilian conditions, possesses characteristics which make its cultivation attractive for its insertion in properties of the southern region of Brazil. In view of the possibility of the dissemination of the cultivation of blueberry and of the necessity of knowing the behavior of the species in the climatic conditions of the south of Brazil, it was established as objective to evaluate the productive habit, the phenological development of plants and the handling of pruning and its effects on the productive characteristics of plants as well as the qualitative attributes of fruits for the conditions of the mesorregion of Pelotas, RS. For the conduction of the research, the experiment was carried out in a commercial property located in Morro Redondo, RS, in a production system of ecological basis. Plants of the cultivars Climax, Bluegem and Powderblue were utilized, pertaining to the Rabbiteye group, of low exigency in cold. The evaluations carried out were phenological behavior, characterization of the culture with regard to the fructification habit as well as the application of treatments with different time periods and intensity of dry pruning while it was being evaluated, during the harvest, the number of fruits, the content of soluble solids, Ph., acidity, color, the relationship among soluble solids and the total titratable acidity, anthocyanins, total phenols, ant oxidative activity and production per plant. The results demonstrate that the phenological behavior of the plants follows a pattern of thermal necessity to complete the cycle (on average, 1911, 1927, 4 and 2026.5 GD and 176, 177 and 184, respectively, for the cultivars Climax, Bluegem and Powderblue). As to the habit of fructification, a similarity was verified among the cultivars and the length of branches with respect to the proportion of vegetative gems to floral gems. On average, there are 10.27 floral gems for long branches and 6.33 for the short branches. The productive behavior of branches demonstrates that the more apical a gem is the greater will be the number and quality of the fruits. As to the effect of the intensity of the pruning over the production of plants, it was verified that plants submitted to light pruning presented greater production than those submitted to medium and normal pruning for the three cultivars evaluated. The attributes of physical-chemical quality were, in general, superior in the period of normal pruning for the cultivars Climax and Powderblue. In general, phenological and plant characterization data as to number and distribution of buds and the effect of the position of the bud over the fruits as well as the handling of the pruning associate themselves in determining the most appropriate dates for the practice of cultivation and may serve as an indicator to optimize the utilization of manual labor in the property and converge to improve the production under quantitative and qualitative aspects.

L’émollience est un terme définissant la capacité d’une matière première à adoucir, amollir, ou lubrifier la peau. Dans le domaine de la cosmétique, les émollients sont utilisés pour modifier la consistance, la viscosité ou la polarité d’une formulation. Il existe un nombre non négligeable d’émollients pouvant être utilisés en cosmétique. Cependant, les données aussi bien physico-chimiques que sensorielles disponibles dans la littérature sont encore très rares, rendant le choix des émollients complexe. De plus, les analyses sensorielles habituellement réalisées par les fournisseurs constituent une méthode de caractérisation particulièrement chronophage et coûteuse.Parmi les différents types d’émollients, les dérivés siliconés se démarquent par des propriétés bien spécifiques. Il s’agit notamment d’un très bon étalement, un toucher doux, non huileux et non collant, ou encore d’un effet sec sans effet de fraicheur. Cependant, malgré ces propriétés sensorielles exceptionnelles, de récentes études soulèvent la question de la toxicité d’un dérivé cyclique particulièrement utilisé dans les produits cosmétiques : le décaméthylcyclopentasiloxane (D5). Ainsi, deux problématiques font le sujet de ces travaux : une portant sur la recherche d’un substituant biosourcé au D5 et pour laquelle des molécules commerciales et synthétisées ont été caractérisés et comparés par des mesures physico-chimiques et sensorielles. La seconde problématique repose sur la recherche de corrélations entre les données physico-chimiques et sensorielles dans le but de faciliter le travail des formulateurs lors du screening des émollients par la prédiction de certaines de leurs propriétés sensorielles. / Emolliency is a word used to define the ability of a compound to soften or lubricate the skin. ln the cosmetic field, emollients are used to modify the consistency, the viscosity or the polarity of a formulation. Many emollients can be used in cosmetic products. However, in the literature both physicochemical and sensory data ar still lacking, making it difficult to choose an emollient. Furthermore, the sensory analysis usually performed to characterize emollients are particularly time-consuming and thus, expensive. Among the different chemical families of emollients, silicone derivatives stand out thanks to their specific properties. Indeed, they are characterized by an excellent spreading on skin and hair, a smooth skin feel, non-greasy and non-sticky, or by a dry skin feel without a fresh effect. However, even though these sensory properties are exceptional, recent studies wonder about the toxicity of a cyclic silicone particularly used in cosmetic products: the decamethylcyclopentasiloxane (D5). Thus, this work deals With two main objectives. The first one consists in the research of a bio-based alternative to the D5 For this purpose, a number of commercial and synthesized molecules were characterized and compared With physicochemical measurements and sensory analysis, allowing the observations of trends between structures and properties. The second objective relies on the study of correlations between physico-chemical and sensory data in order to predict the emollient properties of cosmetic ingredients. This would ease the work of formulators during the screening of ingredients.

Comprendre l'effet de réactions chimiques sur les fluides en écoulement est une problématique au coeur de nombreuses applications telles que la remédiation de sols pollués ou le stockage géologique du CO2. Dans ce cadre, l'objectif de notre travail est de comprendre par une approche expérimentale dans quelle mesure une réaction chimique peut modifier le développement et les propriétés de motifs convectifs résultant d'instabilités hydrodynamiques dues à des gradients de densité dans le champ de gravité. Nos expériences sont effectuées par mise en contact de solutions aqueuses réactives ou de liquides non réactifs dans une cellule de Hele-Shaw verticale. Ce réacteur modèle constitué de deux plaques en verre séparées par un mince interstice est en effet communément utilisé pour l'étude de mouvements de fluides à l'échelle du laboratoire. Nous analysons dans divers cas les structures spatio-temporelles résultant du développement de profils de densité instables engendrés par des réactions chimiques, des processus de dissolution ou de diffusion croisée. Lors de notre thèse, nous avons tout d'abord étudié l'interaction entre une réaction acide-base et les instabilités hydrodynamiques dues à un gradient de densité, plus particulièrement la double diffusion et l'instabilité de Rayleigh-Taylor. Nous avons montré que cette simple réaction chimique de type A+B—>C brise la symétrie haut-bas caractéristique des motifs convectifs non réactifs. Nous nous sommes ensuite intéressés à une réaction chimique de cinétique plus complexe :la réaction oscillante de Belousov-Zhabotinsky. Nous avons séparé les réactifs dans l'espace de manière à localiser la réaction à l'interface entre deux solutions de composition différente. Notre objectif est d'ainsi obtenir un oscillateur localisé et d'en comprendre l'effet sur les instabilités hydrodynamiques. Pour ce faire, nous avons d'abord caractérisé les motifs réaction-diffusion qui se développent dans cette géométrie particulière. Nous avons montré qu'en l'absence de convection, la ségrégation spatiale des réactifs donne lieu à des variations spatiales de l'excitabilité, et par conséquent à l'apparition d'un ou deux trains d'ondes localisés spatialement. Dans le cas convectif, nous avons observé que ces trains d'onde peuvent également apparaître de manière localisée en fonction du type d'instabilité hydrodynamique qui se développe et que les réactions chimiques permettent d'obtenir de nouveaux motifs originaux. Nous avons également caractérisé les motifs hydrodynamiques qui apparaissent à cause de la diffusion croisée dans des microémulsions. Nous avons montré que, si le gradient de concentration d'une espèce peut engendrer un flux d'une autre espèce, une stratification instable de densité peut en résulter, ce qui engendre de la convection. Enfin nous avons étudié la dissolution convective d'une phase organique (formate d'alkyle) dans une phase aqueuse. Nous avons montré que lorsque le degré de miscibilité entre les deux phases augmente au-delà d'un certain seuil, les mouvements de fluide sont plus intenses. Nos résultats ont permis de comprendre l'effet de réactions bimoléculaires ou oscillantes ainsi que de la dissolution ou de la diffusion croisée sur les propriétés de structures de type réaction-diffusion-convection. Ces travaux ouvrent la voie à l'étude de nouveaux motifs spatio-temporels auto-organisés couplant le pouvoir organisateur des réactions d'une part et de l'hydrodynamique d'autre part et ce, tant dans des solutions aqueuses que dans des milieux plus complexes comprenant différentes phases. / The understanding of the effect of chemical reactions on fluid motions is an issue at the heart of numerous applications, such as polluted soil remediation or geological storage of CO2. In this context, the goal of our work is to understand through an experimental approach to what extent a chemical reaction is able to modify the development and the properties of buoyancy-driven convective patterns. Our experiments are carried out by putting in contact reactive aqueous solutions or non reactive liquids in a vertical Hele-Shaw cell. This model reactor consists in two glass plates separated by a thin gap and is commonly used to study fluid motions at the laboratory scale. We analyze in various cases the spatio-temporal structures resulting from the build-up of unstable density gradients due to chemical reactions, dissolution processes or cross-diffusion. During our thesis, we first studied the interplay between an acid-base reaction and buoyancy-driven instabilities, namely double diffusion and the Rayleigh-Taylor instability. We have shown that this simple A+B -->C type of reaction breaks the up-down symmetry which is characteristic of the non reactive patterns. Next we focused on a chemical reaction featuring more complex kinetics, namely the oscillating Belousov-Zhabotinsky reaction. The reactants were initially segregated in space in order to spatially localize the reaction at the interface between two solutions with different composition. Our aim is to obtain a localized chemical oscillator and to study its effect on buoyancy-driven flows. To do so, we first characterized the corresponding reaction-diffusion patterns which develop from this particular initial condition. We showed that, in the absence of convection, the spatial segregation of the reactants produces spatial gradients in the excitability and hence the nucleation of one or two spatially localized wave trains. We observed that in the presence of convective motions, these wave trains can also appear and remain localized, according to the type of buoyancy-driven instability which is at play. Moreover the chemical reaction triggers the onset of additional patterns. We have also characterized the hydrodynamic patterns which appear due to cross-diffusion in microemulsions. We have shown that, if a concentration gradient of one species is able to trigger a flux of another species, an unstable density stratification may appear and cause the onset of convection. Finally we have studied the convective dissolution of an organic phase (alkyl formate) into an aqueous phase. We have shown that, above a certain threshold, an increase in the miscibility between the two phases leads to an increase in the intensity of the fluid motions. Our results help to understand the effect of bimolecular or oscillating reactions, dissolution processes and cross-diffusion on the properties of reaction-diffusion-convection structures. This work paves the way towards the study of novel self-organized spatio-temporal patterns coupling the organizing power of chemical reactions and of hydrodynamic flows, both in aqueous solutions and multiphase media. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

Dans des contextes industriels spécifiques, coller un revêtement épais élastomère à des canalisations en acier constitue le meilleur moyen de les protéger de la corrosion en milieu marin. Ce travail de thèse a principalement pour objectif de mieux appréhender le comportement à long terme de ces assemblages acier/colle/revêtement en milieu marin. Deux approches complémentaires ont été définies. La première se base sur des outils statistiques pour traiter les données de caractérisations physico-chimiques des matériaux issus des assemblages utilisés en service depuis plus de trente ans. A partir de ces données hétérogènes (les assemblages sont différents en termes de formulations des matériaux, de procédé de collage et de conditions de vieillissement); des groupes homogènes présentant des scénarios de vieillissement identiques ont été identifiés et les mécanismes majeurs de dégradation du revêtement ont été établis. La seconde approche se focalise sur les assemblages actuellement utilisés dans les opérations de rénovation. Une démarche expérimentale a donc été mise en place en laboratoire afin d’accélérer de manière contrôlée le vieillissement des matériaux et assemblages. Les objectifs sont multiples. Pour chaque matériau (revêtement et colle), il s’agissait de comprendre les mécanismes de dégradation et les cinétiques d’absorption d’eau qui expliquent les évolutions de propriétés mécaniques et physico-chimiques observées au cours du vieillissement. De même, les interfaces ont été caractérisées et les paramètres de procédé qui influent sur la tenue de l’interface métallique ont été identifiés. Cette approche découplée a permis de mieux comprendre le comportement en milieu marin de l’assemblage d’étude à partir de celui des matériaux et interfaces présentes. / In some industrial applications, bonding rubber coatings to metallic pipelines is a suitable solution to protect them from marine corrosion. This study deals with the long term behavior of such metallic coated pipelines in a marine environment. Two different approaches have been developed. The first focuses on degradation data of pipelines used for around thirty years in normal service conditions. As these bonded assemblies are different in terms of material formulations, manufacturing processes and aging conditions, statistical tools were used to identify homogeneous groups with identical aging mechanisms. Also, based on these results, the main degradation mechanisms of the rubber coating were established. The second approach focused on pipelines used currently in renovation operations. An experimental methodology was developed in the laboratory to accelerate aging processes. The bulk materials, surfaces and interfaces were characterized physically, chemically and mechanically before and after natural sea water ageing. This enabled an understanding of the mechanisms and kinetics governing adhesion and degradation to be developed. It also allowed the influence of sea water aging on the failure strength of the assembly of interest to be investigated.

Sida rhombifolia L belongs to the family Malvaceae, it is native to the American continent and can be found in all regions of Brazil. It is popularly known as prickly sida , and used in traditional medicine as anti-inflammatory, antidiabetic and lipid lowering. The aim of this study was to determine and evaluate the physical and chemical parameters of quality in the four seasons and the aerial parts and roots of the plant drug; determining the content of total polyphenols, flavonoids and tannins in the extracts of the aerial parts and roots of S. rhombifolia in four seasons; evaluating the antimicrobial and antioxidant activity in these same extracts; investigating the hypoglycemic and lipid lowering activity of extracts that have a higher content of flavonoids, as well as to analyze biochemical parameters of liver, kidney and pancreatic toxicity and cytotoxicity in cells NCTC clone 929 by incorporation of neutral red dye. The drug was collected at the four seasons in Santa Maria, RS, separated into aerial parts and roots and made hydroethanolic extracts 70% from each of these collections. The physico-chemical parameters varied according to the plant part analyzed and the season. The values found for strange matter, determination of water and ash insoluble in hydrochloric acid are consistent with those established for herbs. The winter collection showed higher content of total ash, both to shoots (21.20%) and roots (17.63%). The swelling rates varied significantly among the aerial parts and roots, and the highest rates obtained for each of the samples were collected in summer (35.47%) and autumn (18.40%), respectively. There were significant differences between the content of total polyphenols and flavonoids throughout the year and these have focused differently from the aerial parts and roots. The content of tannins and did not suffer seasonal variation nor the distribution between the parties analyzed the plant. The extracts of the aerial parts (172.50 g / mL) and roots (374.08 g / mL) of winter presented the best antioxidant activity. Extracts of S. rhombifolia showed good antibacterial activity while showed no activity against fungi. The extracts of the aerial parts and roots of the summer of the winter showed no hypoglycemic and lipid lowering activity in healthy animals, the markers of liver, kidney and pancreatic damage did not vary in relation to the control group, and the IC50 obtained at the cytotoxicity assays were 8.88 mg/mL e 12.57 mg/mL, respectively. / Sida rhombifolia L. pertence à família Malvaceae, é nativa do continente americano e pode ser encontrada em todas as regiões do Brasil. É conhecida popularmente por guanxuma, e utilizada na medicina tradicional como antiinflamatória, hipoglicemiante e hipolipidemiante. O objetivo deste trabalho foi determinar e avaliar os parâmetros físico-químicos de qualidade nas quatro estações do ano e nas partes aéreas e raízes da droga vegetal; realizar o doseamento de polifenóis totais, flavonoides e taninos condensados nos extratos das partes aéreas e raízes de S. rhombifolia nas quatro estações; avaliar a atividade antioxidante e antimicrobiana nestes mesmos extratos; investigar a atividade hipoglicemiante e hipolipidemiante dos extratos que apresentarem maior conteúdo de flavonoides, assim como analisar parâmetros bioquímicos de toxicidade hepática, renal e pancreática e citotoxicidade em células NCTC clone 929 por incorporação do corante vermelho neutro. A droga vegetal foi coletada nas quatro estações do ano no município de Santa Maria, RS, separada em partes aéreas e raízes e feitos extratos hidroetanólicos 70% de cada uma destas coletas. Os parâmetros físico-químicos variaram de acordo com a parte da planta analisada e a estação. Os valores encontrados para matéria estranha, determinação de água e cinzas insolúveis em ácido clorídrico estão de acordo com os estabelecidos para drogas vegetais. A coleta de inverno apresentou maior conteúdo de cinzas totais, tanto para as partes aéreas (21,20%) quanto para as raízes (17,63%). Os índices de intumescência variaram significativamente entre as partes aéreas e raízes, e os maiores índices obtidos para cada uma das coletas foram nas amostras do verão (35,47%) e outono (18,40%), respectivamente. Houve diferença significativa entre os conteúdos de polifenóis totais e flavonoides ao longo do ano e estes concentraram se diferentemente entre as partes aéreas e raízes. O conteúdo de taninos não sofreu variação entre as partes analisadas da planta e de sazonalidade. Os extratos das partes aéreas (172,50 μg/mL) e das raízes (374,08 μg/mL) do inverno foram os que apresentaram melhor atividade antioxidante. Os extratos de S. rhombifolia apresentaram boa atividade antibacteriana e não apresentaram atividade contra fungos. Os extratos das partes aéreas do verão e das raízes do inverno não demonstraram atividade hipoglicemiante e hipolipidemiante em animais sadios. Os marcadores de danos hepáticos, renais e pancreáticos não variaram em relação ao grupo controle, e as IC50 obtidas nos testes de citotoxicidade das partes aéreas e raízes foram 8,88 mg/mL e 12,57 mg/mL, respectivamente.

Ce travail de thèse concerne l'évaluation biologique et physico-chimique de deux biomatériaux : verre pure associé au risedronate (46S6-xRIS) et une vitrocéramique poreuse dopée avec l'oxyde de zinc et le nitrure de titane noté 46S6-10Zn-2Ti. Le premier est un matériau hybride composé du verre (46S6) et d'un bisphosphonate le risedronate à différentes teneurs (xRIS) avec x= 8, 12 et 20%. Le deuxième est une vitrocéramique ayant une porosité créée par l'élimination de N après calcination. Les analyses physico-chimiques après les tests in vitro du 46S6-xRIS montrent une modification de la cinétique de la bioactivité de ces composites selon la quantité de risedronate ajoutée au 46S6. Les analyses in vivo ont été aussi menées sur le 46S6-10Zn-2Ti. Cette vitrocéramique a été implantée dans des condyles fémoraux de rattes ostéoporotiques, phénomène créé par l'irradiation des rattes à différentes doses de rayons γ. L'investigation biologique après irradiation montre un déséquilibre entre la peroxydation lipidique et les enzymes antioxydants. L'implantation en site osseux avec le 46S6-10Zn-2Ti a permis la restauration de cette balance. L'étude histologique montre le rétablissement du tissu osseux. Cependant, celui ci décroit avec l'augmentation de la dose des rayons gamma. Pour l'exploration physico-chimique, plusieurs techniques complémentaires ont été utilisées pour évaluer la cinétique d'ossification. La bioconsolidation de notre vitrocéramique a été également évaluée après implantation chez des lapins. Le microscanner (mCT) montre la résorption du 46S6-10Zn-2Ti et l'osséo-intégration des cellules osseuses dans les pores du bio-implant alors que, l'étude histologique montre que le 46S6-10Zn-2Ti est presque totalement dégradé et remplacé par le tissue osseux. Le MEB met en évidence la dégradation du 46S6-10Zn-2Ti et son remplacement par un dépôt apatitique. Les spectres MAS-RMN du ³¹P et u ²⁹Si illustrent la dégradation progressive du 46S6-10Zn-2Ti en faveur du développement de l'apatite biologique. / This work focuses on the biological and physicochemical evaluations of two biomaterials: a bioactive glass associated to risedronate (46S6-xRIS) and a porous glass ceramic doped with zinc oxide and titanium nitride noted 46S6-10Zn-2Ti. The first is a hybrid material composed of bioactive glass (46S6) and a bisphosphonate, the risedronate with different contents (xRIS) with x=8, 12 and 20%. The second is a ceramic glass having a porosity, which has been created following the elimination of N after heating. Physicochemical analysis after the in vitro essays of 46S6-xRIS show the modification of the bioactivity kinetic of these composites proportional to the quantity of risedronate added to the 46S6. The in vivo analyses were also conducted in the 46S6-10Zn-2Ti. This glass ceramic was implanted in the femoral condyles of osteoporotic rats. This phenomenon was created after its irradiation at different doses of γ-rays. The biological investigations after irradiation show an imbalance between the lipid peroxidation and antioxidants enzymes. The implantation of 46S6-10Zn-2Ti in bone tissue restored the oxidative balance. The histological study manifests the restoration of bone tissue. However, this restoration decreased with the rising of γ-rays doses. For the physiochemical exploration, several complementary techniques were used to evaluate the kinetic of ossification. The porous glass ceramic was evaluated also in the bioconsolidation process after implantation in rabbit. The X-ray Micro-Computer Tomography (mCT) shows the resorption of the 46S6-10Zn-2Ti and the osseointegration of bones cells in the biomaterial pores. Moreover, the histological study illustrates that the degradation and the resoption of the 46S6-10Zn-2Ti is almost total. The SEM highlights the degradation of the 46S6-10Zn-2Ti and its replacement by an apatitic deposit. The MAS-NMR spectra of ³¹P and of ²⁹Si illustrate a progressive degradation of 46S6-10Zn-2Ti in favor of the development of a biological apatite.

Philosophiae Doctor - PhD / This study is aimed at investigating the feasibility of using the radiometric technique as an alternative to traditional methods for determining soil physico-chemical parameters which are important for terroir characterization. In-situ and ex-situ radiometric analyses of soil from three vineyard blocks of Simonsig Wine Estate in the Stellenbosch district (Western Cape, South Africa) were studied. A mobile MEDUSA gamma-ray detection system comprising a CsI(Na) crystal (length 15 cm, diameter 7 cm) and associated electronics mounted on a portable trolley were used for partial terroir characterisation. Thereafter activity concentrations of 40K, 232Th series and 238U series in soil (top ~30 cm) from the measured MEDUSA spectra (0 - 3 MeV) were extracted by means of the full-spectrum analysis (FSA) method. A lead-shielded HPGe detector was used for analyzing collected soil samples while soil physico-chemical parameters were analysed using standard methods at research and commercial laboratories. / South Africa

Doctor Educationis / The research focused on the synthesis, characterisation and activity of zeolite supported metal catalysts for the Friedel-Crafts alkylation of benzene with t-butyl chloride. Alkyl benzenes are traditionally produced via systems that employ the use of Lewis acids or strong mineral acids. There have been widespread concerns over these approaches based on their environmental impacts and separation difficulties. Recent approaches have endeavoured the much to use more environmentally eco-friendly systems and zeolites have proved to be versatile support materials. The use of zeolites has also shown to greatly improve product selectivity as well as easing separation constraints. However the adoption of zeolites on large scale Friedel-Crafts alkylation has been hampered by the high cost of zeolite production from commercial sources. On the other hand fly ash has been found to be a viable starting material for zeolite synthesis. Apart from that South Africa is faced with fly disposal challenges and there is continual accumulation of fly ash at the coal fired power stations, which provide about 77 % of the power produced in the country. In this light the use of fly ash will help to reduce the disposal constraints as well as providing a cheap starting material for zeolite synthesis. In this study the hierarchical Zeolite X has been successfully synthesised from fly ash via a hydrothermal treatment. The zeolite was then loaded with Fe/Mn via two approaches namely liquid phase ion exchange and incipient wetness impregnation. For comparison purposes seasoned commercial support materials namely HBEA and MCM- 41 were also loaded with the same metals and characterised with various techniques namely; HRSEM, EDS, HRTEM, XRD, SAED, ICP-OES and N2 adsorption analysis, It was found from the characterisation undertaken that the integrity of the respective supports was generally retained upon metal loading. Both the ICP-OES and the EDS proved that the desired metals were successfully introduced onto the zeolitic support materials. The calculated percentage metal loading for the catalysts prepared via incipient wetness impregnation was closely related to the actual values obtained from the ICP-OES analysis for both the monometallic and the bimetallic catalysts (Fe/Mn). It was observed that the amount of metal that can be introduced on a zeolite via liquid phase ion exchange is largely dependent on the cation exchange capacity of the zeolite Supported metal catalysts for FC alkylation Page v and of the catalysts prepared using 0.25 M Fe solution it was found that Zeolite X had the highest Fe wt% loading of 11.4 %, with the lowest loading of 2.2 % obtained with the MCM-41 supported catalyst. The XRD patterns for the both HBEA and the MCM-41 supported metal catalysts resembled the patterns of the respective prestine support materials except in the case of catalysts with anFe wt % of more than 10, which exhibited peaks due to the Fe2O3 crystallites. In the case of the hierarchical Zeolite X, the metal loaded support had a significant reduction in the XRD peak intensities. The prepared catalysts were tested for the alkylation of benzene with t-butyl chloride. The benzene was also used as the solvent. The alkylation reaction was carried out in a round bottomed flask under reflux conditions and stirring at a temperature of 45 oC over a period of 5 h. A total of 18 catalysts was tested and the highest percentage conversion of 100 % was obtained with the 10%FeH after a reaction time of 2 h. The general trend obtained with the majority of the catalysts was characterised with a rapid initial increase and then steady state was achieved. Generally after a reaction time of 3 h almost all the catalysts had reached steady state in terms of the percentage conversion obtained. The outcomes reflect that the inclusion of Mn does not enhance the conversion but rather decreases it. It was also found that the Mn was not active in the alkylation of benzene as shown by the inactivity of the 10%MnM, where 10% by weight Mn was loaded on MCM-41. However the other monometallic catalysts containing Mn supported on Zeolite X and HBEA were found to be active. The activity is attributed to the presence of Brønsted acid sites in these zeolites which are not present in MCM-41. The selectivity studies reflect that the inclusion of Mn does slightly improve the selectivity towards the formation of the monoalkylated product (t-butyl benzene). The highest selectivity of 91.1 % was obtained with the 10%FeMnM after a reaction time of 4 h. MCM-41 supported catalysts had a relatively higher selectivity compared to the other supports. Considering the Fe monometallic catalysts tested it generally can be said that the yield were in the order HBEA > MCM-41 > Zeolite X. It however should be noted that the percentage yield is calculated from the conversion and selectivity percentages, this implies that the factors affecting these parameters will consequently affect the percentage yield obtained. Supported metal catalysts for FC alkylation Page vi The alkylation reaction was found to be characterised by the formation of two intermediate products which could not be identified. These products were formed during the transient start up stages of the reaction and would disappear from the reaction mixture with longer reaction times, and after 3 h in almost all the reactions studied the intermediates were not detected in the reaction mixture. The main products found were the monoalkylated product (desired product) and the para isomer (1,4-t-di-butyl benzene). There were no other dialkylated isomers or trialkylated products detected. The formation of the para isomer was usually after a reaction time of 2 h in most reactions. The research managed to show that the hierarchical Zeolites X can be synthesised from fly ash and ion exchange and incipient wetness impregnation are appropriate approaches that can be used to introduce Fe/Mn onto the support materials studied. The catalysts prepared were active to varying degrees in the Friedel-Crafts alkylation of benzene with t-butylchloride, with the exception of the 10%MnM which was found to be inactive.

L’objectif de la thèse est de caractériser la poudre du kishk libanais, un lait fermenté traditionnel, et d’optimiser sa technologie de transformation dans une démarche d’industrialisation. Des échantillons de poudre de kishk traditionnel ont été collectés, et leurs propriétés physico-chimiques, rhéologiques, microbiologiques et sensorielles ont été étudiées, en fonction du type de lait utilisé. Il en résulte que le kishk préparé à base de lait de chèvre est plus riche en matières grasses que les autres types. La distribution granulométrique est très large, quel que soit le type de lait, avec présence simultanée de fines particules à forme irrégulière et d’agrégats de grande taille. Les particules de poudre sont revêtues d’une épaisse couche de lipides leur conférant un caractère cohésif et une grande résistance au cisaillement. Il s’avère aussi que la soupe de kishk présente un comportement rhéofluidifiant, et ses propriétés sensorielles sont fortement liées à la région de production et au type de lait. L’effet des conditions de production optimisée sur les propriétés de la poudre et de la soupe de kishk a été également étudié. Les résultats sont prometteurs et montrent que la structure de la poudre de kishk et son comportement rhéologique n’ont pas été altérés. En effet, les deux poudres de kishk présentent des propriétés rhéologiques quasi similaires, avec une faible aptitude à l’écoulement, malgré des différences au niveau de la composition chimique et la taille des particules. Au niveau rhéologique et sensoriel, la soupe de kishk issue de la production optimisée semble plus épaisse et consistante que la soupe traditionnelle, sans dépréciation notable des qualités organoleptiques du kishk. / The aim of this thesis is to characterize Lebanese kishk powder, a traditional fermented milk, and to optimize its processing technology. Samples of traditional kishk powder were collected, and their physicochemical, rheological, sensory and microbiological properties were studied based on the type of milk. As a result, kishk prepared with goat milk is richer in fat than other types. The particle size distribution is very wide, regardless of the type of milk, with simultaneous presence of fine irregularly shaped particles and large aggregates. Powder particles are coated with a thick layer of fat conferring a cohesive character and a high shear strength. Kishk soup has a shear-thinning behavior, and its sensory properties are strongly related to the production region and the type of milk. The effect of optimized production conditions on the properties of kishk powder and soup was also studied. The results are promising and show that the structure and rheological behavior of kishk powder were not altered. Indeed, the two kishk powders exhibit almost similar rheological properties, with low flowability, despite slight differences in chemical composition and particle size. Finally, kishk soup resulting from the optimized production seems thicker and consistent than traditional soup, without significant loss of the organoleptic properties of kishk.

Les tensioactifs dérivés de sucres représentent la principale famille de tensioactifs bio-sourcés et constituent de bons candidats pour substituer les tensioactifs dérivés du pétrole puisqu'ils sont issus de ressources renouvelables et peuvent être autant, voire plus performants dans diverses applications, comme la formulation (détergents, cosmétiques,…), la récupération assistée du pétrole ou des minéraux, etc. Différentes propriétés amphiphiles permettent de caractériser la performance des tensioactifs dans de telles applications, comme la concentration micellaire critique, la tension de surface à la concentration micellaire critique, l'efficience et le point de Krafft. Prédire ces propriétés serait bénéfique pour identifier plus rapidement les tensioactifs possédant les propriétés désirées. Les modèles QSPR sont des outils permettant de prédire de telles propriétés, mais aucun modèle QSPR fiable dédié à ces propriétés n'a été identifié pour les tensioactifs bio-sourcés, et en particulier les tensioactifs dérivés de sucres. Au cours de cette thèse, de tels modèles QSPR ont été développés. Une base de données fiables est nécessaire pour développer tout modèle QSPR. Concernant les tensioactifs dérivés de sucres, aucune base de données existante n'a été identifiée pour les propriétés ciblées. Cela a donné suite à la construction de la première base de données de propriétés amphiphiles de tensioactifs dérivés de sucres, qui est en cours de valorisation. L'analyse de cette base de données a mis en évidence différentes relations empiriques entre la structure de ces molécules et leurs propriétés amphiphiles, et permis d'isoler des jeux de données les plus fiables et au protocole le plus homogène possibles en vue du développement de modèles QSPR. Après établissement d'une stratégie robuste pour calculer les descripteurs moléculaires constituant les modèles QSPR, qui s'appuie notamment sur des analyses conformationnelles des tensioactifs dérivés de sucres et des descripteurs des têtes polaires et chaînes alkyles, différents modèles QSPR ont été développés, validés, et leur domaine d'applicabilité spécifié, pour la concentration micellaire critique, la tension de surface à la concentration micellaire critique, l'efficience et le point de Krafft. Pour les trois premières propriétés, des modèles quantitatifs performants ont pu être obtenus. Si les descripteurs quantiques ont apporté un gain prédictif important pour la tension de surface à la concentration micellaire critique, et un léger gain pour la concentration micellaire critique, aucun gain n'a été observé pour l'efficience. Pour ces trois propriétés, des modèles simples basés sur des descripteurs constitutionnels des parties hydrophile et hydrophobe de la molécule (comme des décomptes d'atomes) ont aussi été obtenus. Pour le point de Krafft, deux arbres de décision qualitatifs, classant la molécule comme soluble ou insoluble dans l'eau à température ambiante, ont été proposés. Les descripteurs quantiques ont ici aussi apporté un gain en prédictivité, même si un modèle relativement fiable basé sur des descripteurs constitutionnels des parties hydrophile et hydrophobe de la molécule a aussi été obtenu. Enfin, nous avons montré comment ces modèles QSPR peuvent être utilisés, pour prédire les propriétés de nouvelles molécules avant toute synthèse dans un contexte de screening, ou les propriétés manquantes de molécules existantes, et pour le design in silico de nouvelles molécules par combinaison de fragments. / Sugar-based surfactants are the main family of bio-based surfactants and are good candidates as substitutes for petroleum-based surfactants, since they originate from renewable resources and can show as good as, or even better, performances in various applications, such as detergent and cosmetic formulation, enhanced oil or mineral recovery, etc. Different amphiphilic properties can characterize surfactant performance in such applications, like critical micelle concentration, surface tension at critical micelle concentration, efficiency and Kraft point. Predicting such properties would be beneficial to quickly identify surfactants that exhibit desired properties. QSPR models are tools to predict such properties, but no reliable QSPR model was identified for bio-based surfactants, and in particular sugar-based surfactants. During this thesis, such QSPR models were developed. A reliable database is required to develop any QSPR model. Regarding sugar-based surfactants, no database was identified for the targeted properties. This motivated the elaboration of the first database of amphiphilic properties of sugar-based surfactants. The analysis of this database highlighted various empirical relationships between the chemical structure of these molecules and their amphiphilic properties, and enabled to isolate the most reliable datasets with the most homogeneous possible protocol, to be used for the development of the QSPR models. After the development of a robust strategy to calculate molecular descriptors that constitute QSPR models, notably relying upon conformational analysis of sugar-based surfactants and descriptors calculated only for the polar heads and for the alkyl chains, different QSPR models were developed, validated, and their applicability domain defined, for the critical micelle concentration, the surface tension at critical micelle concentration, the efficiency and the Kraft point. For the three first properties, good quantitative models were obtained. If the quantum chemical descriptors brought a significant additional predictive power for the surface tension at critical micelle concentration, and a slight improvement for the critical micelle concentration, no gain was observed for efficiency. For these three properties, simple models based on constitutional descriptors of polar heads and alkyl chains of the molecule (like atomic counts) were also obtained. For the Krafft point, two qualitative decision trees, classifying the molecule as water soluble or insoluble at room temperature, were proposed. The use of quantum chemical descriptors brought an increase in predictive power for these decision trees, even if a quite reliable model only based on constitutional descriptors of polar heads and alkyl chains was also obtained. At last, we showed how these QSPR models can be used, to predict properties of new surfactants before synthesis in a context of computational screening, or missing properties of existing surfactants, and for the in silico design of new surfactants by combining different polar heads with different alkyl chain