La réduction de l’impact des activités humaines sur l’environnement est au sujet de nombreux programmes de recherche. Ainsi, dans le domaine du transport aérien a été créé le projet Clean-Sky, regroupant les thèmes de recherche associés. La thèse, partie de ce dernier, a pour objectif de réduire l’impact environnemental de la production de composants en alliages avancés à base de Titane. La production actuelle ayant une empreinte écologique non négligeable, un procédé de fabrication alternatif est étudié, il s’agit du moulage par injection de poudres métalliques. La première partie de cette consiste donc en la recherche d’une formulation de mélange optimale parmi les solutions classiques et innovantes. Elles sont triées en fonction de leurs aptitudes, déterminées par caractérisations physico-chimiques, à assurer le bon déroulement de chaque étape du procédé. Un nombre réduit de solution étant ainsi dégagé, il s’agit de passer aux étapes d’injection, de déliantage et de frittage. Plusieurs géométries de pièces sont testées dans chacun de ces cas, afin de valider l’adaptation aux différentes contraintes imposées. Lors de ces trois phases, des analyses physico-chimiques complètes permettent de mettre en avant la ou les formulations les plus aptes à permettre la production de ces composants. Une fois la solution fixée, chaque étape du procédé est optimisées, afin de faciliter le transfert industriel et d’assurer la rentabilité du nouveau processus de fabrication. Ces travaux de doctorat ont permis de mettre en avant deux formulations, répondant aux critères définis en début de thèse. Les étapes de mélange, injection, déliantage et frittage ont été optimisées et le transfert industriel est possible. / Reducing the ecological footprint of human activities is, today, the aim of most of the research programs. In Europe, the « Clean Sky » project funds research activities to make air transport « greener ». This PhD, being part of it, is about improving production of Titanium Aluminide based components. Nowadays production having a strong environmental impact, an alternative way has been investigated: metal injection molding. The first step of this work was focused on a bibliographic study, to select relevant, common and innovative mixtures to be used in the process. Throughout the process, these mixtures have been tested, physically and chemically analyzed, to get data about the optimal mixture. Several components geometries have been tested, during injection, debinding, and sintering steps. Once the mixture(s) chosen, process’ parameters have been optimized to make industrial transfer easier, and lower its overall cost. The developments achieved during this PhD led to two qualified mixtures, and optimized mixing, molding, debinding and sintering steps.

En ce début de XXIème siècle l’essor des nanotechnologies est indéniable et ne semble pas près de ralentir. En effet, les secteurs industriels de pointe misent sur les innovations remarquables permises par les nouvelles propriétés de la matière à l’échelle nanométrique. Cependant, les efforts scientifiques et budgétaires, mis en place pour comprendre les potentiels risques sanitaires des nano-objets pour l’homme et l’environnement, s’avèrent peu fructueux tant la diversité des nano-objets est étendue. De plus, il n’existe pas de consensus règlementaire pour la nanotoxicologie, ce qui entraine un manque d’homogénéité, et parfois de cohérence, entre les données issues de la recherche. Dans ce contexte, la présente étude porte sur l’amélioration de la compréhension de l’activité biologique des nanoparticules. Des nanoparticules fluorescentes de silice, synthétisées à façon, ont permis d’étudier séparément l’impact de deux de leurs caractéristiques physico-chimiques (taille et fonctionnalisation de surface). L’altération membranaire, la réaction pro-inflammatoire et la génération de stress oxydant induites par la mise en contact des nanoparticules avec une lignée de macrophages murins ont été étudiées. En complément, des méthodes permettant de distinguer les nanoparticules internalisées de celles adsorbées à la membrane cellulaire ainsi que d’observer en cinétique la phagocytose, ont été développées. La nature et l’intensité des effets biologiques observés ont montré que les nanoparticules n’étaient pas inertes et que leur impact dépendait bien de leur taille et de leur fonctionnalisation de surface ainsi que de la dose étudiée. / In the 21st century nanotechnologies are growing fast and are continuously evolving. Indeed, high-tech industries rely on remarkable innovations enabled by the new properties of matter at the nanoscale. In addition, the nanomedicine field seems hopeful to cure human health problems such as heart or liver diseases, brain damage or cancers. However, despite expansive scientific efforts the potential risks of nano-objects on human health and on the environment are still poorly understood due to the wide variety of nano-objects. In addition, no consensus about nanotoxicology exists yet, sometimes leading to inhomogeneous and inconsistent findings. In this context, the present study aimed at a better understanding of the nanoparticles biological effects. Fluorescent silica nanoparticles with well-controlled size and surface functionalization were synthesized to study separately the impact of these two physico-chemical characteristics on cell response. Murine macrophages (from the RAW 264.7 cell line commonly used as a reference for nanotoxicology studies) were exposed to the different nanoparticles, and membrane alteration, induction of pro-inflammatory effect and generation of oxidative stress were investigated. In addition, in order to distinguish uptaken nanoparticles from those adsorbed at the cell membrane and to observe phagocytosis over time, methods were developed. Results demonstrated that the studied nanoparticles were not inert. Moreover the biological effects were found to depend on nanoparticles size, surface functionalization and dose.

Le traitement thermique est basé sur la modification chimique des biopolymères par thermodégradation, en évitant l'ajout de produits chimiques. Ce traitement améliore la stabilité dimensionnelle et la durabilité fongique du bois. Ces améliorations se font au détriment des propriétés mécaniques qui ont tendance à s'affaiblir. Aujourd'hui, plusieurs types de procédés sont utilisés. Ils se distinguent entre autre par la nature du milieu dans lequelle se déroule le traitement. La durabilité de ce nouveau matériau bois est liée au degré de thermodégradation, dépendant des conditions et de l'intensité du traitement. Un pilote de traitement par conduction, travaillant sous vide ou sous azote, mesurant la masse en dynamique est utilisé afin de mieux comprendre l'influence de l'atmosphère. Les résultats obtenus montrent que l'utilisation du vide permet d'éliminer, de l'enceinte de traitement, les produits volatils formées au cours du traitement conduisant à des taux de lignine de Klason plus faibles du fait de la non recondensation des produits de dégradation. Cette limitation de recondensation des produits volatiles engendre des pertes de masse, pour une même intensité de traitement plus faibles, confirmés par des taux de polysaccharides plus élevés pour un traitement sous vide. Des études de cinétiques des réactions de thermodégradation ont confirmé la plus grande sensibilité des feuillus vis-à-vis de la thermodégradation (comparé aux résineux). De plus, ces analyses ont permis d'identifier les principaux produits de thermodégradation du bois qui varient en fonction de l'intensité du traitement et a permis de montrer une thermosensibilité plus importante de la lignine que de l'holocelluloses pour la gamme de températures utilisée. Le fruit de ces travaux est donc une progression significative des connaissances de bases sur les mécanismes de thermodégradation et leurs relations avec les paramètres de traitement / Thermal treatment is based on biopolymer chemical degradation by heat transfer, without additional chemical products impregnation. This process improves the dimensional stability and the decay resistance of wood. These improvements come at the expense of wood mechanical properties of wood which weak. Several types of heating processes exist currently differing mainly by the nature of the inert atmosphere used during treatment. The durability of this new wood material is correlated to the degree of polymers thermal degradation depending on the conditions and the treatment intensity. A conducting heat treatment pilot using nitrogen or vacuum and allowing dynamic record of mass loss is used to understand better the atmosphere influence. The results show that utilization of vacuum permit the elimination of volatile products formed during heat treatment and accumulated in oven, leading to lower extractives and Klason lignin contents due to the non recondensation of thermal degradation products. Limitation of the formation of recondensation products generates a lower mass loss for same treatment intensity and explains the lower polysaccharides degradation during a vacuum process. Fine chemical analyses and the study about thermal degradation reaction kinetics have allowed confirming the higher sensibility of hardwood than softwood to thermal degradation. In addition, these analyses have permitted the volatile thermal degradation products identification related to the treatment intensity. Subsequently, results have shown a higher thermal sensibility of lignin than holocelluloses for temperatures below 230°C. This work is a significant increase in basic knowledge about the mechanisms of wood thermal degradation and their relations with the processing parameters

L'objectif de cette thèse a été de mesurer comment les modifications des régimes hydrologiques, plus particulièrement les exondations, régissent 1) certains aspects du fonctionnement des zones humides, 2) l'organisation et la dynamique à court terme des communautés végétales aquatiques et 3) la survie et la réponse plastique des végétaux aquatiques. Cette thèse aborde les questions à des échelles spatio-temporelles différentes. Premièrement, à l'échelle de la décennie, j'ai mesuré la conséquence de la baisse de la hauteur d'eau des zones humides péri-fluviales sur leur physico-chimie. Deuxièmement, à l'échelle de la saison, j'ai mesuré l'influence des caractéristiques sédimentaires des zones humides sur la réponse à court terme des communautés végétales à l'exondation. Enfin, à l'échelle de quelques semaines, je me suis intéressée à l'aptitude des espèces d'angiospermes aquatiques à mettre en place un ajustement plastique face à l'exondation, en conditions expérimentales de laboratoire et in situ, j'ai recherché les déterminismes de cette réponse (écologiques, morphologiques, phylogénétiques). En termes de caractéristiques physico-chimiques des eaux de surface, l'étude sur 15 ans de la dynamique de zones humides péri-fluviales subissant des exondations, ne conclue pas, comme cela est habituellement décrit dans la littérature, à une augmentation de la teneur en nutriments de la masse d'eau, mais plutôt des changements suggérant des variations du fonctionnement hydrogéologique des zones humides, en faveur d'une plus grande influence de la nappe de versant dans leur alimentation. La réponse in situ des communautés végétales à l'exondation diffère selon le type de sédiment. La résistance et la résilience des communautés décroissent toutes deux avec la capacité de rétention d'eau du sédiment. La capacité des plantes aquatiques à tolérer l'exondation, en conditions expérimentales, semble différer selon leur position phylogénétique, mais pas selon leur forme de croissance (rosettes ou caulescentes) / The objective of this thesis was to measure how changes in hydrological regimes, particularly dewatering govern 1) aspects of the functioning of wetlands, 2) the organization and short-term dynamics of aquatic plant communities and 3 ) survival and plastic response of aquatic plants. This thesis addresses issues at different spatial and temporal scales. First, at the decade scale, I measured the effect of water-level decreases in riverine wetlands on their physico-chemistry characteristics. Second, at the season scale, I measured the influence of sedimentary characteristics of wetlands on short-term response of plant communities to dewatering. Finally, at the scale of a few weeks, I was interested in the ability of aquatic angiosperm species to develop a plastic adjustment to dewatering, in experimental laboratory conditions and in situ, and I looked determinism of this response (ecological, morphological, phylogenetic). In terms of physico-chemical characteristics of surface waters, the 15- year study of the dynamics of riverine wetlands undergoing dewatering, not reached, as is usually described in the literature, with an increase of water body nutrient contents, but rather changes suggesting variations of the hydrogeological functioning of wetlands in favor of a greater influence of the hillslope groundwater table in their water supply. In situ response of plant communities to dewatering differs according to sediment type. Both, resistance and resilience of communities decrease with the sediment water retention capacity. The ability of aquatic plants to tolerate dewatering, in experimental conditions, seems to differ according to their phylogenetic position, but not according to their growth form (rosettes or caulescentes). Species tolerating dewatering show phenotypic adjustments such as denser aerial organs and high plasticity of the leaves, which may explain the maintenance of a similar growth rate in terrestrial and aquatic conditions in these species

Les choix et préférences des consommateurs pour les aliments sont largement conditionnés par leurs propriétés sensorielles, et notamment par les perceptions aromatiques dans le cas des boissons alcoolisées. Un des enjeux des industriels du secteur pour contrôler et développer les ventes des produits est de mieux comprendre les déterminants de la qualité sensorielle de ces produits. Les travaux réalisés dans le cadre de ce projet de thèse concernent les cognacs et visent à appréhender les liens entre la composition des produits, les étapes du processus d’élaboration, dont la phase de vieillissement, et leurs caractéristiques sensorielles finales. L’objectif est notamment de comprendre l’impact des constituants de la matrice des cognacs sur la libération et la perception des composés d’arôme. Pour répondre à cet objectif, une stratégie fondée sur des approches sensorielle et physicochimique a été mise en œuvre. Les travaux réalisés en évaluation sensorielle ont permis de montrer l’absence d’impact des constituants non-volatils et de réaffirmer l’importance des composés d’arôme dans la perception des différences sensorielles entre les cognacs. Le suivi des libérations de composés d’arôme par PTR-MS au cours de la consommation des cognacs a été possible par la mise au point de conditions opératoires compatibles avec la teneur élevée en éthanol des produits. Ces travaux ont montré que les composés d’arôme clés pour la perception des cognacs étaient libérés en plus grandes quantités dans les cognacs les plus âgés. En revanche, aucune différence entre les produits n’a été constatée au niveau de la temporalité de ces libérations. L’application des approches statistiques prédictives a finalement permis de montrer qu’il est possible de prédire les propriétés sensorielles des cognacs à partir de certaines de leurs caractéristiques physicochimiques, et que les corrélations établies entre les variables physicochimiques et sensorielles pouvaient être expliquées qualitativement grâce aux connaissances existantes dans la littérature et à celles des experts, notamment concernant leur processus d’élaboration. / Consumer’s choices and preferences for foods are widely influenced by their sensory properties, and especially by aromatic perceptions in the case of alcoholic beverages. One of the challenges of wine and spirit industries for controlling and developing product sales is to gain insights on the determinants of the sensory quality of their products. The work carried out during this PhD project concerns cognacs and aim to apprehend the links between product composition, the stages in their elaboration process, including maturation, and their final sensory properties. An important objective is to understand the impact of cognac matrix components on aroma compounds release and perception. To fulfill this objective, a strategy based on the use of physicochemical and sensory approaches was set up. Sensory evaluation enabled to highlight the absence of impact of non-volatile components and to reaffirm the essential effect of aroma compounds for the perception of sensory differences between cognacs. The monitoring of the release of aroma compounds by PTR-MS during cognac consumption has been possible by the setting up of operating conditions allowing the analysis of high ethanol-containing beverages. These works have shown that key aroma compounds for cognac perception were released in higher amounts in the oldest cognacs. However, no difference was observed concerning their temporality of release. The development of statistical approaches finally showed that it was possible to predict the sensory properties of cognacs from their physicochemical characteristics. Correlations between physicochemical and sensory variables could be qualitatively explained in reference to the knowledge on the elaboration process of cognac in the literature and held by experts.

Dans un contexte où le développement durable est devenu une priorité majeure, les entreprises du secteur du bâtiment doivent faire face, à de nouvelles exigences en termes de respect de l’environnement. En particulier, lors de la mise en œuvre du béton dans les coffrages, une huile de démoulage d’origine minérale faiblement biodégradable est couramment utilisée comme couche séparatrice anti-adhérente. La nature de cette huile génère des risques importants de pollution environnementale. De nouvelles formulations d’huile de décoffrage d’origine végétale ont ainsi été développées.L’apparition de cette nouvelle gamme de produit nécessite une connaissance suffisante de leur comportement à l’interface béton/huile/coffrage. Ce mémoire contribue à l’étude de l’influence de la formulation du béton sur le comportement tribologique à l’interface béton/coffrage en présence de deux huiles de démoulage de nature différente (une huile végétale et une huile minérale). La zone du béton à l’approche du coffrage a été étudiée à l’état durci et frais sans huile de démoulage. Tout d’abord, l’évolution de la densité apparente du béton à l’approche d’une paroi a été évaluée en fonction de la pression de contact et du volume de pâte. Puis, une analyse complète de cette zone à l’interface à l’état frais a été réalisée afin d’estimer le rapport E/L et la quantité de pâte mobilisée à l’approche de la paroi coffrante. Une étude physico-chimique a été effectuée en reconstituant les milieux interstitiels de l’interface béton/huile/coffrage contenant un dosage différent en superplastifiant et en huile. Plusieurs techniques adaptées à ces milieux complexes, ont été utilisés afin d’évaluer la formation de savons et de déterminer la stabilité des émulsions obtenues. Cette thèse se conclue par une étude du frottement du béton frais contre une paroi coffrante avec et sans huile de démoulage à l’aide d’un tribomètre plan/plan. Plusieurs formulations de béton sont étudiées. Les résultats obtenus ont permis de comprendre le mode d’action des éléments fins et le dosage en superplastifiant aux interfaces béton/coffrage et béton/huile/coffrage. Dans le cas de l'huile d'origine végétale, le savon formé à partir des esters et des acides gras contribue à réduire les frottements en stabilisant l’émulsion et en organisant l’interface. Cependant, la présence du superplastifiant est indispensable pour avoir des performances élevées dans le cas de l’huile minérale. / In a context where sustainable development has become a major priority, the companies in the building field must face to new requirements in terms of respect of the environment. In particular, during the concrete pouring, a mineral release agent, poorly biodegradable is currently used as separating layer non-stick. The nature of this oil creates significant risks of environmental pollution. New formulations of release agent of vegetable origin were developed.The appearance of this new product range requires a sufficient knowledge of their behavior at the interface concrete/release agent/formwork. This report contributes to the study the effect of the concrete composition on the tribological behavior at the interface concrete/formwork with two release agents of different nature (vegetable release agent and mineral release agent). The zone of concrete near the formwork was studied without release agents. First, the evolution of the density of the concrete at the approach of a wall was evaluated as a function of the contact pressure and the past volume. Then, a comprehensive analysis of this fresh layer was carried out to estimate the W/B ratio and the amount of paste mobilized close to the formwork. A physicochemical study was performed by reconstituting the interstitial medium of the interface concrete/release agent/formwork containing a different dosage of oil and superplasticizer. Several adapted techniques to these complex medium were used to evaluate the formation of soaps and to determine the stability of the obtained emulsions. This thesis ends with a study of the friction of fresh concrete against the formwork with and without release agent using a plan/plan tribometer. Many formulations of concrete are studied. The results were allowed to understand the mechanism of action of the fines element and the dosage of superplasticizer at the interfaces concrete/formwork and concrete/release agent/formwork. In the case of vegetable release agent, the soap formed from the esters and fatty acids contributes to reduce the friction by stabilizing the emulsion and organizing the interface. However, the presence of the superplasticizer is necessary to obtain a high performance for the mineral release agent.

A maca (Lepidium meyenii Walpers) é uma planta herbácea bienal da família Brassicae, cultivada principalmente na região dos Andes da América do Sul. A parte subterrânea vem sendo consumida por muito tempo devido a seu valor nutricional e energético, mas é mais conhecida no mercado peruano e internacional por alegadas propriedades terapêuticas. Esta raiz apresenta até 76% de carboidratos, dos quais 30% é amido. Este trabalho teve como objetivos estudar: as propriedades físico-químicas e funcionais do amido isolado; os parâmetros enzimáticos durante o armazenamento e a purificação parcial de enzimas amilolíticas. Em relação às propriedades do amido, este apresentou um teor de amilose de 20% valor semelhante aos encontrados em raízes e tubérculos similares. A turbidez das suspensões de amido apresentou estabilidade durante o armazenamento. A temperatura de gelatinização e a viscosidade da pasta foram a 45,7° e 46°C, respectivamente. Com base nos dados obtidos, o amido de maca seria indicado para alimentos que requeiram temperaturas moderadas no processamento, não sendo apropriado para o emprego em alimentos congelados. Os parâmetros enzimáticos medidos tais como teor de amido total, teor de açúcares solúveis, atividade amilolítica total, atividade de α e β amilases, não mostraram diferenças significativas entre as medidas durante um período de armazenamento de 16 dias. As microscopias eletrônicas de varredura (MEV) dos grânulos de amido mostraram grãos íntegros com superfícies lisas, com algumas depressões ao redor dos grânulos os quais poderiam indicar o inicio de ataque enzimático, ou fraturas na purificação. Em relação à purificação de enzimas amilolíticas, foi possível separar uma fração ativa com a carboximetilcelulose (CMC) seguida de cromatografia liquida de alta resolução (CLAE) que permitiu a separação de duas frações protéicas, analisadas por eletroforese SDS-PAGE e eletroforese bidimensional (2D). Os polipeptídeos identificados no gel 2D apresentaram massa molecular semelhante entre 22 a 27 kDa, e os pontos isoelétricos entre 4,8 e 7,3. / Maca (Lepidium meyenii Walpers) is a biennial herbaceous plant from Brassicae family, grown mainly in the Andes of South America. The underground part has been consumed for a long time due to its nutritional value and energy, but is best known in the Peruvian and international market for alleged therapeutic properties. This root has up to 76% carbohydrates, of which 30% is starch. This work aimed to study: the physico-chemical properties of isolated starch, the enzymatic parameters during storage and partial purification of amylases. In relation to the properties of starch, the amylose content showed a 20% value similar to those found in roots and tubers alike. The turbidity of starch suspensions was stable during storage. The gelatinization temperature and viscosity of the paste were 45.7 ° and 46 ° C, respectively. Based on data obtained from the starch of litter would be given to foods that require moderate temperatures in processing and is not suitable for use in frozen foods. The enzymatic parameters measured such as total starch content, soluble sugars, total amylolytic activity, activity of α and β amylases, showed no significant differences between the measures over a storage period of 16 days. Electronic microscopy (SEM) of starch granules showed grains with smooth surfaces, with some depressions around the granules which could indicate the beginning of enzymatic attack, or fractures in the purification. Regarding the purification of amylases was possible to separate an active fraction with carboxymethylcellulose (CMC) followed by high-resolution liquid chromatography (HPLC) which allowed the separation of two protein fractions, analyzed by SDS-PAGE and two-dimensional electrophoresis (2D ). The polypeptides had a molecular mass between 22 and 27 kDa and isoelectric points ranging from 4.8 to 7.3.

O arroz (Oryza sativa L.) é um dos cereais mais produzidos e consumidos no mundo, caracterizando como principal alimento para mais da metade da população mundial. Sua importância é destacada principalmente em países em desenvolvimento, tais como o Brasil, desempenhando papel estratégico em níveis econômico e social. Atualmente, é crescente o número de pesquisas que integram desde o melhoramento vegetal e o manejo da adubação até o aproveitamento dos nutrientes pelo organismo humano. O melhoramento de plantas pode ajudar a melhorar a dieta humana, com o desenvolvimento de plantas com maiores teores de vitaminas e micronutrientes. A introdução de produtos agrícolas biofortificados como o arroz, complementará as intervenções em nutrição existentes. Sendo assim, tornase imprescindível conhecer como as condições de cultivo influenciam na qualidade do grão e na importância para obtenção de um alimento com maior valor biológico e nutricional e com menores concentrações de antinutricionais. O objetivo deste trabalho foi analisar as características físico-químicas e nutricionais do arroz (Oryza sativa L.) integral, promovidas por diferentes adubações (experimento I) e aos grãos biofortificados (experimento II). Foram realizadas análises de composição centesimal, composição mineral, diálise in vitro de minerais, vitaminas do complexo B, conteúdo de compostos fenólicos e fitatos em grão, além das análises de parâmetros de qualidade em arroz como conteúdo de amilose aparente, propriedade de pasta e análise instrumental de cor. Os resultados obtidos no estudo assemelham-se aos citados nas literaturas quanto á composição centesimal e mineral, enfatizando a influência da cocção na composição nutricional do grão e em seus compostos como fenólicos e fitatos. Para o dialisado de cálcio e zinco no arroz biofortificado, a variação nos valores foi em média de 1,14% a 3,26% para cálcio e 0,80% a 3,43% para zinco. No experimento II, as perdas de vitaminas para o arroz integral biofortificado após o cozimento foi em torno de 33,4%, 52,17% e 76% para vitamina B1, vitamina B2 e vitamina B6, respectivamente. Por fim, conclui-se que a produção de variedades melhoradas seja através de adubações ou da escolha de melhores cultivares, que apresentam maior teor de minerais e vitaminas, foram eficientes para a melhora da disponibilidade nutricional dos grãos. / Rice (Oryza sativa L.) is one of most cereals produced and consumed in the world, characterized as the primary food for more than half the world population. Its importance is highlighted especially in developing countries such as Brazil, playing a strategic role in economic and social levels. There is increasing the number of studies since that integrate plant breeding and fertilizer management to use the nutrients the human body. Plant breeding can help improve the human diet, with the development of plants with higher levels of vitamins and micronutrients. The introduction of biofortified crops like rice, will complement existing nutrition interventions. Thus, it becomes essential to know as the cultivation conditions influence the quality of grain and the importance to obtain a food with higher nutritional and biological value and with lower concentrations of antinutritional. Threfore, the aim of this study was to analyze the pshycochemical and nutritional properties of rice (Oryza sativa L.) in full, caused by different fertilization (experiment I) and subjected to biofortification (experiment II). Were performed to analyze chemical composition, mineral, dialysis in vitro of minerals, vitamins B, content of phenolic compounds and phytates in grain, in addition to the analysis of quality parameters in rice as apparent amylase content, folder property and instrumental analysis of color. The results obtained in this study are similar to those cited in other literature as to the mineral and chemical composition, emphasizing the influence of cooking on the nutritional composition of grain and as phenolic compounds and phytates. For the dialysate calcium and zinc in rice biofortified crops, the variation in the values averaged 1.14% to 3.26% for calcium and 0.80% to 3.43% for zinc. Losses of vitamins to the rice after cooking was around 33.4%, 52.17% and 76% for vitamin B1, vitamin B2 and vitamin B6, respectively. Finally, we conclude that the production of improved varieties is through fertilization or the best choice of cultivars, that have a higher content of minerals and vitamins, were effective to improve the availability of nutrients of the grains.

<p>U okviru ove disertacije uspe&scaron;no je sintetisano 14 novih protičnih jonskih tečnosti na bazi amina. Strukture su potvrđene snimanjem NMR i IC spektra. Izmerena je gustina svih jonskih tečnosti u temperaturnom opsegu&nbsp; T&nbsp; = (293,15&nbsp; &ndash;&nbsp; 353,15) K, kao i gustina njihovih vodenih rastvora u temperaturnom opsegu&nbsp; T&nbsp; = (293,15 &ndash; 313,15) K. Fizičko-hemijska karakterizacija je takođe propraćena merenjem viskoznosti i električne provodljivosti binarnih sme&scaron;a u celom rasponu&nbsp; molarnih frakcija i na različitim temperaturama (T&nbsp; = (293,15&nbsp; &ndash;&nbsp; 313,15) K). Na osnovu dobijenih rezultata utvrđeno je da sve protične jonske tečnosti imaju izražen structure making efekat. Ispitana je antimikrobna aktivnost protičnih jonskih tečnosti na bazi amina prema deset sojeva fungi: Trichoderma sp., Penicillium sp.(1-3), Cladoporium sp., Aspergillus sp. (1,2), A. flavus, F. graminearum i P. citrinium,&nbsp; osam sojeva bakterija:&nbsp; B. subtillis (6633), S. aureus (6538), E. faecalis (19433), K. rhizophila (9341),&nbsp; E. coli (11229), S. enteritidis (13076), P. mirabilis (12453), P. aeruginosa (15692) i dva soja kandida:&nbsp; C. albicans (ATCC 10231) i C. albicans (L) .&nbsp; Rezultati su pokazali da svih četrnaest jonskih tečnosti pokazuju antimikrobno delovanje. Za proučavane protične&nbsp; jonske tečnosti, antimikrobna aktivnost zavisi od dužine alkil lanca, pri tome pokazujući maksimalnu aktivnost sa anjonima koji sadrže 3 i 4 atoma ugljenika u nizu. Rezultati su pokazali da PILs pokazuju bolje antimikrobno dejstvo ako istovremeno sadrži i terminalno hlorovani C atom. Međutim, PILs pokazuju veću aktivnost ako je terminalni C atom monohalogeniran, jer monohalogenirani derivati poseduju veći afinitet za interakciju sa ćelijskom membranom. Najefikasnije PILs (ClA, 3-ClP, 4-ClB, Ac i For) su izabrane da se testiraju kao alternativni rastvarači umesto timola. Svih pet protičnih jonskih tečnosti uspe&scaron;no je testirano kao zelena alternativa za uobičajne organske rastvarače koji se koriste za či&scaron;ćenje i konzervaciju papirne povr&scaron;ine. Značajna antimikrobna svojstva primećena u ovoj doktorskoj tezi sugeriraju da proučavane protične jonske tečnosti mogu imati potencijalnu primenu u radu sa papirnim atifaktima, kao i pri njihovom či&scaron;ćenju i konzervaciji, zamenjujući na taj način primenu konvencionalnih rastvarača i organske supstance otrovne za ljude i životnu sredinu.</p> / <p>In this doctoral thesis the 14 amine based protic ionic liquids were newly synthesized. The validity of all structures were checked and confirmed by NMR and IR spectroscopy. Densities of pure ionic liquids and their diluted aqueous solutions have been measured over the whole composition range at selected temperatures from (293.3 to 353.15) K for pure ionic liquids, and from (293.15 to 313.15) K for diluted aqueous solutions. Physico-chemical&nbsp; characterization was also performed&nbsp; measuring the viscosity and electrical conductivity of binary mixtures in the entire range of mole fractions and at different temperatures (T&nbsp; = (293.15&nbsp; &ndash;&nbsp; 313.15) K). It was concluded that all investigated PILs have structure making tendency. Further, antimicrobial activity of amine based protic ionic liquids has been investigated using ten fungi strains: Trichoderma sp., Penicillium sp. (1-3), Cladoporium sp., Aspergillus sp. (1,2), A. flavus, F. graminearum i P. citrinium, eight ATCC bacterial strains: B. subtillis (6633), S. aureus (6538), E. faecalis (19433), K. rhizophila (9341), E. coli (11229), S. enteritidis (13076), P. mirabilis (12453), P. aeruginosa (15692) and two Candida&nbsp; strains:&nbsp; C. albicans (ATCC 10231) i C. albicans (L). The results indicated that all fourteen ionic liquids showed antimicrobial activity.&nbsp; For the studied PILs, the antimicrobial activity dependent on the alkyl chain length, showing maximal activity with anions containing 3 and 4 carbon atoms. The results revealed that the PILs show better antimicrobial activities if the longer alkyl chain is presented but in the same time contain chlorinated terminal C atom. However, PILs showed higer activity if the terminal C atom is monohalogenated, since the monohalogenated derivatives possess higher affinity to interact with cell membrane. The most effective PILs (ClA, 3-ClP, 4-ClB, Ac and For)&nbsp; were chosen to be tested as alternative solvents instead of thymol. All five PILs were successfully tested as the green alternatives to conventionally used organic solvents for paper cleaning and conservation. The significant antimicrobial properties observed in this doctoral thesis suggest that studied PILs may have potential applications in the paper art and artefact cleaning and conservation replacing thus, conventional solvents and organic substances that are toxic for humans and environment.</p>

<p>U okviru doktorske disertacije ispitana je mogućnost proizvodnje<br />fermentisanog mlečnog napitka uz primenu različitih vrsta i koncentracija<br />nekonvencionalnog startera čajne gljive: a) nativnog inokuluma-I<br />(10% i 15%) b) koncentrovanog mikrofiltracijom - MFI (10% i 15%) i c)<br />koncentrovanog uparavanjem - UPI (1,5%, 3,0%, 10% i 15%). Varijante<br />fermentisanog mlečnog napitka dobijene su kori&scaron;ćenjem mleka sa 0,9%<br />i 2,2% mlečne masti. Za pobolj&scaron;anje fizičko-hemijskih i teksturalnih<br />karakteristika proizvoda u mleko pre inokulacije dodato je 0,02% enzima<br />transglutaminaze (aktiviran na 40&deg;C, a posle 2 sata je inaktiviran na<br />80&deg;C, 1 minut). Fermentacija mleka (pri temperaturi 42&deg;C) uz kori&scaron;ćenje<br />inokuluma čajne gljive praćena je do postizanja pH vrednosti 4,5.<br />Nakon proizvodnje analizirana je nutritivna vrednost fermentisanih<br />mlečnih napitaka: sadržaj masti, proteina, laktoze, galaktoze, glukoze,<br />fruktoze, mlečne i sirćetne kiseline, etanola, vitamina (B1, B2, B6 i<br />C), minerala (Ca, Mg, K, Na, Pb, Cd, Cu, Zn) i masnih kiselina. Sadržaj<br />odabranih komponenata u napicima praćen je tokom 10 dana skladi&scaron;tenja.<br />Fizičko-hemijske osobine (kiselost, sinerezis i sposobnost vezivanja<br />vode), teksturalne karakteristike (čvrstoća, konzistencija, kohezivnost i<br />indeks viskoziteta) i viskozitet uzoraka praćeni su nakon proizvodnje i<br />posle 10 dana skladi&scaron;tenja. Ukupan broj bakterija sirćetne kiseline (BSK)<br />i kvasaca u fermentisanim napicima analiziran je nakon proizvodnje i<br />tokom skladi&scaron;tenja. Varijante fermentisanih mlečnih napitaka senzorno<br />su ocenjene nakon proizvodnje.<br />Na osnovu rezultata ispitivanja utvrđeno je da fermentacija mleka<br />uz primenu nekonvencionalnog startera čajne gljive predstavlja složen<br />biohemijski proces pri čemu fermentacija traje od 9 do 12 sati i prosečno<br />je dva puta duža od fermentacije mleka u proizvodnji probiotskog i<br />tradicionalnog jogurta. Sadržaj laktoze tokom fermentacije mleka manji<br />je prosečno za 19,6% u odnosu na sadržaj laktoze u mleku. Uzorci<br />proizvedeni sa nativnim inokulumom uz primenu transglutaminaze i<br />koncentrata proteina surutke imaju za 15% niži sadržaj laktoze, a uzorak<br />15% I za 2% niži sadržaj u odnosu na uzorak 10% I. Uzorci proizvedeni<br />sa 10% MFI i 15% MFI imaju za 11%, odnosno 21% niži sadržaj laktoze<br />nakon proizvodnje u poređenju sa odgovarajućim uzorcima proizvedenim<br />uz primenu nativnog inokuluma. Sniženje sadržaja laktoze je<br />praćeno povećanjem sadržaja galaktoze i L-mlečne kiseline u svim uzorcima.<br />D-mlečna kiselina, sirćetna kiselina i etanol zastupljeni su u veoma<br />malim koncentracijama.<br />Imajući u vidu značaj vitamina C u ishrani i količinu detektovanu<br />u fermentisanom mlečnom napitku, konzumiranjem 500 g napitka<br />dobijenog primenom čajne gljive mogu da se zadovolje dnevne potrebe<br />za vitaminom C.<br />Tokom proizvodnje fermentisanih napitaka sadržaj vitamina B1<br />poraste za 5,09%, vitamina B2 za 2,65% i B6 za 2,03% u odnosu na<br />mleko. U fermentisanom mlečnom napitku iz mleka sa 2,2% masti<br />sadržaj vitamina B6 je povećan 24,76% u odnosu na sadržaj u polaznom<br />mleku. Fermentisani mlečni napici proizvedeni primenom čajne<br />gljive iz mleka sa 0,9% i 2,2% masti sa dodatkom 10% inokuluma<br />čajne gljive sadrže najvi&scaron;e vitamina B2 koji iznosi 108 (&mu;g/100g), odnosno<br />136 (&mu;g/100g). Mikrobiolo&scaron;ki sastav napitaka se razlikuje u zavisnosti<br />od vrste i sastava kori&scaron;ćenog inokuluma. Najveći broj BSK<br />(4,5 &middot; 104ćelija/mL) i kvasaca (9 &middot; 104 ćelija/mL) je u uzorku 10% MFI,<br />dok je manji u napitku 10% I (BSK: kvasci= 4,05 &middot; 104: 4,5 &middot; 104).<br />Dodatkom transglutaminaze u minimalnoj koncentraciji od<br />0,02% postižu se znatno bolje fizičko-hemijske i reolo&scaron;ke karakteristike<br />fermentisanih mlečnih napitaka dobijenih iz mleka sa 0,9% masti.<br />Generalno posmatrano, kori&scaron;ćenjem 10% nativnog inokuluma za<br />proizvodnju napitaka iz mleka sa 0,9% i 2,2% masti dobijaju se proizvodi<br />optimalnih hemijskih, mikrobiolo&scaron;kih i senzornih karakteristika.<br />Funkcionalni fermentisani mlečni napici proizvedeni uz primenu različitih<br />vrsta i koncentracija čajne gljive su proizvodi visoke nutritivne<br />vrednosti namenjeni različitim kategorijama potro&scaron;ača.</p> / <p> The possibility of fermented milk beverages manufacture<br /> by applying non-convenctional starter culture - tea fungus<br /> inoculum: a) natural inoculum (10% and 15%); b) concentrated<br /> by microfiltration (10% i 15%); c) concentrated by evaporation<br /> (1.5% and 3.0%) have been investigated. All fermented milk samples<br /> were produced from milk of 0.9% and 2.2 % fat content.<br /> Improvement of rheological properties of low fat fermented milk<br /> products by addition of enzyme transglutaminase (TG) was<br /> achieved. Transglutaminase (Activa MP, Ajinomoto Co. Inc.,<br /> Hamburg, Germany) was activated in milk at 40&deg;C for 2 hours,<br /> then it was inactivated by high temperature (80&deg;C for 1 minute)<br /> prior to fermentation. After cooling to optimal temperature<br /> (42&deg;C), chosen starter culture was added in milk. In all cases<br /> fermentation stopped when the pH=4.5 was reached.<br /> Nutritive characteristics of samples: content of proteins,<br /> lactose, galactose, glucose, fructose, lactic and acetic acid, ethanol,<br /> vitamins (B1, B2, B6 and C), minerals (Ca, Mg, K, Na, Pb,<br /> Cd, Cu, Zn) and total fatty acids content were analysed after<br /> production. Selected components were determined after 10 days<br /> of storage. Physico-chemical characteristics (acidity, syneresis,<br /> water-holding capacity), textural characteristics (firmness,<br /> consistency, cohessivnes, and index of viscosity) and viscosity<br /> were measured at 5&deg;C after production and during 10 days of<br /> storage.<br /> On the basis of the obtained results it can be concluded<br /> that milk fermentation lasted from 9 to 12 hours and is two times<br /> longer compared to fermentation during probiotic and traditional<br /> yoghurt production. Lactose content decreased during fermentation<br /> for 19.6% compared to milk. Higher transformation of lactose<br /> was determined in samples produced by using microfiltration<br /> inoculum. Decreasing of lactose content affected the increased<br /> galactose and L-lactic acid content. Content of D-lactic acid,<br /> acetic acid and ethanol were detected in low concentrations. High<br /> concentration of ascorbic acid in beverage contributed that 500 g<br /> fermented milk beverage could fullfill recommended daily intake<br /> for vitamin C. Sample produced from milk of 2.2% fat content<br /> using 10% natural inoculum contained the highest concentration<br /> of vitamin B2 &ndash; 136 (&mu;g/100g).<br /> The highest total cell count of acetic acid bacteria was<br /> 4.5 &middot; 104 cfu/ml and yeasts 9 &middot; 104 cfu/ml in samples produced by<br /> using 10% microfiltrated inoculum. Sample produced from milk<br /> of 0.9% fat content by applying 10% natural inoculum had also<br /> high number of acetic acid bacteria and yeasts in ratio 4.05 &middot; 104 :<br /> 4.5 &middot; 104.<br /> The sample having tea fungus concentrated inoculum<br /> and transglutaminase had the best textural characteristics. Fermented<br /> dairy beverages produced by 0.02% TG application had<br /> much better textural characteristics than those without TG.<br /> Generaly, fermented dairy drinks produced from milk of<br /> 0.9 and 2.2% fat content with addition of natural inoculum in<br /> concentration of 10% showed optimal sensory, nutritive and rheological<br /> characteristics.<br /> Therefore, fermented dairy drinks produced with tea<br /> fungus inoculum could be classified as high valuable functional<br /> food intended for all consumer categories.</p>