A necessidade de um controle de qualidade seguro e confiável em produtos e/ou matérias-primas provenientes das indústrias farmacêuticas e agrícolas torna as análises de seus ativos e constituintes extremamente importantes para os fabricantes, bem como para os usuários desses produtos. Apesar da espectroscopia de Ressonância Magnética Nuclear (RMN) ser uma das mais importantes ferramentas de análise qualitativa, ainda é pouco usada para fins quantitativos. Considerando esses fatos, métodos para análises de produtos farmacêuticos e agrícolas, empregando técnicas de RMN, foram desenvolvidos no presente trabalho. Um método quantitativo de RMN de 1H em alta resolução para análise de paracetamol em diferentes formulações farmacêuticas foi validado de acordo com a Resolução RE nº 899. Neste método foi usado um padrão interno, tornando desnecessária a construção de uma curva analítica. Outros ativos presentes nas formulações também puderam ser quantificados e alguns excipientes, identificados. De acordo com NBR 14029, foram desenvolvidos e validados métodos empregando RMN em alta resolução de 1H e 31P para análise de glifosato em agrotóxicos. Neste caso, foi empregado um padrão externo, o qual possibilitou análises quantitativas sequenciais dos diferentes núcleos sem a necessidade de um novo preparo de amostra. A RMN em alta resolução de 1H também foi avaliada como um método alternativo para a determinação de ácidos graxos em óleos e azeites, dispensando as reações de transesterificações necessárias para as análises cromatográficas. A RMN no domínio do tempo (RMN-DT) foi usada no desenvolvimento de um método para detecção de adulteração de azeites de oliva com óleo de soja. Esse método baseou-se na diferença de viscosidade do azeite e do óleo e possui a grande vantagem de poder ser aplicado em embalagens lacradas. Por fim, diferentes abordagens analíticas empregando a RMN em alta resolução foram feitas para análises do fitoterápico Cardo-Leiteiro (Silybum marianum L. Gaertn., Asteraceae), possibilitando a quantificação simultânea de sete constituintes ativos, incluindo dois pares de diastereoisômeros. Assim, demonstrou-se no presente trabalho o potencial das técnicas de RMN quantitativas, para o controle de qualidade de produtos farmacêuticos e agrícolas, com algumas vantagens sobre os outros métodos analíticos normalmente usados nessas análises. / The need for effective and reliable quality control in products and/or raw materials from pharmaceutical and agricultural industries make analyses of their actives compounds and constituents very important to manufacturers and consumers. Nuclear Magnetic Resonance spectroscopy (NMR) is one of the most important tools for qualitative analysis but it is rarely used as quantitative method. Considering these facts, quantitative NMR methods (qNMR) for analysis of pharmaceutical and agricultural products were developed in this thesis. A high resolution 1H qNMR method for paracetamol, in different pharmaceutical formulations, was validated according to RE Resolution Nº 899. An internal standard was used in this method, therefore, the construction of a calibration curve was unnecessary. Other actives constituents present in the formulations could also be quantified and some excipients, identified. According to NBR 14029, high resolution qNMR 1H and 31P methods were developed and validated for glyphosate. In this case, an external standard was used, which enabled sequential quantitative analyses of different nuclei without the need to prepare a new sample. The high-resolution qNMR 1H was also used as an alternative method for fatty acids determination in oils and olive oils, dispensing transesterifications reactions required for GC analysis. Time domain NMR (TD-NMR) was used to develop a method to detect adulteration of olive oil with soybean oil. This method was based on the viscosity difference between olive oil and soybean oil, and has a great advantage, because it can be applied in sealed packages. Finally, different analytical approaches using high resolution NMR 1H were studied to qualitative and quantitative analysis of milk thistle (Silybum marianum L. Gaertn., Asteraceae), a botanical dietary supplement, enabling the simultaneous quantification of seven active constituents, including two pairs of diastereoisomers. Therefore, it was demonstrated in this thesis the potential of qNMR techniques to quality control of pharmaceutical and agricultural products, with some advantages over other analytical methods, normally used in these analyses.

Submitted by Maria Beatriz Vieira (mbeatriz.vieira@gmail.com) on 2017-06-23T12:29:15Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) tese_fabiana_fonseca_dos_santos.pdf: 3022588 bytes, checksum: 060ec7a7f1d4edb18fdd846563216008 (MD5) / Approved for entry into archive by Aline Batista (alinehb.ufpel@gmail.com) on 2017-06-23T22:08:43Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) tese_fabiana_fonseca_dos_santos.pdf: 3022588 bytes, checksum: 060ec7a7f1d4edb18fdd846563216008 (MD5) / Made available in DSpace on 2017-06-23T22:08:43Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) tese_fabiana_fonseca_dos_santos.pdf: 3022588 bytes, checksum: 060ec7a7f1d4edb18fdd846563216008 (MD5) Previous issue date: 2016-05-19 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / As etapas da ontogenia de oliveiras (Olea europaea L.), desde a germinação das sementes, o período de crescimento juvenil e de transição da fase reprodutiva até mesmo o desenvolvimento da inflorescência frutífera, são longas e problemáticas. Desta forma, objetivou-se acelerar o processo germinativo (superando a latência) e de formação de mudas da cultivar Arbequina, além de caracterizar morfológica e molecularmente, acessos de oliveiras do banco ativo de germoplasma da Embrapa Clima Temperado (Pelotas/RS) para gerar informações que possam contribuir em futuros programas de melhoramento genético de oliveira do Estado do Rio Grande do Sul. Para os experimentos de germinação utilizou-se sementes da cv. Arbequina com e sem o endocarpo, as quais foram semeadas em casa de vegetação e sem endocarpo e embrião para cultivo in vitro. As plantas obtidas da germinação in vitro (sementes sem endocarpo), foram transferidas para condição ex vitro e submetidas a diferentes tratamentos com nutrientes para acelerar o seu crescimento. Já as análises moleculares foram baseadas na avaliação de 20 loci SSR, em 72 acessos. Destes 20 loci SSR sete foram utilizados, juntamente com seis caracteres fenotípicos, sendo dois qualitativos e quatro quantitativos, relacionados à folha e à flor, com objetivo de caracterizar a variabilidade genética de 12 importantes cultivares, para verificar seu desenvolvimento. Sumarizou-se três matrizes, de dados morfológicos quantitativos, dados morfológicos qualitativos e uma de dados moleculares, e a partir dessa matriz originou-se o dendrograma. Ainda, foram realizadas análises de parâmetros de variabilidade genética dos dados moleculares. A ‗Arbequina‘ sem endocarpo semeada in vivo obteve baixo potencial germinativo,(8,5% de germinação) já as que foram semeadas em condição in vitro de sementes sem endocarpo e embriões isolados com (42,11% e 55,33% de germinação, respectivamente) e reduziram o tempo da germinação em até cinco vezes (de 90 para 15 dias com embriões). As sementes (sem endocarpo) semeadas in vitro (63% de germinação) para aclimatação em casa de vegetação não requerem nutrientes nitrogênio, fósforo e potássio. O dendograma obtido a partir da matriz de similaridade genética UPGMA, calculada pelo índice de Dice, utilizando os dados dos loci SSR, não foi capaz de distinguir os acessos agrupados por países. A abordagem Bayesiana revelou alta relação genética no germoplasma de olivas da Embrapa Clima Temperado, possivelmente devido a maioria pertencer ao mesmo centro de origem, indicando a coancestralidade das cultivares estudadas. Foi possível a identificação de dois pools, com alta relação com os diferentes grupos que compõem a coleção. O conjunto de marcadores SSR escolhidos apresentaram-se polimórficos, permitindo a caracterização de todos os acessos do Banco ativo de Germoplasma da Embrapa Clima Temperado (Pelotas/RS). O resultado da sumarização das matrizes originou um dendrograma que separou os acessos por origem, sendo os acessos Galega e Penafiel originários de Portugal, Frank e VB2, do Brasil, Canino e Coratina, da Itália, e os restantes B21, Gordales, Gran Vitale e Nelson, todos do Brasil confirmando a hipótese de que estes acessos de germoplasma de oliveiras da Embrapa tem uma base genética comum. Contudo, estes resultados indicam um nível médio de variabilidade morfológica e molecular, análises estas complementares, forneceram uma mais completa compreensão da diversidade disponível nestes acessos da coleção de oliveiras. Os resultados desse estudo servem para caracterizar os acessos de oliveiras da coleção da Embrapa Clima temperado (Pelotas/RS) e serão utilizados para os programas de melhoramento genético de oliveira no Brasil, o qual encontra-se em estágio inicial. / The stages of ontogeny olive (Olea europaea L.), from germinating seeds, juvenile period of growth and reproductive phase transition even the development of fruit inflorescence, are long and problematic. Thus, aimed at speeding up the germination process (overcoming latency) and at seedling cultivar Arbequina, besides characterize morphologically and molecularly the access active bank of olive germplasm from Embrapa Temperate Climate (Pelotas / RS) to generate information that may help in future olive breeding programs in Rio Grande do Sul State. For the germination experiments seeds of cv. Arbequina were used with and without the endocarp, which have been sowed in the greenhouse without cored and embryo to in vitro cultivation. The plants obtained through in vitro germination (seed without the endocarp), were transferred to ex vitro conditions and subjected to different treatments with nutrients in order to accelerate their growth. While the molecular analyzes were based on the evaluation of 20 loci SSR in 72 acesses. From those 20 loci SSR seven loci have been used, along with six phenotypic characters, two qualitative and four quantitative, related to leaf and flower, in order to characterize the genetic variability 12 of important cultivars to check their development. Three arrays have been summarized from quantitative and qualitative morphological, also one from molecular data. Due to this matrix dendrogram has been originated. Furthermore, genetic variability analysis were performed of parameters of molecular data. The 'Arbequina' cored seeded in vivo obtained low germination potential (8.5% germination) however those seeds sowed in vitro condition without cored and isolated embryos (42.11% and 55.33% germination, respectively) moreover reduced the time of germination up to five times (from 90 to 15 days with embryos). The seeds (without the endocarp) in vitro (63% germination) for acclimatization in greenhouse do not require nutrients nitrogen, phosphorus and potassium. The dendrogram obtained from the genetic similarity matrix UPGMA Dice index calculated by using the data of SSR loci has not been able to distinguish the access grouped by country. The Bayesian approach has shown high genetic relation to olive germoplasm of Embrapa Temperate Climate, possibly due to the majority belong to the same center of origin, indicating the co-ancestry of cultivars. It has been possible to identify two pools, with high correlation with to the different groups that make up the collection. The set of SSR markers chosen have shown polymorphic, allowing the characterization of all accesses of Active Germplasm Bank of Embrapa Temperate Climate (Pelotas / RS). The result of summarization of the matrices generated a dendrogram that separated the access by origin, being the Galician and Penafiel access originating from Portugal, Frank and VB2 in Brazil, Canine and Coratina in Italy, and the remaining B21, Gordales, Gran Vitale and Nelson, all in Brazil confirming the hypothesis that these germplasm accesses of Embrapa's olive trees have a common genetic basis. Nevertheless, these results indicate an average level of morphological and molecular variability. Complementary analysis provided a more complete understanding of the diversity available in these accesses of the collection of olives. The results of this study serve to characterize the access of olive collection of Embrapa Temperate (Pelotas / RS) and will be used for breeding programs of olive in Brazil, which is at an early stage.

Les sols des oliveraies subissent des pressions environnementales fortes telles que les contraintes pédoclimatiques méditerranéennes et des pratiques agronomiques intensives. Ils requièrent une grande attention face aux changements climatiques. En zone littorale, les stress osmotiques et thermiques s’intensifient. Dans un contexte d’exacerbations de pressions, les sols pourraient subir des modifications profondes de leur qualité, modifications qu’il serait possible d’atténuer en adoptant des pratiques agricoles "durables". Ce projet de thèse a pour objectif d’examiner, en tenant compte de la littoralité, l’impact de pratiques conventionnelles et de conservation sur les activités microbiennes des cycles du C et N et les caractéristiques chimiques du sol. Ont été évaluées dépendamment de la distance à la mer, I)les fonctions des communautés microbiennes de la phyllosphère et de la rhizosphère de l’olivier, II)l’incidence du labour, de co-culture de Fabaceae, d’un enherbement et d’un apport de margions au Liban et en France, III)les réponses microbiennes à des stress hydriques après différentes pratiques. Ce travail a porté plus précisément sur les activités enzymatiques et cataboliques microbiennes intervenant dans la transformation de la matière organique dont la qualité a été étudiée par RMN du solide13C. Ce travail a permis d’observer une littoralité des fonctionnements microbiens avec une atténuation probable des émissions de CO2 par l’utilisation des pratiques de conservation. Par conséquent il est nécessaire de développer en oléiculture intensive des pratiques garantissant la stabilité des fonctions écologiques supportées par les relations sols/microorganismes/plantes. / Olive grove soils are subjected to harsh environmental pressures such as Mediterranean constraints and intensive agriculture practices. They require a great attention in the context of climate change. In coastal areas, osmotic and thermal stresses are intensified. Under these conditions of intensified pressure, significant changes in soil quality may occur and these changes can be mitigated by ‘sustainable’ farming practices. Thus, this thesis project aimed at evaluating, under coastal constraints, the impact of conventional and conservation practices on microbial activities involved in C and N cycles, and soil chemical characteristics. Depending on the distance from the sea, we evaluated i) functions of microbial communities of olive rhizosphere and phyllosphere, ii) the effect of tillage, Fabaceae co-culture, natural grass, OMW in Lebanon and France, iii) microbial responses to water stress under different practices. This work focused on microbial activities involved in the transformation of organic matter, whose quality was studied by solid state NMR 13C. Therefore, this work reported a ‘coastal print’ on microbial functioning and a likely reduction of CO2 emissions through the application of conservation practices. Therefore, it is necessary to develop, under olive tree culture intensification, practices ensuring stability of ecological functions supported by soils / microorganisms / plants relationships.

<p>U ovoj tezi, uz pomoć literaturnih podataka prezentovano je geografsko poreklo masline i maslinovog ulja, njegova upotreba tokom istorije, proizvodni proces, senzorska svojstva, nutritivna vrednost i sastav masnih kiselina i održivost. U eksperimentalnom delu teze detaljno je analizirano pet uzoraka devičanskih maslinovih ulja-DMU proizvedenih na različitim maslinarskim područjima Libije tokom dve uzastopne proizvodne godine. Krakteristike ovih ulja su upoređene sa karakteristikama ekstra devičanskih maslinovih ulja najpoznatijih svetskih proizvođača, Italije. &Scaron;panije i Grčke. Najvažnije masne kiseline u maslinovom ulju su sedam glavnih masnih kiselina- MK koje su detektovane u uzorcima DMU. Oleinska, palmitinska i linolna kiselina su dominantne, dok su druge MK detektovane u malim količinama.Najveći procenat palmitinske kiseline nadjen je u DMU sa područja Tripoli (P &le; 0,05). Oleinska kiselina je dominantna u svim uzorcima DMU.Ustanovljeno je da je Libijsko DMU sa područja Gharyan poseduje najvi&scaron;u koncentraciju oleinske kiseline, mononezasićenih masnih kiselina, najvi&scaron;i sadržaj bioaktivnih jedinjenja i najbolju nutritivnu vrednost.Bioaktivna jedinjenja u maslinovom ulju su tokoferoli, fenoli i pigmenti. Ova jedinjenja čine maslinovo ulje veoma zdravim. Ispitivana je, takođe, i fotostabilnost DMU pod uticajem fluorescentnog svetla u periodu od 35 dana. Ovi eksperimenti su sprovedeni sa tri uzorka DMU sa poreklom iz Libije u poređenju sa uljem iz Italije. Uzorci su bili izloženi fluorescentnom svetlu u providnoj i tamno smeđoj staklenoj ambalaži. Posmatrane su izmene karakteristika boje i rezultati su pokazali da fluorescentna svetlost utiče na smanjenje kvaliteta DMU vi&scaron;e u uzorcima u transparentnoj ambalaži u poređenju sa onima u tamno smeđoj ambalaži.Osim toga, ispitana je i termostabilnost boje DMU primenom Schaal-Oven testa pod uticajem umerene temperature od 63 &plusmn; 2&deg;C tokom perioda od 28 dana. Najmanje promene karakteristika i parametri najboljeg kvaliteta zabeležene su uzorku Gharyan DMU. Uzorak je sadržavao vi&scaron;e pigmenata i fenolnih jedinjenja u poređenju sa uzorkom iz Italije i gubitak je bio najmanji za parametre boje. Pozitivna veza između jodnog broja i polinezasićenih masnih kiselina je registrovana sa koeficijentom korelacije r = +0,927. Primećena je i snažna pozitivna veza između sadržaja hlorofila i (a*) vrednosti boje, (r = + 0,859). Snažna pozitivna veza između TPC i AC (1/EC50DPPH) je takodje primećena, r je bio + 0,511. S druge strane, (1/EC50DPPH) je pokazao pozitivnu umerenu korelaciju sa TTC, (r = + 0,587).</p> / <p>In this thesis, with the help of literature data, the geographical origin of olive and olive oil, its use during history, production process, sensory properties, nutritive value and composition of fatty acids and sustainability were presented. In the experimental part of the thesis, five samples of virgin olive oils-VOO produced in various olive growing regions of Libya were analyzed in detail over the two consecutive production years. The qualities of these oils are compared with the characteristics of extra virgin olive oils of the world&#39;s most famous producers, Italy. Spain and Greece. The most important fatty acids in olive oil are the seven major fatty acids - FA that are detected in the VOO samples. Oleic, palmitic and linolenic acid are dominant, while other FAs are detected in small amounts. The largest percentage of palmitic acid was found in the VOO from the Tripoli area (P &le; 0.05). Oleic acid is dominant in all VOO samples. It has been found that the Libyan VOO from the Gharyan region has the highest concentration of oleic acid, monounsaturated fatty acids, the highest content of bioactive compounds and the best nutritional value. Bioactive compounds in olive oil are tocopherols, phenols and pigments. These compounds make olive oil very healthy. The VOO&#39;s photostability under the influence of fluorescent light for a period of 35 days was also examined. These experiments were carried out with three samples of VOO originating in Libya in comparison with oil from Italy. Samples were exposed to fluorescent light in transparent and dark brown glass containers. Changes in color characteristics were observed and the results showed that fluorescent light influences the quality of VOO more in samples in transparent packaging compared to those in dark brown packaging. In addition, the VOO color thermostability was tested using a Schaal-Oven test under the influence of a moderate temperature of 63 &plusmn; 2&deg;C over a period of 28 days. The smallest changes in characteristics and parameters of the best quality were recorded in the Gharyan VOO sample. The sample contained several pigments and phenolic compounds compared to the sample from Italy and the loss was the smallest for the color parameters. The positive relationship between iodine and polyunsaturated fatty acids is registered with the coefficient of correlation r = + 0.927. A strong positive relationship between the content of chlorophyll and (a*) of the color value was noted, (r = + 0.859). A strong positive association between TPC and AC (1/EC50DPPH) was also observed, r was + 0.511. On the other hand, (1/EC50DPPH) showed a positive moderate correlation with TTC, (r = + 0.587).</p>

Les biofloculants sont une alternative durable aux sels métalliques et aux polymères de synthèse pour le traitement des eaux par coagulation floculation (CF). La littérature a surtout décrit les paramètres optimaux pour l’application des matériaux biosourcés en CF. En étudiant deux exemples, Opuntia ficus indica, connu pour ses propriétés coagulantes et les margines, un déchet peu valorisable issu de la trituration des olives, nous proposons une méthodologie pour déterminer la nature des molécules actives et appréhender le mécanisme de CF impliqué. L’expérimentation a été menée sur un effluent synthétique à base de kaolinite. Les conditions optimales de CF, ont été déterminées par la méthode classique du jar test couplée à de la zétamètrie et de la microscopie. Pour les margines, les conditions optimales sont obtenues pour un pH de 11 et une dose d’extrait de 62.5 mg L-1. La couleur des margines impose néanmoins l’utilisation de 50 mg L-1 de coagulant métallique (Al2 (SO4)3). Nous avons ensuite basé notre étude sur une approche comparative de différentes fractions hydrosolubles en fonction du pH, dans les deux cas les molécules actives ont montré une solubilité maximale au pH optimal de CF. La détermination des pKa, la réalisation de dosages colorimétriques (protéine, sucres, polyphénols, tanin) et l’analyse infrarouge du matériel brut a permis d’envisager les familles de molécules impliquées (dans les deux cas, les tanins / flavonoïdes et les sucres). Des expériences de CF effectuées après digestions enzymatiques permet de confirmer l’identification des molécules impliquées dans le mécanisme. Ainsi la CF se fait par adsorption et pontage pour les deux matériaux. La faisabilité du traitement d’eaux résiduaires (industrie textile, lixiviat de décharge) par des extraits d’Opuntia ficus indica a été validé. Les tanins/ flavonoïdes et particulièrement la quercétine pour le cactus, s’adsorbent sur les colloïdes de l’effluent puis un polymère d’amidon (cactus) ou de cellulose (margine) permet la floculation par adsorption et pontage. / Biofloculants represent a sustainable alternative to metal salts and to synthetic polymers for water treatment by coagulation flocculation (CF). The optimal parameters of biomatrerials applicated in CF were mainly described by literature data. Opuntia ficus indica, known for its flocculating properties and olive mill waste (OMW), which its reuse not deeply examined, were chosen in our study. A methodology was proposed in order to determine the nature of the active molecules and to better understand the involving mechanism in CF. The experiment was conducted on a synthetic water based on kaolinite. The optimal conditions of CF were determined by jar test coupled with zeta potential and microscopy. For OMW, the optimum conditions are obtained for a pH of 11 and an extract dose of 62.5 mg L-1. The removal of OMW colors requires the use of 50 mg L-1 of a metal coagulant (Al2 (SO4)3). Afterwards, our study was based on a comparative approach of different water-soluble fractions as function of pH. The active molecules showed a maximum solubility at the optimal pH of CF, in both cases. The characterization of the raw materials by pKa, colorimetric assays (proteins, sugars, polyphenols and tannins) and the infrared analysis allowed to determine the molecules involved in CF (In both cases, tannins / flavonoids and sugars). CF experiments performed after enzymatic approach confirm the identification of molecules involved in the mechanism and suggest that the two materials operate through an adsorption and bridging mechanism. The efficiency of wastewater treatment (textile industry, landfill leachate) by Opuntia ficus indica extracts has been validated. Tannins/ flavonoids and especially quercetin for cactus promotes a colloidal material destabilization (coagulant) through anion exchanges and bridges; otherwise, the starch (cactus) or cellulose (OMW) forms a large cross-linked polymeric network responsible for bridging.

La chanson d'Yde et Olive, an early fourteenth-century epic poem from the Picard region, exemplifies the medieval custom of text renewal that seeks to adapt pagan materials to fit Christian doctrine. Largely based on the plot of the Ovidian fable Iphis and Ianthe from The Metamorphoses, its main character Yde undergoes a metaphorical transformation from a woman into a man. Moreover, much like the Ovide moralisé, a Christianized adaptation of the Latin original, Yde et Olive's message can be understood as a Christian parable for the purging of the sinful soul. To set up the poem's didactic message, the poet carefully infuses the story with contemporary social concerns, such as the theme of incest and gender disruption, both potentially offensive forces to the medieval social structure. In the backdrop of these threats to society, the heroine's overcoming of her struggles becomes all the more meaningful, leading to a clear moral message to the reader. While being a hybrid in genre and structure, the poem shows many borrowings from Christian hagiography, especially from the later, more romance-influenced versions of the Vitae of female transvestite saints. In these narratives, the heroine's spiritual development is typically portrayed in terms of "becoming male," which can also be understood as an erasure of sexual difference to approach God in a Neoplatonic sense. Moreover, the development of Yde's own hybrid state leading to the climax of revealing her new sex exemplifies medieval literary criticism, elaborating on the central theme of uncovering truth by exposing the hidden gem beneath the rough surface.

Les sociétés économiquement développées sont confrontées à la problématique du vieillissement de leur population associée à la recrudescence des pathologies dégénératives. Parmi les manifestations du vieillissement, l'atteinte de l'appareil locomoteur (ostéoporose et sarcopénie) est considérée comme un problème majeur de santé publique. De ce fait, le développement de mesures préventives permettant de préserver la santé des séniors constitue un véritable enjeu de santé publique. La recherche scientifique fournit de nombreuses preuves concernant l'importance de l'alimentation dans la diminution ou l'exacerbation de certaines maladies. Ces observations confirment le vieux concept soutenant que l'adoption d'une alimentation équilibrée permet le maintien d'un état de santé satisfaisant, en particulier avec l'avancée en âge. A ce jour, le potentiel de l'huile d'olive, en tant que telle ou comme vecteur de nutriments lipophiles d'intérêt pour la prévention nutritionnelle de l'ostéoporose et de la sarcopénie, n'a jamais été testé. La prévalence de l'ostéoporose étant très supérieure chez la femme ménopausée qui souffre également d'une perte musculaire accélérée, cette population a été ciblée dans la présente étude. Dans une première étape, des résultats originaux ont été obtenus concernant l'effet de l'ovariectomie sur le métabolisme musculaire. Ainsi, notre travail montre qu'après ablation des ovaires, la synthèse protéique musculaire est réduite, en association avec une diminution d'un marqueur de la protéolyse de ce tissu. Pris dans son ensemble, ces résultats démontrent un ralentissement du renouvellement protéique musculaire suite à l'ovariectomie. En termes de mécanismes mis en jeu, une augmentation de l'infiltration lipidique tissulaire a été observée. En parallèle du ralentissement du renouvellement musculaire après ovariectomie, une augmentation du renouvellement osseux, classiquement décrit dans la littérature, a été mis en évidence. Dans un second temps, l'effet de l'huile d'olive et plus particulièrement des polyphénols présents dans cet aliment en association avec la vitamine D et l'acide ocosahexaénoïque et leur éventuelle synergie a été évalué à l'aide d'un modèle d'ostéoporose post-ménopausique. Des souris ovariectomisées ont été soumises à une des 4 huiles suivantes : huile de maïs, huile d'olive raffinée, huile d'olive extra vierge ou huile de poisson. Pour chaque huile, un groupe supplémentaire de souris ovariectomisées a reçu de l'huile enrichie en vitamine D. Cette étude a permis de mettre en évidence un effet protecteur de l'association de l'huile d'olive extra vierge et de la vitamine D sur la perte osseuse induite par l'ovariectomie chez la souris. En effet, l'accélération du renouvellement osseux consécutive à la carence estrogénique est freinée par cette association de nutriments, qui diminuent également l'expression des marqueurs du stress oxydant et de l'inflammation. Les résultats obtenus sont en cours de validation chez l'Homme grâce à une investigation clinique réalisée chez des femmes ménopausées. Celle-ci a été mise en place au cours de ces travaux de thèse. / Economically developed societies face the problem of an aging population combined with the increase in degenerative diseases. Among the signs of aging, musculoskeletal pathologies (osteoporosis and sarcopenia) are considered major public health problems. Therefore, the development of preventive measures to preserve seniors’ health is a real public health issue. Scientific research provides ample evidence of the importance of diet in diseases reduction or exacerbation. These observations confirm the old concept arguing that the adoption of a balanced diet helps to maintain a healthy life, especially with advancing age. To date, the potential of the olive oil, as such or as a vector of lipophilic nutrients, for the prevention of osteoporosis and sarcopenia, has never been tested. As the prevalence of osteoporosis is much higher in postmenopausal women who also suffer from an accelerated muscle mass loss, this population was targeted in this study. In a first step, original results were obtained regarding the effect of ovariectomy on muscle metabolism. Thus, our work showed that after removal of the ovaries, muscle protein synthesis was reduced in association with a decrease in the expression of a proteolysis marker of this tissue. Taken together, these results suggest a slowing down of muscle protein turnover after ovariectomy. In terms of mechanisms, an increase in lipid tissue infiltration was observed. The slowdown in muscle protein renewal after ovariectomy was associated with an increased bone turnover, classically described in the literature. In a second step, the effect of olive oil and more particularly its polyphenols in combination with vitamin D and docosahexaenoic acid and their possible synergy was assessed using a postmenopausal osteoporosis model. Ovariectomized mice were subjected to one of the following oils: corn oil, refined olive oil, extra virgin olive oil or fish oil. Four additional groups of ovariectomized mice received the oil fortified with vitamin D. This study demonstrated a protective effect of the combination of virgin olive oil and vitamin D on bone loss induced by ovariectomy in mice. Indeed, the acceleration of the bone turnover induced by the estrogen deficiency was inhibited by this combination of nutrients, which also decreased the expression of oxidative stress and inflammation markers. These results are currently being validated in a clinical investigation conducted in postmenopausal women, which has been established during this thesis work.

The issue of food traceability is one that affects a great number of sectors and policy areas. Within the EU, there is increasing demand from consumers, businesses and institutions to have more direct access to information about how food is produced, transformed, and distributed. Currently, however, practices in the industry are very much open to human error. Databases are highly vulnerable to inaccuracies and hacking, as well as deliberate faults caused by corruption or fraudulent conduct. With food traceability being so closely related to trade and public health issues, there is arguably increasing incentive for the EU to seek alternative tools to increase transparency and accountability throughout supply chains. Consequently, this paper will examine a possible alternative to current practices by evaluating the applicability of 'blockchain' technology, namely a system of digitised, decentralised ledgers, which could allow key stakeholders to access information about the provenance of food immediately, comprehensively and securely. The analysis will focus specifically on Extra Virgin Olive Oil (EVOO), one of the most adulterated products in the food industry, identifying gaps and opportunities in current traceability systems. The research question tackled in this paper, therefore, may be formulated as follows: how and to what extent could blockchain technology constitute a sustainable solution for improving the traceability of EVOO within the EU? The paper begins with a brief overview of the issue and an explanation of the research methodology used, followed by an elaboration of key terms and concepts and a detailed explanation of the principles underlying blockchain technology. Subsequently, the key challenges and opportunities associated with blockchain-based traceability systems are examined through a case study, followed by an analysis aimed at assessing the sustainability of blockchain solutions for the EVOO sector. The conclusion, lastly, provides an overview of relevant findings and proposes a final assessment.

The production of olive oil has seen an increase in recent years due to a broader understanding of the health benefits of the Mediterranean Aliment Culture. With this expanding industry we also see an increase in the waste products associated with olive oil production. Given the high polluting content of the waste streams and the economic costs associated with its removal and processing, waste remediation and disposal has become a significant point of interest for both producers and local bodies. In this project, wastes of the olive oil production industry are examined for their use as the raw material for a novel product used in the control of horticulturally important diseases, examining the effect of extraction protocols on the activity of the final product. Active fractions of the olive oil wastes were identified from literature and protocols for their extraction and recovery developed; incorporating both standard solvent extraction and novel ultrasound-assisted extraction. Criteria for the analysis of extract quality were outlined and potential target applications identified. The biophenolic compounds of olive wastes were identified as providing the majority of the active fraction, so protocols were developed for the recovery of these compounds. Standard solvent extraction and ultrasound-assisted extraction were examined for their effectiveness of biophenolic recovery and their effect on product quality. Certain horticulturally important diseases were identified as potential targets, and bioassays undertaken to determine the ability of a crude extract to inhibit and control these diseases. It was found that the action of ultrasound during extraction provides a greater degree of recovery of biophenolic compounds, with minimal loss of product quality; as determined by bioassays and total biophenol determination. This increase in recovery is due primarily to the destruction of cellular material resulting in higher rates and absolute yields of recovery. This work provides evidence of the occurrence of some interesting phenomenon in the recovery of biophenols from olive wastes that deserves further examination. The crude olive leaf extract was shown to have an inhibitory effect on bacteria and effectively no inhibitory effect on fungal species in the total biophenol ranges tested. Erwinia amylovora and Staphylococcus aureus both showed a large susceptibility to the olive leaf extract. Results showed a higher degree of susceptibility of Gram positive bacteria and a potential resistance in soil microbes. For bacterial species, total biophenol concentrations of 0.15 to 3.50 mg GAE/ml provided inhibitory effects, while with the fungal species tested, no inhibitory effects were found at total biophenol concentrations of up to 2.50 mg GAE/ml. Some evidence exists that there is an opportunity for the economic recovery of olive biophenols for use as a novel product, but more work is required to determine specific applications and/or targets of use, as well as optimisation of the extraction and purification protocol. A sample removed from interfering compounds will allow the examination of activity of particular compounds and hence a better understanding of the action of the olive waste extract.

The purpose of this study is to trace how Sara Willis Parton achieved unprecedented literary celebrity status as Fanny Fern during the first three years of her professional career, 1851-1853. While most critics point to her famously lucrative contract with the most popular newspaper of the 1850s, the New York Ledger, in 1854 as the beginning of her fame, I argue that she had already fully achieved that fame and had done so by writing for small Boston newspapers and publishing a highly successful collection of her articles by 1853. Further, Fern was able to achieve such a high level of success because of a keen business sense, intuitive marketing savvy, an ability to promote herself, an original writing style, and a creative use of personas. My study provides an important addition to Fern scholarship by addressing the largely overlooked early years of her writing career. To date, scholars either make no mention of her first three years or do so only to demonstrate the point that Fern achieved notable success when she signed a contract for one hundred dollars a column with Robert Bonner, publisher and editor of the New York Ledger. Prior to that contract, Fern worked as a freelance writer for the Boston Olive Branch and the Boston True Flag, earning less than five dollars for each sketch she submitted. The critical assumption has been that her initial work prepared her for the fame she would achieve writing for Bonner, but in fact Bonner would not have hired her had she not already achieved significant fame, for Bonner hired only highly celebrated writers. My study explores how Fanny Fern became a famous writer. When she began writing, Fern wrote under a number of previously unknown pseudonyms for local newspapers, but within three years her distinctive style, rhetorical skill, and iconoclastic persona had made ―Fanny Fern a household name. Fern‘s unique ability to engage a popular audience, I would argue, is the principal difference between Fern and other famous contemporary women writers.