Made available in DSpace on 2015-05-14T13:21:42Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 3270377 bytes, checksum: f7faeeb5a1fdf2284d994edc54a6a265 (MD5) Previous issue date: 2013-08-26 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / This work presents a simple and non-expensive based on digital image and pattern recognition techniques for the classification of edible vegetable oils with respect to the type (soybean, canola, sunflower and corn) and the conservation state (expired and non-expired period of validity). For this, images of the sample oils were obtained from a webcam, and then, they were decomposed into histograms containing the distribution of color levels allowed for a pixel. Three representations for the color of a pixel were used: red-green-blue (RGB), hue-saturation-intensity (HSI) and grayscale. Linear discriminant analysis (LDA) was employed in order to build classification models on the basis of a reduced subset of variables. For the purpose of variable selection, two techniques were utilized, namely the successive projections algorithm (SPA) and stepwise (SW) formulation. Models based on partial least squares-discriminant analysis and (PLS-DA) applied to full histograms (without variable selection) were also employed for the purpose of comparison. For the study evolving the classification with respect to oil type, LDA/SPA, LDA /SW and PLS-DA models achieved a correct classification rate (CCR) of 95%, 90% and 95%, respectively. For the identification of expired non-expired samples, LDA / SPA models were found to the best method for classifying sunflower, soybean and canola oils, achieving a TCC of 97%, 94% and 93%, respectively, while the model LDA/SW correctly classified 100% of corn oil samples. These results suggest that the proposed method is a promising alternative for inspection of authenticity and the conservation state of edible vegetable oils. As advantages, the method does not use reagents to carry out the analysis and laborious procedures for chemical characterization of the samples are not required / Este trabalho apresenta um método simples e de baixo custo, baseado na utilização de imagens digitais e técnicas de reconhecimento de padrões, para a classificação de óleos vegetais comestíveis com relação ao tipo (soja, canola, girassol e milho) e ao estado de conservação (prazo de validade expirado e não expirado). Para isso, imagens das amostras de óleos vegetais foram obtidas a partir de uma webcam e, em seguida, as mesmas foram decompostas em histogramas contendo as distribuições dos níveis de cores permitidos a um pixel. Três modelos para a cor de um pixel foram utilizados: vermelho-verde-azul (RGB), matiz-saturação-intensidade (HSI) e tons de cinza. A análise discriminante linear (LDA) foi utilizada para o desenvolvimento de modelos de classificação com base em um subconjunto reduzido de variáveis. Para fins de seleção de variáveis, duas técnicas foram utilizadas: o algoritmo das projeções sucessivas (SPA) e o stepwise (SW). Modelos baseados na análise discriminante por mínimos quadrados parciais (PLS-DA) aplicados aos histogramas completos (sem seleção de variáveis) também foram utilizados com o propósito de comparação. No estudo envolvendo a classificação com respeito ao tipo, modelos LDA/SPA, LDA/SW e PLS-DA atingiram uma taxa de classificação correta (TCC) de 95%, 90% e 95%, respectivamente. Na identificação de amostras expiradas e não expiradas, o modelo LDA/SPA foi considerado o melhor método para a classificação das amostras de óleos de girassol, soja e canola, atingindo uma TCC de 97%, 94% e 93%, respectivamente, enquanto que o modelo LDA/SW classificou corretamente 100% das amostras de milho. Estes resultados sugerem que o método proposto é uma alternativa promissora para a inspeção de autenticidade e estado de conservação de óleos vegetais comestíveis. Como vantagem, a metodologia não utiliza reagentes, a análise é rápida e procedimentos laboriosos para a caracterização química das amostras não são necessários

O pinhão-manso (Jatropha curcas L) é uma espécie da família da Euforbiácea que tem se destacado por ser uma planta perene, rústica e com elevada produção de óleo. A avaliação dos efeitos da poda e da irrigação no crescimento e produção do pinhão-manso é relevante para o manejo de um cultivo com essa espécie. Este estudo teve como objetivo principal avaliar os efeitos de diferentes tipos de poda e manejos hídricos no cultivo do pinhão-manso em Piracicaba, SP. O experimento foi conduzido na área experimental do Departamento de Engenharia de Biossistemas (ESALQ/USP), com plantas de quatro anos de idade dispostas em espaçamento 3 x 4 m, totalizando 833 plantas ha-1. Os tratamentos foram arranjados de forma aleatória em blocos compostos de quatro repetições, sendo que os fatores foram constituídos de dois manejos hídricos (irrigado e sem irrigação) e três tipos de poda, sendo P1 (sem poda), P2 (1,5 m de altura x 1,5 m de diâmetro de copa) e P3 (poda a 2 m de altura e 1,5 m de diâmetro da copa). A irrigação teve influência no diâmetro da copa, nas taxas de crescimento absoluto em altura e diâmetro, na taxa de crescimento relativo em diâmetro e nas variáveis produtivas. O fator poda apresentou diferenças em todas as variáveis de crescimento, sendo a poda drástica (P2) a que exibiu as maiores taxas médias de crescimento. As plantas irrigadas apresentaram os maiores rendimentos por planta e por hectare. A análise de ressonância magnética nuclear de hidrogênio (RMN de 1H) revelou que a irrigação e a poda não influenciaram o teor de óleo nas sementes de pinhão-manso. Em relação ao perfil graxo, a irrigação teve influência em plantas submetidas a poda drástica (P2), de modo que a ausência de irrigação favoreceu o maior acúmulo de ácido oleico no óleo. Pela análise energética, observou-se que os fertilizantes foram os insumos com maior participação na demanda energética (42,57 GJ ha-1) para os dois sistemas estudados, seguido dos combustíveis (32,96 GJ ha-1). A área irrigada consumiu 100,4 GJ ha-1, sendo 16% devido ao acionamento do pivô central. A energia bruta dos frutos de pinhão-manso foi de 69,82 e 45,31 GJ ha-1 para o sistema irrigado e o sem irrigação, respectivamente. O balanço energético (BE) para as duas áreas foi negativo e a lucratividade energética (EROI) foi de 0,63 para a área irrigada e 0,49 para a área sem irrigação, evidenciando a ineficiência e a não sustentabilidade do cultivo de pinhão-manso nas condições deste estudo para geração de energia. / Jatropha (Jatropha curcas L) is a species from Euforbiácea family that has been widely studied because of some particular characteristics such as being a perennial plant, its rusticity and the high oil production. The evaluation of pruning and irrigation on growth development and yield of jatropha is very important for the culture management. The objective of this study was to evaluate the effects on jatropha under different types of pruning and water management in Piracicaba, SP. The experiment was conducted in the experimental area of the Department of Biosystems Engineering (ESALQ/USP) during the fourth year crop growing and with 3 x 4 m planting spacing, totalizing 833 plants ha-1. The treatments were randomly arranged in blocks with two water management (irrigation and rainfed) and three pruning types (P1, no pruning; P2, with 1.5 m height x 1.5 m canopy diameter and; P3, with 2.0 height x 1.5 m canopy diameter). In each block, there were three pruning types with 4 blocks in each water management. Irrigation have influenced the canopy diameter values, absolute growth rates for height and canopy diameter, relative growth rate for canopy diameter and yield parameters., pruning management have influenced in all growth parameters, with drastic pruning (P2) representing the highest average growth rates. The irrigation have showed the highest yield per plant and per hectare. The analysis of Nuclear Magnetic Resonance of hydrogen (1H NMR) have shown that the irrigation and pruning have not influenced the oil content on jatropha seeds. Regarding the fatty profile, the irrigation management have influenced only the P2, since that no irrigation have influenced to largest accumulation of oleic acid in the oil. In energy analysis, it was noted that fertilizers were the inputs with the largest participation in energy input (42.57 GJ ha-1) for both water management, followed by fuels (32.96 GJ ha-1). The irrigated area consumed 100.4 GJ ha-1 energy, representing 16% due to the central pivot usage. The gross energy of jatropha fruits was 69.82 and 45.31 GJ ha-1 for irrigated and rainfed system, respectively. The energy balance for the two areas was negative and the energy return over investment, with 0.63 and 0.49 for irrigated and rainfed, respectively, have showed the inefficiency and unsustainability of jatropha cultivation to generate energy.

Made available in DSpace on 2015-04-22T19:34:51Z (GMT). No. of bitstreams: 1 tese final capitulo 2 a 6.pdf: 676743 bytes, checksum: 94bb8fab0aa966e3c47acb177fd19ae7 (MD5) Previous issue date: 2012-12-14 / FAPEAM - Fundação de Amparo à Pesquisa do Estado do Amazonas / In Brazil, the species Carapa guianensis Aublet. and Carapa procera DC are known as andiroba. In the Amazon region, andiroba oil is considered medicinal and used primarily as an anti-inflammatory. The fruits of these species were collected and separated (seeds, peels seeds and pericarp) and separately extracted with different solvents in order of increasing polarity. From the seeds of the species C. guianensis were isolated the mixture of the limonoids 6α-acetoxygedunin and 7-deacetoxy-7-oxogedunin, and the mixture of the limonoids 7-deacetylgedunin and 6α-acetoxy-7-deacetylgedunin (first time isolated in the fruits of andiroba), and also those same limonoids were isolated separately. The hexane extract of the pericarp of the same species were isolated limonoids methyl angolensate and 6-hydroxy-methyl angolensate (first time described in the species). For comparison purposes, a method in HPLC/DAD was developed for quantification of the limonoids isolated in samples of extracts from different parts of the fruit of the two species. Two commercial samples of andiroba oil produced in the traditional way were also analyzed. The results of analyzes of the extracts obtained in the samples of both species showed the accumulation of almost all the limonoids in the seeds oil, and the limonoid 7-deacetylgedunin can be used as a chemical marker for the differentiation between species. The analysis of samples of commercial andiroba oil produced in the traditional way for method developed in HPLC / DAD showed differences in concentrations of limonoids analyzed. The extracts of the two species were assayed for larvicidal activity against Aedes aegypti, in which the precipitate from the oil of C. guianensis was the most interesting with an LC50= 36.9 ± 1.0 mg/mL. In the inhibition assay of the enzyme acetylcholinesterase showed inhibition of almost all limonoids and extracts tested, except the limonoid 7-deacetoxy-7-oxogedunin. These results are first time described in the literature for andiroba and are quite promising. / No Brasil, as espécies Carapa guianensis Aublet. e Carapa procera D.C. são conhecidas como andiroba. Na região Amazônica, o óleo de andiroba é considerado medicinal e utilizado principalmente como anti-inflamatório. Os frutos dessas espécies foram coletados e separados (amêndoas, cascas das amêndoas e pericarpos) e extraídos separadamente com solventes em ordem crescente de polaridade. Das amêndoas da espécie C. guianensis foram isolados a mistura dos limonoides 6α-acetoxigedunia e 7-desacetoxi-7-oxogedunia, e a mistura dos limonoides 7-desacetilgedunina e 6α-acetoxi-7-desacetilgedunina (isolado pela primeira vez nos frutos de andiroba), além desses mesmos limonoides em separado. Do extrato hexânico do pericarpo da mesma espécie foram isolados os limonoides angolensato de metila e 6-hidroxi-angolensato de metila (inédito na espécie). Para fins de comparação, um método foi desenvolvido em CLAE/DAD para quantificar os limonoides isolados nas amostras de extratos obtidos das diferentes partes dos frutos das duas espécies. Duas amostras comerciais de óleo de andiroba produzidos de forma tradicional também foram analisadas. O resultado das análises nas amostras dos extratos obtidos das duas espécies indica o acúmulo de quase todos os limonoides isolados no óleo das amêndoas e que o limonoide 7-desacetilgedunina pode ser utilizado como marcador químico para a diferenciação entre as espécies. A análise das amostras dos óleos de andiroba tradicionais comercializados pelo método desenvolvido em CLAE/DAD mostrou diferenças em termos de concentrações dos limonoides analisados. Os extratos das duas espécies foram testados para a atividade larvicida contra Aedes aegypti, nos quais o precipitado obtido do óleo da C. guianensis foi o mais interessante apresentando uma CL50 de 36,9 ± 1,0 μg/mL. No ensaio de inibição da enzima acetilcolinesterase foi observada inibição para quase todas as amostras dos extratos testados, bem como dos limonoides isolados, exceto o limonoide 7-desacetoxi-7-oxogedunina. Esses resultados são apresentados pela primeira vez para a andiroba e são bastante promissores.

Ce travail porte sur une étude comparative des huiles végétales (esters naturels) issues de différentes graines, esters synthétiques, et minérales sur la base des caractéristiques de génération et de propagation des streamers qui s’y développent, des tensions de claquage ainsi que des décharges se propageant sur un isolant solide en présence de ces huiles. Il ressort des résultats obtenus qu’en géométrie pointe – plan, sous tension continu, la tension de génération en polarité positive est toujours supérieure à celle mesurée en polarité négative et elle est plus élevée dans les huiles esters que dans les huiles minérales quelle que soit la polarité de l’électrode pointe. En ce qui concerne la propagation de streamers sous tension impulsionnelle de foudre, les longueurs finales (ou longueurs d’arrêt) Lf des streamers positifs sont environ10 fois supérieures à celles des streamers négatifs. Pour atteindre la même Lf, il faut beaucoup plus de tension en polarité négative qu’en polarité positive. Par conséquent, les tenues diélectriques sont plus élevées en polarité négative qu’en polarité positive. D’autre part, Lf est plus élevée dans les huiles végétales que dans certaines huiles minérales. La tension de claquage des huiles isolantes, déterminée selon la norme CEI 60156, suit généralement une distribution Normale. Les probabilités de claquage peuvent alors être déterminées suivant la distribution Normale en prenant un échantillonnage suffisamment grand (n>30). Il est également montré que les huiles végétales et l’ester synthétique présentent des tensions de claquage (U1%, U10% et U50%) plus élevées que les huiles minérales sous tension alternative. La tension de claquage moyenne est aussi plus élevée dans les esters que dans les huiles minérales sous tension impulsionnelle de foudre. La morphologie, la longueur d’arrêt et le courant des décharges se propageant sur un isolant solide (carton) immergé dans les liquides étudiés, dépendent de l’amplitude et de la polarité de la tension, de l’épaisseur du solide et de la nature des huiles. Lf augmente quasi-linéairement avec la tension appliquée et diminue lorsque l’épaisseur du solide augmente. Pour une tension et une épaisseur données, les décharges qui se développent sur l’interface carton/huile végétale sont plus longues que celles sur l’interface carton/huile minérale. Par ailleurs, Lf est plus élevé en polarité positive qu’en polarité négative, ce qui indique que la polarité la plus contraignante est la polarité positive. Ila été également mis en évidence l’existence d’une décharge secondaire de signe opposé à celui de la tension appliquée, résultat de l’accumulation de charges d’espace à la surface de l’isolant solide. Enfin, la dimension fractale D des décharges diminue lorsque l’épaisseur du solide augmente. Plus l’épaisseur du solide est grande, plus le degré de ramification des décharges est moins important. Pour une tension et une épaisseur données, D est généralement plus élevée dans l’huile minérale que dans l’huile végétale. / This work is aimed at the comparative study of vegetable oils (natural esters) issued from different seeds, synthetic ester oil and mineral oils, based on the characteristics of generation and propagation of streamers, breakdown voltages and creeping discharges propagating over solid insulator (pressboard) immersed in these oils. It has been shown that, in a point – plane electrode geometry, the DC threshold voltage Us is higher when the point is positive than when it’s negative; Us is higher in vegetable oils than in mineral oils for both polarities of voltage. Under lightning impulse voltage, the streamers are filamentary in all different tested oils whatever the polarity of voltage. The final (or stopping) length Lf of streamers are about ten times higher when the point is positive than when it’s negative. The voltage required to reach the same Lf is higher with a negative point than with a positive point.Thus the positive polarity is unfavourable for the industrial applications. In addition, Lf is longer in vegetable oils than in some mineral oils. The breakdown voltage of insulating oils, measured according to IEC 60156 standard specifications generally follows a normal distribution. The probability of breakdown can hence be determined according to the normal distribution with a large amount of samples (n>30). So, vegetable oils and synthetic ester have breakdown voltages (U1%, U10% and U50%) higher than mineral oils under AC; and the mean breakdown voltage is also higher in esters oils than in minerals oils under lightning impulse voltage. The morphology, final length Lf and current of discharges propagating over a solid insulator (pressboard) immersed in the liquid tested, depend on the amplitude and polarity of the voltage, the thickness of insulator as well as the nature of insulating oils. It has been shown that Lf increases quasi-linearly with the applied voltage and decreases when the thickness of insulator increases. For a given applied voltage and thickness of insulator, Lf is higher with a pressboard/vegetable oil interface than with a pressboard/mineral oil interface.In addition, Lf is also longer when the point is positive than when it’s negative. The recorded currents revealed the existence of a secondary discharge of opposite sign to that of the applied voltage. This phenomenon is due to the accumulation of charges at the surface of insulator.Finally, the fractal dimension D of creeping discharges decreases when the thickness of insulator increases. For a given applied voltage and thickness of solid, D is generally higher in mineral oils than in vegetable oils.

La valorisation du carbone renouvelable joue un rôle croissant dans l'industrie chimique. Ces travaux rapportent l'utilisation d'huiles végétales comme matières premières en substitution de celles d'origine fossiles pour la synthèse de monomères bio-sourcés destinés à la production de polyesters ou de polyamides.La production du 9 oxononanoate de méthyle, comme molécule plateforme, à partir d'esters méthyliques d'huile de colza a été réalisée par coupure oxydante (ozonolyse) sans solvant à température ambiante, suivie d'une réduction des intermédiaires par hydrogénation catalytique sous pression de H2 et de Pd(5)/C. Ainsi, le rendement en aldéhyde-ester est de 92%. Ce procédé a été appliqué à la synthèse de molécules plateformes avec des longueurs de chaînes de 9 à 13 atomes de carbone. Une matière première renouvelable, des conditions de réaction douces, le recyclage du catalyseur et des co-produits non toxiques et valorisables ont permis de développer un procédé durable plus respectueux de l'environnement. La réduction de la fonction aldéhyde a été menée par hydrogénation catalytique, à 50°C dans le méthanol, pour former l'alcool-ester correspondant. Le nickel de Raney ainsi que le Pd(5)/C offrent des rendements en 9-hydroxynonanoate de méthyle supérieurs à 90 %, mais le premier catalyseur conduit à un temps de réaction plus court. L'amination réductrice de la fonction aldéhyde a été menée avec succès à partir de NH3 gazeux et de Pd(5)/C, à 50°C dans le méthanol, pour conduire majoritairement à la synthèse de l'amino-ester primaire. La quantité de NH3(g) influence la sélectivité et au moins trois équivalents sont nécessaires pour limiter la formation d'amino-ester. / A high interest has been devoted to the use of renewable carbon in the chemical industry. The goal of this work is the substitution of fossil oils by vegetable oils to synthesize bio sourced monomers for polyesters and polyamides production. The synthesis of methyl 9-oxononanoate as a platform molecule from fatty acid methyl esters of rapeseed oil was carried out in solvent free ozonolysis at room temperature. Intermediary ozonides was reduced to aldehydes by catalytic hydrogenation under H2 pressure and in the presence of Pd(5)/C catalyst giving a 92% carbonyl yield. This process was applied to a wide range of unsaturated esters with a chain length within 9 and 13 carbon atoms. This process allows the selective conversion of renewable materials to value added chemicals, in mild conditions and in the presence of a recyclable catalyst. Moreover, the co products are non toxic and valuable. Hydrogenation of aldehyde group was performed in the presence of methanol at 50°C under hydrogen pressure. Raney Nickel and Pd(5)/C exhibit a yield to methyl 9 hydroxynonanoate higher than 90%. Reductive amination of the aldehyde functional group was investigated with success in the presence of NH3(g) and Pd(5)/C at 50°C in methanol to produce primary amino ester. The amount of ammoniac is directly correlated to the selectivity of the reaction. As a consequence a minimum amount of 3 eq. of ammoniac is required to avoid the formation of secondary amino-ester.

This paper presents a methodology for optimizing the distribution transformers project, considering the capitalized cost, employing concurrently in your project amorphous core and insulating vegetable oil. The use of amorphous core technology provides a significant reduction of the load losses as the use of the insulating vegetable oil which is a non-toxic fluid and rapidly biodegradable when in contact with the environment, it allows increasing the machine's operating temperature . The use of these two materials have provided considerable percentage improvements in efficiency and cost / power compared to conventional distribution transformers manufactured. The methodology is aimed to create and select designs that have a lower total cost, namely the sum of the transformer manufacturing cost capitalized cost of losses during the useful life envisaged for the equipment. In addition, it presents the case study of a 75 kVA designed distribution transformer and manufactured with amorphous core and insulating vegetable oil, routine employed optimization (developed in VBA Excel), the theoretical results obtained from the optimized design and the experimental results. / Este trabalho apresenta uma metodologia de otimização do projeto de transformadores de distribuição, considerando o custo capitalizado, que empregam concomitantemente em seu projeto núcleo amorfos e óleo vegetal isolante. O emprego da tecnologia de núcleo amorfo proporciona significativa redução das perdas em vazio, enquanto a utilização do óleo vegetal isolante, que é um fluído não tóxico e de rápida biodegradação quando em contato com o meio ambiente, possibilita o aumento da temperatura de operação do equipamento. A utilização desses dois materiais propiciaram melhoras percentuais consideráveis na eficiência e na relação custo/potência em comparação aos transformadores de distribuição convencionalmente fabricados. A metodologia visa criar e selecionar projetos que tenham um menor custo total, ou seja, a soma do custo de fabricação do transformador com o custo capitalizado das perdas durante a vida útil considerada para o equipamento.Além disso, é apresentado o estudo de caso de um transformador de distribuição de 75 kVA projetado e fabricado com o núcleo amorfo e óleo vegetal isolante, a rotina de otimização empregada (desenvolvida em VBA Excel), os resultados teóricos obtidos a partir do projeto otimizado e os resultados experimentais.

Abstract Biodegradation is an aerobic or anaerobic degradation reaction where bacteria use organic materials as an energy source. In the aerobic biodegradation reaction, bacteria need oxygen as an electron acceptor, whereas an anaerobic reaction takes place in the absence of oxygen. Compounds degrade totally or partially, and produce simple inorganic species, such as CO2, CH4, NH3, NO3−, and H2O, as well as by-products that may be non-biodegradable and/or toxic. In this thesis, the biodegradability of recycled vegetable oils, surface-active agents, and condensing waters from the process of wood drying were studied using the manometric respirometric BOD OxiTop method. The biodegradation of organic compounds was measured under the standard conditions (OECD 301F), and also in other matrices, such as different waters and soils. These are very different environments with respect to the biodegradation reaction in nature. The main differences in waters and soils are their organic and inorganic nutrient contents, bacteria strains, and temperatures. The BOD OxiTop method is based on automatic pressure detection in a closed reactor vessel. Oxygen is consumed and carbon dioxide is formed in the aerobic reaction. The pressure decrease is detected after the carbon dioxide is adsorbed into a NaOH pellet or solution. The pressure change is dependent on oxygen consumption. The degree of biodegradation is calculated from the BOD value of the sample. The studied recycled vegetable oils were found to be 60–83% biodegradable, and the added surface-active agent did not affect their biodegradation. Biodegradation of tall oil soaps was also examined in sand, topsoil, groundwater, and surface water, as well as under OECD 301F standard conditions. Tall oil soaps were proven to be 50–85% biodegradable. Concrete solvent agent (CSA) was also proven to be 78–83% biodegradable under standard conditions. Another detergent, cetyltrimethylammonium bromide (CTAB), was found to be toxic, whereas Triton X-100 biodegraded by only 6% in solution. Biodegradation of the soil matrix was found to be enhanced with added surface-active agents. This can be explained by better wetting of small pores with surface-active agents, as compared to the behavior of pure water. The biodegradation of the matrix occurred even with toxic surface-active agents. Organic pollutants of wastewaters from the process of wood drying were 25–61% biodegradable during a 28-day period, and were proven to be quite pure when considering the carbon content of the samples. Based on these results, the disposal into drainage of condensing waters from wood drying may be regarded as safe, which from an economical viewpoint is a very important conclusion. / Tiivistelmä Biohajoavuus on luonnollinen aerobinen tai anaerobinen hajoamisprosessi, jossa bakteerit käyttävät orgaanista materiaalia energian lähteenä. Aerobisessa reaktiossa bakteerit tarvitsevat happea elektronien vastaanottajaksi, kun taas anaerobinen reaktio tapahtuu hapettomissa olosuhteissa. Yhdisteet hajoavat joko täysin tai osittain sekä tuottavat yksinkertaisia epäorgaanisia yhdisteitä, kuten CO2, CH4, NH3, NO3− tai H2O. Reaktiossa voi myös muodostua sivutuotteita, jotka voivat olla biohajoamattomia ja/tai toksisia. Tässä työssä on tutkittu kierrätettyjen kasviöljyjen, pinta-aktiivisten aineiden sekä jätevesien sisältämien orgaanisen aineksien biohajoavuuksia käyttäen manometristä respirometristä BOD OxiTop-menetelmää. Biohajoavuutta mitattiin standardiolosuhteiden (OECD 301F) lisäksi muissakin olosuhteissa, kuten erilaisissa maissa ja vesissä. Nämä ovat kaikki hyvin erilaisia ympäristöjä luonnossa tapahtuville biohajoavuusreaktioille. Pääasialliset erot ovat sekä orgaanisten että epäorgaanisten ravinteiden määrässä, bakteerikannoissa ja lämpötilassa. BOD OxiTop-menetelmä perustuu automaattiseen paineen muutoksen havainnointiin suljetussa astiassa. Aerobisessa reaktiossa kuluu happea ja muodostuu hiilidioksidia, joka imeytetään NaOH-pelletteihin tai -liuokseen ja tästä muodostuu alipaine. Paineen muutokset muunnetaan hapenkulutuksen arvoiksi, joista lasketaan biohajoavuusaste. Tutkittujen kierrätettyjen kasviöljyjen biohajoavuusasteet vaihtelivat välillä 60–83 %, eikä lisätty pinta-aktiivinen aine vaikuttanut kyseisten ekoöljyjen biohajoavuuteen. Mäntysaippuoiden biohajoavuus tutkittiin standardiolosuhteiden lisäksi hiekassa, mullassa, pohjavedessä sekä pintavedessä. Niiden biohajoavuusasteet vaihtelivat välillä 50–85 %. Betoninpesuaineen biohajoavuusaste standardiolosuhteissa oli 78–83 %. Kahdesta tutkituista pinta-aktiivisista aineista setrimoniumbromidi (CTAB) oli myrkyllinen liuosolosuhteissa eikä täten biohajonnut ja Triton X-100 biohajosi vain 6 %. Pinta-aktiivisen aineen lisääminen maahan aiheutti matriisina käytetyn maan biohajoamisen. Tämä voitiin selittää siten, että pintajännityksen laskemisen jälkeen neste voi paremmin tunkeutua maan pieniin huokosiin ja näin tuoda hajoamatonta orgaanista ainesta ja uusia bakteereita biohajoavuuskäyttöön. Tämä ilmiö havaittiin myös myrkyllisen pinta-aktiivisen aineen lisäyksen jälkeen. Jätevesien sisältämät orgaaniset ainekset hajosivat 25–61 % 28 päivän aikana ja niiden havaittiin olevan hiilen määrän huomioon ottaen hyvin puhtaita. Tässä tutkimuksessa saatujen tulosten perusteella tutkitut puunkuivauksen kondenssivedet voidaan laskea viemäriin, mikä on erittäin tärkeä tulos ekologiselta ja taloudelliselta kannalta katsottuna.

Doctor of Philosophy / Department of Chemistry / Duy H. Hua / I. Ovalicin is a natural product isolated from the culture of fungus Pseudorotium ovalis Stolk, it selectively inhibit type 2 methionine amino-peptidase (MetAP 2), which related to many physiological activities such as angiogenesis. Total synthesis of [plus or minus] ovalicin, its C4(S*), C4(S*)C5(S*) stereo-isomers, and C5 regio-isomer were synthesized via an intramolecular Heck reaction of (Z)-3-(t-butyldimethyl silyloxy)-1-iodo-1,6-heptadiene utilizing a catalytic amount of palladium acetate. Subsequent epoxidation, dihydroxylation, methylation (or stereochemistry inversion before or after methylation) and oxidation led to a variety of ketones, key intermediates for synthesis of ovalicin and its analogues. Introduction of side-chain to ketones by lithium (Z)-6-methylhepta-2,5-dien-2-ide and following functional group transformation led to ovalicin and its analogues. Anti-trypanosomal activities of various ovalicin analogues and synthetic intermediates were evaluated. II. Bio-based polymers from vegetable oils are renewable and environment-friendly materials. Dihydroxylated, trihydroxylate, tetrahydroxylated and hexahydroxylated triglycerides, triamino and triisopropylamino glycerides were synthesized from model triglyceride glyceryl trioleoate. These monomers were cross-linked with 1, 4-phenylene diisocynate to make polyurethanes and polyureas. The physical properties of these polymers were examined by gel content and swelling value measurements, thermodynamic and viscoelastic properties were studied from TGA, DSC and DMA measurements. The structure-property relationship was discussed based on these measurements. III. Diacetylenic fatty acids were widely applied in material science to regulate alignment on surface and stabilize self-assembled nanomaterials. A novel synthetic method of diacetylenic fatty acids from vegetable oils was developed. Its self-assembling properties on alumina surface were measured and discussed.

Les apiaceae peuvent être définies en tant qu' Aroma-Tincto-Oleo-Crop (ATOC), plantes qui contiennent à la fois une huile végétale et une huile essentielle. Appliquer le concept d'agroraffinage aux ATOC revient à proposer un procédé séquentiel alliant une co-extraction huile végétale et huile essentielle à une valorisation des résidus en tant que source de molécules biosourcées et de susbtrat pour la formulation d'agromatériaux . Les objectifs de cette thèse seront donc d'étudier la faisabilité biologique et technologique d'application du concept d'ATOC-raffinage à la coriandre (Coriandrum sativum L.). Le chapitre I présente l'état de l'art bibliographique sur l'extraction et l'analyse des huiles végétales et huiles essentielles de coriandre tandis que dans le chapitre II sont décrits les matériels et méthodes mis en oeuvre au cours de la thèse tant au niveau échantillonnage, extraction, analyse que traitement des données. Le chapitre III est centré sur l'étude des différents paramètres biologiques pouvant influencer la bioaccumulation des huiles végétales et huiles essentielles dans la coriandre (différentes variétés, différents organes de la plante, différents stades de développement biologique) et leur impact sur l'activité anti-oxydante des extraits obtenus à partir des résidus d'extraction. Dans le chapitre IV, la technologie d'extrusion (mono-vis et bi-vis) a été appliquée aux graines de coriandre dans le but d’évaluer la faisabilité du pressage mécanique du fruit de la coriandre pour l’extraction d'une huile végétale aromatisée. L’influence des conditions expérimentales sur le rendement d'extraction en huile végétale (diamètre de buse et distance buse-vis (extrudeur mono-vis) ou configuration de vis, coefficient de remplissage et température de pressage (extrudeur bi-vis)) a été étudiée tandis que la faisabilité de la valorisation du résidu solide d'extraction en agromatériaux (thermo-pressage) a été montrée. / Apiaceae could be defined as Aroma Tincto Oleo Crops (ATOC), e.g. plants containing both vegetable oil and essential oil. Applying agroreffinery concept to ATOC led to propose a sequential fractionation process coupling co-extraction of vegetal oil and essential oil to a valorization of by-product residues as biosourced active molecules and substrates for designing agromaterials. The aim of this thesis is to determine the biological and technological feasability of application of the ATOC-refinery concept to coriander (Coriandrum sativum L.) Chapter I reports a bibliographic state of the art study on extraction and characterisation of coriander vegetal oil and essential oil while chapter II describes materials and methods setting up during the thesis for sampling, extraction, analysis and data processing. Chapter III focus on the study of major various biological parameters influencing bioaccumulation of vegetal oil and essential oil in coriander (different plant varieties, different plant organs, different biological stages) and their impact on anti-oxidant activity of extracts obtained from extraction residues. In chapter IV, coriander fruits are processed by extrusion technology (mono screw and twin-screw extruder) in order to evaluate the feasability of mechanical pressing for extracting a flavored vegetal oil. Influence of operating parameters on vegetal oil extraction yields (nozzle diameter and nozzle/screw distance (single-screw extruder) or screw configuration, device’s filling coefficient and pressing temperature (twin-screw extruder)) is studied while the feasability of valorization of extraction cake as agromaterial (thermopressing) was stated.

Les fruits de coriandre ont été identifiés comme une source riche en huile végétale de haute qualité, à forte teneur en acide pétrosélinique et en huile essentielle. Un système d'extraction innovant a été conçu et développé en utilisant la technologie d'extrusion bi-vis. Il a permis l’obtention d'un produit nouveau, à savoir une huile végétale de coriandre aromatisée et à haute valeur ajoutée, d’un condensat présentant une concentration élevée en huile essentielle et d’un tourteau révélant une forte teneur en protéines. Le tourteau a montré son intérêt en tant que liant naturel pour la production de panneaux de fibres renouvelables issus de la paille de coriandre, un résidu de la culture de la plante, conduisant à des agromatériaux auto-liés et ayant un rapport performance/coût élevé. Les fibres de la paille de coriandre ont également présenté une bonne capacité de renforcement lorsqu’elles étaient utilisées comme charge naturelle dans des biocomposites thermoplastiques à base de polypropylène ou de biopolyéthylène, permettant le moulage par injection de matériaux peu couteux et aux propriétés mécaniques prometteuses. Ce travail présente ainsi une forte contribution à la mise en place d'une véritable bioraffinerie intégrée de la coriandre et à la démonstration de sa mise en oeuvre à une échelle industrielle. / Coriander fruits of French origin were identified as a rich source of a high-quality vegetable oil, with a high petroselinic acid content, and essential oil. An innovative extraction system was designed and developed using twin-screw extrusion technology and resulted in the recovery of a novel flavored coriander oil with high added value, as well as a hydrosol product with a high essential oil concentration and a press cake with an important protein fraction. The press cake was shown valuable as a natural binding agent for the production of renewable materials from coriander straw, a crop residue, and led to binderless boards with a high performance-cost ratio. Simultaneously, the coriander straw fibers displayed good reinforcing capacity as a natural filler in thermoplastic biocomposites from polypropylene or biopolyethylene, resulting in cost-effective materials with attractive properties. This work thus presents a strong contribution to the setup of a true integrated biorefinery for coriander fruits and its industrial implementation on a relevant production scale.