Arundo donax (Giant Reed) is quickly being developed as a rapidly-growing, robust, and highly productive bioenergy crop, with large scale cultivation of this species planned for the Columbia River basin of the Pacific Northwest (USA). Despite its potential as a next generation biomass crop, relatively few studies have examined the physiological performance of A. donax under agricultural conditions. Unlike traditional crops, A. donax is known to be a high-emitter of the volatile compound isoprene, which may significantly impact regional air quality, but it has not been widely cultivated in North America and little is known about how this species will perform in the Pacific Northwest. Over two field seasons, we measured isoprene fluxes from A. donax plants in both greenhouse conditions and in an agricultural field setting under a variety of conditions and fertilizer treatments. We also measured several other attributes of A. donax productivity and leaf physiology including chlorophyll content, photosynthesis rate, stomatal conductance, specific leaf mass, water use efficiency and gas exchange. We found that A. donax physiologically performs well under cultivation in the Columbia River basin, but that it also emits isoprene at significantly higher rates than previous reports indicate. We also found that both isoprene emission and leaf physiology were highly affected by agricultural management decisions, including nitrogen and irrigation management. Our findings indicate that crop management strategies can be developed that simultaneously seek to minimize isoprene emission while maximizing biomass production in this newly emerging bioenergy crop.

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Flüchtige organische Verbindungen (volatile organic compounds, VOCs) haben vielseitige Funktionen in der Biosphäre und Atmosphäre. VOCs sind an ober- und unterirdischen Interaktionen beteiligt. Zum Beispiel können von Mikroorganismen emittierte VOCs das Pflanzenwachstum beeinflussen und von Pflanzen emittierte VOCs sich auf das Verhalten von Pathogenen und Herbivoren auswirken. Nur wenig ist über die Rolle von VOCs in der Kommunikation von Ektomykorrhizapilzen (EMF) mit ihren Wirtspflanzen bekannt. EMF gehen Symbiosen mit Baumarten wie Pappeln (Populus spp.) ein. Pappeln sind als Biomasseproduzenten von großer ökonomischer Bedeutung, emittieren jedoch eine hohe Konzentration des klima-relevanten VOCs Isopren in die Atmosphäre. Die Rolle von Isopren in biotischen Interaktionen von Pappeln mit Herbivoren ist unklar. Zudem ist es wichtig zu verstehen wie EMF-Inokulation den Metabolismus von Pappeln und dadurch deren oberirdische Interaktion beeinflussen. Hauptziel dieser Arbeit war es, die Kommunikation durch VOCs zwischen Pflanzen und Pilzen zu untersuchen. Zu diesem Zweck wurden die Modellarten Laccaria bicolor und Populus × canescens verwendet. Um die Spezifität von VOC-Mustern sowie Pflanzen-Reaktionen zu untersuchen, wurden einige andere EMF und nicht-Mykorrhiza bildende Pilze getestet sowie die Nicht-Wirtspflanze Arabidopsis verwendet. Um die Bedeutung von Isopren oder EMF auf oberirdische Herbivorie zu untersuchen, wurde die Präferenz des Pappelblattkäfers (Chrysomela populi) und des Weidenblattkäfers (Phrotara vitellinae) für nicht-Isopren emittierende Pappeln überprüft. Insbesondere wurden folgende Fragestellungen untersucht: i) Können EMF und Pilze anderer Lebensweisen aufgrund ihrer VOC-Emissions-Muster voneinander unterschieden werden? ii) Sind pilzliche VOCs an der Erkennung von EMF durch Pappel und Arabidopsis beteiligt und wenn dies zutrifft, welche Verbindungen der Volatilen-Mischung sind an der Reaktion beteiligt? iii) Ist die Isopren-Emission von Pappeln für die Orientierung von Pappelblattkäfern von Bedeutung? iv) Beeinflusst eine Inokulation von Pappeln mit EMF die Abwehr gegen den Pappelblattkäfer C. populi und wenn, welche Transkriptionsveränderungen in den Blättern von EMF-inokulierten im Vergleich zu nicht-inokulierten Pflanzen sind an dieser Reaktion beteiligt? Untersuchungen über Mykorrhiza-Interaktion mit Pappeln erfordern kontrollierte Kultivierungs-Systeme. Daher werden detaillierte Protokolle für die Anzucht von Pappelarten mit und ohne EMF unter axenischen und Freiland-Bedingungen angegeben. Zur Untersuchung der Interaktion zwischen Pappeln und EMF werden zwei-geteilte Wachstumssysteme für die Kultivierung der Pflanzen ohne direkten Kontakt zu EMF beschrieben. i) Um die Spezifität und Gemeinsamkeiten von VOCs von EMF und anderen, nicht-Mykorrhiza bildenden Pilzen zu untersuchen, wurden VOC-Muster von Pilzen verschiedener Lebenssweisen verglichen. In der vorliegenden Arbeit wurden die VOC-Emissionen der drei EMF Cenococcum geophilum, L. bicolor und Paxillus involutus (Stämme MAJ und NAU), der drei Pathogene Armillaria mellea, Pholiota squarrosa und Verticillium longisporum sowie der zwei Saprophyten Stropharia rugosoannulata und Trichoderma viride im Gasraum der Kulturen gesammelt. Die Pilze wurden in Petrischalen auf einem synthetischen Medium, welches eine geringe eigene VOC-Emission aufwies, angezogen. Alle VOCs, welche in Kontrollschalen ohne Pilz gemessen wurden, wurden aus dem Datensatz entfernt. Nach Entfernung dieser 40 Hintergrund-VOCs der Kontrollplatten verblieben 54 Pilz-VOCs. Die untersuchten Pilze unterschieden sich stark in ihrem VOC-Emissions-Profil. Nur 15 VOCs wurden bei allen Lebensweisen identifiziert; darunter die typische Pilz-VOC 1-octen-3-ol. Fünfzehn VOCs wurden zuvor noch nicht bei Pilzen gemessen und einige VOCs wurden nur bei einem Pilz oder einer Lebensweise gefunden. Insbesondere die Emission der Sesquiterpene (SQTs) unterschied sich stark zwischen den Pilzen. Multivariate Analysen der VOC-Profile gruppierte die Pilzarten nach ihren Lebensweisen. ii) Zur Ermittlung, ob Pilz-VOCs wichtige Signalstoffe für Pflanzen sind, unabhängig von ihrer Fähigkeit eine Mykorrhiza bilden zu können, wurden die Wirtspflanze P. × canescens und die Nicht-Wirtspflanze A. thaliana VOCs der EMF L. bicolor und C. geophilum ausgesetzt. Pflanzen und Pilze wurden in einem geschlossenen System mit zwei separaten Kompartimenten und gemeinsamem Gasraum kultiviert. Sammeln der Pilz-VOC-Emissionen in den Kontrollplatten mit den Pflanzen zeigte, dass Arabidopsis nur wenige VOCs emittierte, wohingegen sowohl in den Kulturen von L. bicolor als auch in der gemeinsamen Kultur von L. bicolor mit Pflanzen vor allem SQTs detektiert wurden. Die Seitenwurzelbildung von Arabidopsis und Pappel wurde durch L. bicolor-VOCs angeregt. C. geophilum, welcher nicht fähig ist SQTs zu bilden, hatte keine Wirkung auf die Wurzelstruktur. Unterdrückung der SQT-Synthese in L. bicolor durch Inhibierung des Mevalonat-Biosyntheseweges mit Lovastatin verminderte die Stimulierung der Seitenwurzelbildung signifikant. Diese Ergebnisse deuten darauf hin, dass pilzliche SQTs Seitenwurzelbildung auslösen. Das schwach emittierte Thujopsen stimulierte die Seitenwurzelbildung sowohl in Abwesenheit des Pilzes als auch bei einer Unterdrückung der SQT-Biosynthese des Pilzes durch Lovastatin. Das SQT β-Caryophyllene hatte keinen Einfluss auf die Wurzelstruktur. Diese Arbeit zeigt, dass pilzliche SQTs, darunter das spezifische Thujopsen, wichtige Signalstoffe in der Interaktion zwischen EMF und Wirts- sowie Nicht-Wirtspflanzen darstellen. iii) Die Käfer C. populi und P. vitellinae sind typisch vorkommende Schädlinge in Pappelplantagen und können signifikante ökonomische Verluste verursachen. Zur Ermittlung, ob von Pappelblättern emittiertes Isopren von C. populi und P. vitellinae Käfern wahrgenommen wird und eine Rolle bei der Orientierung dieser Käfer spielt, wurden verschiedene Fraßversuche mit den Käfern und Isopren-emittierenden und transgenen nicht-Isopren-emittierenden Pappeln durchgeführt. Sowohl in Gewächshaus- als auch in Laborversuchen zeigten weder die Larven noch die Käfer eine Präferenz für Isopren-emittierende oder nicht-emittierende Linien. Unerwarteter Weise wurden eine verstärkte Eiablage und ein höherer Fraßschaden auf Isopren-emittierenden gegenüber nicht-emittierenden Linien unter Freilandbedingungen festgestellt. Metabolomanalysen wiesen auf Veränderungen in den Blättern, welche von der Pappellinie abhängig waren, und auf Effekte auf Terpen-Muster hin. Die Käfer waren in der Lage verschiedene Terpene wahrzunehmen, waren aber nicht in der Lage Isopren wahrzunehmen. Daher könnten kleine Veränderungen der VOC-Emission in den transgenen nicht-Isopren emittierenden Pappellinien durch Unterdrückung der Isopren-Produktion und/oder ausgelöste Veränderungen im Metabolom-Profil die Käfer-Präferenz verändert haben. Obwohl das Hauptziel der Untersuchung - Isopren - keinen Einfluss auf das Käferverhalten hatte, wurde das Käferverhalten auf den Pappeln durch Konsequenzen der Modifikation beeinflusst. Das Ausmaß dieses Effektes war jedoch marginal. iv) Unter natürlichen Bedingungen interagieren Pappeln zeitgleich mit unterirdischen und oberirdischen Organismen. Zur Untersuchung, ob eine Inokulation von Pappeln mit EMF in den Blättern molekulare Veränderungen hervorruft und ob diese Veränderungen das Verhalten von Pappelblattkäfern beeinflussen, hatten C. populi-Käfer die Wahl zwischen Pappeln, welche mit L. bicolor inokuliert waren, und solchen, die nicht inokuliert waren. C. populi präferierten die Nicht-inokulierten sowohl als Nahrung als auch zur Eiablage. RNA-Sequenzierung des Blatttranskriptoms deutete an, dass der Käferbefall eine starke Abwehrreaktion in den Pflanzen auslöste. Auch die EMF-Inokulation beeinflusste das Blatt-Transkriptom, jedoch nur von wenigen Genen. Im Vergleich zu den nicht-inokulierten Pappeln wiesen die inokulierten Pappeln verringerte Transkript-Abundanzen von Genen des Abscisinsäure-Signalweges und der Flavonoid-Biosynthese sowie erhöhte Transkript-Abundanzen der Biosynthesegene von Aldoximen auf, welche kürzlich als Abwehrstoffe identifiziert wurden. Diese Ergebnisse lassen vermuten, dass EMF die Abwehr gegen Herbivore aktivieren und dadurch den natürlichen Schutz von Pappeln verbessern. In jungen Pappeln verursachen EMF jedoch auch ein signifikant geringeres Wachstum. Zusammenfassend zeigen die Ergebnisse dieser Dissertation, dass EMF-VOC-Profile sich von jenen anderer Pilze oder anderer Lebensweisen unterscheiden und dass eine bestimmte chemische Gruppe, die SQTs, als Signalmoleküle in frühen Interaktionen mit Pflanzen fungieren. Zum ersten Mal konnte eine Pilz-VOC, Thujopsen, identifiziert werden, welche für die Stimulierung der Seitenwurzelbildung in Pflanzen verantwortlich ist. Es wurde gezeigt, dass die Haupt-Pappel-VOC Isopren nur eine geringe Rolle in oberirdischen Interaktionen mit dem Herbivoren C. populi spielt. EMF führten zu Transkriptveränderungen in Pappelblättern und einer reduzierten Attraktivität für C. populi Käfer. Die Ergebnisse dieser Dissertation können für biotechnologische Verbesserungen von Pappeln und verstärktem Schutz von Pappeln in Biomasseplantagen verwendet werden.

Les composés organiques volatils (COV) sont des composants clé en chimie atmosphérique. Ils participent à des réactions photochimiques dans la basse atmosphère et jouent ainsi un rôle majeur dans le cycle de l'ozone troposphérique et la formation d‘aérosols organiques secondaires. A l'échelle globale, ces COV sont à 10% d'origine anthropique et à 90% d'origine biotique. Les enjeux liés aux émissions de COVB sont d‘autant plus importants en région méditerranéenne en raison du potentiel d‘émission élevé ainsi que des évènements réguliers de pollution photochimique. Cette thèse propose, à travers deux campagnes de mesures intensives, la caractérisation expérimentale des COVB et de leurs produits d‘oxydation dans deux sites ruraux représentatifs de la végétation méditerranéenne.Dans le cadre du projet CANOPEE (ANR-JCJC 2011-2014) une campagne de mesure a eu lieu à l‘Observatoire du chêne pubescent de Haute Provence (O3HP). Des mesures de concentrations et de flux d‘émission ont été réalisées à l‘échelle de la canopée dans le but de quantifier l‘export des COVB hors canopée et d‘étudier la chimie intra-Canopée. Dans la forêt de l‘O3HP, des concentrations en isoprène très élevées ont été mesurées, en particulier au sein de la canopée où elles ont atteint 16 ppbv les journées les plus chaudes. Selon le facteur d‘émission de 7.2 mg m-2 h-1 déterminé, la forêt de chênes pubescents de l‘O3HP fait partie des écosystèmes les plus fortement émetteurs d‘isoprène à travers le monde. Parmi les COV oxygénés, seul le méthanol a des flux d‘émission significatifs, avec un taux d‘émission moyen égal à 0.3 mg m-2 h-1. Un des points forts de ce travail a consisté en l‘étude du transport et de la chimie intra-Canopée. D‘après nos estimations, les processus intra-Canopée sur le site de l‘OHP jouent un rôle mineur sur les flux nets d‘isoprène sortant de la canopée.La deuxième campagne de mesure s‘inscrit dans le cadre du programme ChArMEx (Chemistry-Aerosol Mediterranean Experiment). Elle a pris place sur le site du Cap Corse, situé à distance des sources anthropiques et qui abrite une diversité d'espèces végétales. Les résultats obtenus ont permis la quantification et spéciation de nombreux COVB. Un grand contraste dans la signature des émissions de COVB a été observé entre les deux sites d‘étude. Ainsi, tandis que l‘isoprène est responsable de plus de 90% des COVB en termes de concentrations à l‘OHP, il ne représente que 35% de leurs concentrations totales au Cap Corse. Les 65% restants sont composés de nombreux monoterpènes. Ces résultats ont également mis en évidence la chimie rapide des COVB et l‘importance de leur contribution à la formation de composés secondaires oxygénés dans les conditions de photochimie intense qui caractérisent le bassin méditerranéen en période estivale.Au Cap Corse, comme à l‘O3HP, les COVB représentent le puit dominant des radicaux hydroxyles. En présence de NOx et pour des concentrations équivalentes à celles de l‘OHP ou du Cap Corse, le potentiel des COVB à former de l‘ozone a été évalué à 10 ppbv en moyenne. / Volatile organic compounds (VOCs) are key components in atmospheric chemistry. They participate in photochemical reactions in the lower atmosphere and thus play a major role in the formation of tropospheric ozone and secondary organic aerosols. Biogenic VOCs (BVOCs) constitute approximately 90% of global VOC emissions. In the Mediterranean region, the emissions and reactivity of BVOCs are enhanced due to high temperatures and sunny conditions. In this context, this work proposes, through intensive field campaigns, the experimental characterization of BVOCs and their oxidation products in two rural sites where the vegetation is representative of the Mediterranean region. Within the framework of the CANOPEE program (ANR-JCJC 2011-2014) an intensive field campaign took place at the Oak Observatory of the Observatoire de Haute Provence (O3HP). Measurements of concentrations and emission fluxes were carried out in order to quantify the export of BVOC off the canopy and study in-Canopy processes. High concentrations of isoprene were measured with daily maximum ambient concentrations ranging between 2-16 ppbv inside the forest. According to the emission factor of 7.2 mg m-2 h-1 determined, downy oak forest of the O3HP is one of the strongest emitters of isoprene worldwide. Evidence of direct emission of methanol was also found exhibiting an average emission rate equal to 0.3 2 mg m-2 h-1. One of the strengths of this work consisted in the study of transport and intra-Canopy chemistry. In-Canopy chemical oxidation of isoprene was found to be weak and did not seem to have a significant impact on isoprene concentrations and fluxes above the canopy. The second field campaign is part of the ChArMEx (Chemistry-Aerosol Mediterranean Experiment) program. It took place on the remote site of Cap Corse, characterized by a strong diversity of plant species. The rich dataset obtained allowed the quantification and speciation of many BVOCs. A great contrast in the signature emissions was observed between the two study sites. Thus, while isoprene is responsible for over 90% of BVOCs in terms of concentrations at the O3HP, it represents only 35% of their total concentrations in Cap Corse. The remaining 65% are composed of many monoterpenes. These results have also highlighted the rapid chemistry of BVOCs and the importance of their contribution to the formation of secondary oxygenated compounds under intense photochemistry conditions, typical of the summertime in the Mediterranean basin. Biogenic BVOCs represented the dominant hydroxyl radicals sink at the O3HP as well as in Cap Corse. In the presence of NOx, the potential of the measured BVOCs to produce ozone has been estimated at about 10 ppbv on average.

Este trabalho descreve a aplicação de redes neurais \"feed-forward\" com três camadas em diferentes áreas da Engenharia Química. O objetivo principal do projeto é a modelagem, simulação e posterior otimização do processo de produção de isopreno empregando técnicas de redes neurais em substituição as equações de modelagem fenomenológica. A planta industrial testada é a unidade de produção de isopreno da BRASKEM (antiga COPENE). O sistema consiste essencialmente de um reator de dimerização e uma série de colunas de destilação. Uma vez que redes neurais são capazes de aprender eficientemente o processo a partir de informações extraídas diretamente de dados da planta, para este trabalho o modelo de rede neural gerado foi construído a partir de dados históricos operacionais coletados a cada 15 minutos durante o período de 1 ano. Em uma primeira etapa é realizada a análise dos dados operacionais de modo a detectar e eliminar erros grosseiros e sistemáticos. Em seguida, a modelagem e simulação do processo são realizadas. O modelo de redes neurais gerado é, então, empregado na otimização qualitativa/quantitativa do processo, construindo um \"grid\" de busca detalhado da região de interesse, através um mapeamento completo da função objetivo no espaço das variáveis de decisão. A segunda etapa diz respeito à predição de azeótropos, visando um melhor entendimento do comportamento do sistema da seção de extração de isopreno. Nas duas etapas, a grande vantagem em utilizar modelos de redes neurais, além de ajustar dados, é a capacidade que estes apresentam em representar eficientemente sistemas multivariáveis, complexos e não lineares, aprendendo o sistema, sem o conhecimento das leis físicas e químicas que o regem. Comparações entre a predição dos modelos propostos e os dados experimentais foram executadas e resultados muito bons foram conseguidos do ponto de vista industrial. ) Esta metodologia fornece informações interessantes e de maior compreensão para a análise dos engenheiros de processo do que os procedimentos convencionais correspondentes. Além disso, este trabalho mostra que a metodologia de redes neurais é promissora para varias aplicações indústrias, tais como análise de dados, modelagem, simulação e otimização de processos, bem como predição de propriedades termodinâmicas. / This work describes the application of a three-layer feed-forward neural network (NN) in different areas of chemical engineering. The main objective of this study is to model, simulate and optimize a real industrial plant, using NN by replacing phenomenological models. The industrial process studied is the isoprene production unit from BRASKEM. The chemical process consists basically of a dimerization reactor and a separation column train. Since NNs are able to extract information from plant data in an efficient manner, for this work, the neural network model was built directly from historical plant data, which were collected every 15 minutes during a period of one year. These data were carefully analyzed in order to identify and eliminate gross error data and non-steady state operation data. The modeling using NN was carried out by parts in order to get information on intermediate streams. Then, the global model was built, by interconnecting each individual model, and used to simulate and optimize the process. The optimization procedure carries on a detailed grid search of the region of interest, by a full mapping of the objective function on the space of decision variables. The second stage of this work deals with the azeotropic prediction using also the neural network approach. The objective of this step was to obtain a better understanding of the system behavior in the isoprene extraction section. Since all the cases studied are non-linear, complex andmultivariable systems, NN approach appears as a technique of interest due to its capability of learning the system without knowledge of the physical and chemical laws that govern it. Comparisons between the model\'s prediction and the experimental data were performed and reasonable results were achieved from an industrial point of view. ) Using neural network approach provides more comprehensive information for an engineer\'s analysis than the conventional procedure. This work shows that the use of NN methodology is promising for several industrial applications, such as data analysis, modeling, simulation and optimization process, as well as thermodynamics properties prediction. However, success in obtaining a reliable and robust NN depends strongly on the choice of the variables involved, as well as the quality of available data set and the domain used for training purposes.

Dans ce travail de thèse nous décrirons tout d'abord la synthèse de nouveaux composés terpénoïdes par télomérisation de l'éthanolamine avec l'isoprène. Ensuite nous présentons l'utilisation de cette méthode pour la fonctionnalisation des poly-carbohydrates non alimentaires comme le chitosane et une hémicellulose (la gomme de guar) dans l'eau. Avec les substrats bifonctionnels (éthanolamine, chitosane), la réaction de télomérisation des diènes peut avoir lieu avec l'amine ou l'alcool pour conduire à la formation d'éthers ou d'alkylamines fonctionnalisés à longue chaine carbonée. Cette réaction est catalysée par des complexes de palladium-phosphine formés in-situ et est réalisée en présence ou en absence d'une base dans différents solvants (Eau, MeOH, i-PrOH, Eau/iPrOH), y compris en milieu biphasique.L'influence des paramètres réactionnels tels que l'effet du solvant, du précurseur de palladium, de la charge en catalyseur, du rapport Ligand/Palladium, de la nature des ligands phosphines, de la température et du temps réactionnel, de la quantité de diène et de la quantité de la base, a été étudiée. L'activité et la sélectivité de la réaction ont été déterminées en réalisant des analyses de chromatographie gazeuse GC (pour les terpénoïdes), des analyses RMN 1D et 2D (pour les terpénoïdes et les polysaccharides modifiées). Ceci a permis la détermination des conversions, ainsi que des degrés de substitution (DS) des polysaccharides modifiés. Des analyses élémentaires {C, H, N} ont été réalisées pour valider les structures et la pureté des produits obtenus. La stabilité thermique des télomères des carbohydrates (chitosane et gomme de guar) a été étudiée par analyse thermogravimétrique (ATG).Avec l'éthanolamine, le rendement total en terpénoïdes varie de 31% à 81 %, distribués entre des monotélomères (50-80%) et des ditélomères (20-50%). Pour les polysaccharides, des degrés de substitution compris entre 0.03 et 0.61 (DS =0.61 dans l'eau) pour les alkyl-chitosane et 0.01 et 0.31 (dans l'eau) pour la gomme de guar modifiée sont obtenus / In this thesis, we will first describe the synthesis of new terpenoid compounds by telomerization of isoprene with ethanolamine. Then we will present the usage of this method for the functionalization of non-food related poly-carbohydrates such as the hemicellulose (guar gum) and the chitosan in water.With the bifunctional substrates (ethanolamine, chitosan), the reaction of telomerization of the dienes can take place between the amine or the alcohol in order to lead either to the formation of the ethers or to the formation of the functionalized alkylamines with a long carbon chain. This reaction is catalyzed by palladium-phosphine complexes formed in situ, and realized in the presence or in the absence of a base in different solvents (water, MeOH, i-PrOH, water/iPrOH), and in biphasic medium.The influence of reactional parameters such as the effect of the solvent, that of the precursor of palladium, that of the catalyst charge, that of the Ligand/Palladium ratio, that of the nature of the phosphines ligands, that of the temperature and the reaction time, as well as the effect of the quantity of diene and of the base were studied.The activity and the selectivity of the reaction were determined using the gas chromatography analysis (for the terpenoids), and 1D & 2D RMN analyses (for the terpenoids and modified polysaccharides). This allowed us to determine the conversions and the degree of substitution of the modified polysaccharides. Elementary analysis (C, H, N) were also performed to validate the structures and the purity of the products obtained. The thermal stability of the carbohydrates telomeres (chitosan and guar gum) was studied by thermogravimetric analysis.With the ethanolamine, the total yield in terpenoids varied between 31% and 81% and was distributed between monotelomers (50-80%) and ditelomers (20-50%).For the polysaccharides, the degree of substitution obtained varied between 0.03 and 0.61 (DS=0.61 in water) for the alkyl-chitosan and between 0.01 and 0.31 (in water) for the modified guar gum

105 f. / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-10-03T13:45:39Z No. of bitstreams: 1 Apresentação_Denise_VersãoFinal.pdf: 4275455 bytes, checksum: 65d7b6e55b90b2695016ec5154b6bbc4 (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-10-03T13:48:30Z (GMT) No. of bitstreams: 1 Apresentação_Denise_VersãoFinal.pdf: 4275455 bytes, checksum: 65d7b6e55b90b2695016ec5154b6bbc4 (MD5) / Made available in DSpace on 2013-10-03T13:48:30Z (GMT). No. of bitstreams: 1 Apresentação_Denise_VersãoFinal.pdf: 4275455 bytes, checksum: 65d7b6e55b90b2695016ec5154b6bbc4 (MD5) Previous issue date: 2012 / A espectroscopia na região do infravermelho próximo (NIRS), associada a técnicas quimiométricas, foi utilizada no desenvolvimento de modelos de calibração multivariada para a predição da composição química de um solvente orgânico- aquoso utilizado na produção de isopreno. Os modelos foram construídos para a predição da concentração dos componentes presentes no solvente: acetona, acetonitrila, água, n-propanol, i-propanol, álcool alílico, t-butanol e DCPD (diciclopentadieno-1,3). Uma análise exploratória dos dados foi realizada para detecção de amostras anômalas, através da análise de componentes principais (PCA). Para seleção dos conjuntos de calibração e validação, o algoritmo SPXY (Sample set Partitioning based on joint x-y distances) foi utilizado. As condições experimentais para a construção dos modelos foram escolhidas através da realização de um planejamento experimental para três variáveis baseado na matriz Doehlert, em que foram estudadas 1) técnica de pré-processamento, 2) faixa de comprimento de onda, obtidas através do algoritmo de seleção de variáveis por regressão dos mínimos quadrados parciais por intervalo (iPLS), e 3) seleção de variáveis espectrais, com a utilização do algoritmo Jack Knife. A técnica de regressão por mínimos quadrados parciais (PLS) foi utilizada para a calibração multivariada. As variáveis de resposta, PC, RMSECV, r2regr, RMSEP, r2valid, Slope Valid e pvalue, obtidas a partir dos modelos definidos no planejamento experimental, foram otimizadas simultaneamente, através da função de desejabilidade. Novos modelos de calibração foram construídos a partir dos valores ótimos encontrados para cada variável de entrada. Pelo menos 85 amostras de calibração foram usadas em cada modelo, sendo necessários entre 1 e 10 fatores para assegurar o melhor desempenho de cada modelo. Os coeficientes de determinação de validação cruzada (r2regr) foram maiores que 0,92 para todas as propriedades. Os valores para os RMSEPs variaram de 0,39 a 1,66 (% m/m). Portanto, o método desenvolvido mostrou-se viável para determinação da composição química do solvente e auxiliar no controle do processo da unidade de produção de isopreno. / Salvador

Este trabalho descreve a aplicação de redes neurais \"feed-forward\" com três camadas em diferentes áreas da Engenharia Química. O objetivo principal do projeto é a modelagem, simulação e posterior otimização do processo de produção de isopreno empregando técnicas de redes neurais em substituição as equações de modelagem fenomenológica. A planta industrial testada é a unidade de produção de isopreno da BRASKEM (antiga COPENE). O sistema consiste essencialmente de um reator de dimerização e uma série de colunas de destilação. Uma vez que redes neurais são capazes de aprender eficientemente o processo a partir de informações extraídas diretamente de dados da planta, para este trabalho o modelo de rede neural gerado foi construído a partir de dados históricos operacionais coletados a cada 15 minutos durante o período de 1 ano. Em uma primeira etapa é realizada a análise dos dados operacionais de modo a detectar e eliminar erros grosseiros e sistemáticos. Em seguida, a modelagem e simulação do processo são realizadas. O modelo de redes neurais gerado é, então, empregado na otimização qualitativa/quantitativa do processo, construindo um \"grid\" de busca detalhado da região de interesse, através um mapeamento completo da função objetivo no espaço das variáveis de decisão. A segunda etapa diz respeito à predição de azeótropos, visando um melhor entendimento do comportamento do sistema da seção de extração de isopreno. Nas duas etapas, a grande vantagem em utilizar modelos de redes neurais, além de ajustar dados, é a capacidade que estes apresentam em representar eficientemente sistemas multivariáveis, complexos e não lineares, aprendendo o sistema, sem o conhecimento das leis físicas e químicas que o regem. Comparações entre a predição dos modelos propostos e os dados experimentais foram executadas e resultados muito bons foram conseguidos do ponto de vista industrial. ) Esta metodologia fornece informações interessantes e de maior compreensão para a análise dos engenheiros de processo do que os procedimentos convencionais correspondentes. Além disso, este trabalho mostra que a metodologia de redes neurais é promissora para varias aplicações indústrias, tais como análise de dados, modelagem, simulação e otimização de processos, bem como predição de propriedades termodinâmicas. / This work describes the application of a three-layer feed-forward neural network (NN) in different areas of chemical engineering. The main objective of this study is to model, simulate and optimize a real industrial plant, using NN by replacing phenomenological models. The industrial process studied is the isoprene production unit from BRASKEM. The chemical process consists basically of a dimerization reactor and a separation column train. Since NNs are able to extract information from plant data in an efficient manner, for this work, the neural network model was built directly from historical plant data, which were collected every 15 minutes during a period of one year. These data were carefully analyzed in order to identify and eliminate gross error data and non-steady state operation data. The modeling using NN was carried out by parts in order to get information on intermediate streams. Then, the global model was built, by interconnecting each individual model, and used to simulate and optimize the process. The optimization procedure carries on a detailed grid search of the region of interest, by a full mapping of the objective function on the space of decision variables. The second stage of this work deals with the azeotropic prediction using also the neural network approach. The objective of this step was to obtain a better understanding of the system behavior in the isoprene extraction section. Since all the cases studied are non-linear, complex andmultivariable systems, NN approach appears as a technique of interest due to its capability of learning the system without knowledge of the physical and chemical laws that govern it. Comparisons between the model\'s prediction and the experimental data were performed and reasonable results were achieved from an industrial point of view. ) Using neural network approach provides more comprehensive information for an engineer\'s analysis than the conventional procedure. This work shows that the use of NN methodology is promising for several industrial applications, such as data analysis, modeling, simulation and optimization process, as well as thermodynamics properties prediction. However, success in obtaining a reliable and robust NN depends strongly on the choice of the variables involved, as well as the quality of available data set and the domain used for training purposes.

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No. of bitstreams: 1 Dissertação - Maria Oneide Silva de Moraes.pdf: 9993702 bytes, checksum: d0ede70d56d052b19d6265bf315f6128 (MD5) Previous issue date: 2013-03-25 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The absolute values of the photoabsorption cross section of compounds are of great importance in the fields of physics, chemistry, biology, therapy and related fields. Studies of natural products are also of great importance several areas of science and innovation, however, information related to the values of the photoabsorption cross section in the vacuum ultraviolet region are scarce in the literature. In this paper a study of the electronic excitations of the molecule isoprene using a spectrometer energy loss of electrons from low-resolution (0,8– 1,0 eV FWHM) at the Laboratory for Photon and Electron Impact (LIFE-UFRJ). The energy loss spectra of electrons were obtained in the range 3-100 eV at various angles of scattering with incident energy of 1 keV. The spectra of generalized oscillator strength (GOS) for the isoprene molecule were obtained by the Bethe-Born conversion. The spectrum GOS obtained in the angle of impact 2o was extrapolated to the strength oscillator photoabsorption optical using the universal formula Msezane and Sakmar (1997). The photoabsorption cross sections on an absolute scale were determined by of the static polarizability of isoprene applying the sum rule S(-2) in the photoabsorption spectrum. The contributions of the inner layer photoabsorption above 100 eV were estimated from a fit polynomial curve. Other sum rules were used to estimate the values of physical properties isoprene as sum rule S(0) is equal to the number of electrons on the target (36,45 a. u.), the rule logarithmic L(0) is the stopping power of the molecule (18,05 a.u.), the rule logarithmic L(1) is related to the effect straggling referring to fluctuations of the incident beam (22,49 a.u.) and rule logarithmic L(2) for the Lamb shift (55,27 a.u.). The set of spectra GOS obtained at different scattering angles were presented in Bethe surface to isoprene. Two regions stand out: a region dominated by the optical selection rules for electronic transitions of the absorption, and the other region, we observed a strong angular dependence on the momentum of the incident electrons becomes significant.The Bethe surface and the sum rules are unpublished experimental data in the literature. The absolute values of the cross section and the Bethe surface can contribute to a complete understanding of the electronic excitations of the molecule isoprene induced by collisions of charged particles. It is expected that these absolute valuesmay be useful as references to theoretical calculations and experimental in the electronic spectra of isoprene. / Os dados de seção de choque de fotoabsorção de compostos são de grande importância nas áreas de física, química, biologia, terapia e áreas afins. Os estudos de produtos naturais também são de grande importância em diversas áreas científicas e de inovação, porém, informações relacionadasaos valores de seção de choque de fotoabsorção na região ultravioleta de vácuo são incipientes na literatura. Neste trabalho foi feito um estudo das excitações eletrônicas da molécula isopreno utilizando um espectrômetro de perda de energia de elétrons de baixa resolução (0,8 – 1,0 eV FWHM) no Laboratório de Impacto de Fótons e Elétrons (LIFE-UFRJ). Os espectros de perda de energia de elétrons foram obtidos na faixa de 3 a 100 eV em vários ângulos de espalhamentos com energia incidente de 1 keV. Os espectros de força do oscilador generalizado (FOG) para a molécula isopreno foram obtidos pela conversão de Bethe-Born. O espectro de FOG obtido no ângulo de impacto de 2o foi extrapolado para força do oscilador de fotoabsorção ótico utilizando a fórmula universal de Msezane e Sakmar (1997). As seções de choque de fotoabsorção em escala absoluta foram determinadas por meio da polarizabilidade estática do isopreno aplicando a regra de soma S(-2) no espectro de fotoabsorção. As contribuições da fotoabsorção da camada interna acima de 100 eV foram estimadas com o ajuste de uma curva polinomial.Outras regras de somas foram utilizadas para estimar os valores de propriedades físicas para o isopreno como a regra de soma S(0) que é igual ao número de elétrons no alvo (36,45 u. a., unidades atômicas), a regra de soma logarítmica L(0) é o stopping power da molécula (18,05 u. a.), a regra de soma logarítmica L(1) é o efeito straggling referente às flutuações estáticas do feixe incidente (22,49 u. a.) e a regra de soma logarítmica L(2) referente ao deslocamento de Lamb (55,27 u. a.). O conjunto de espectros de FOG obtidos em diferentes ângulos de espalhamento foi apresentado na Superfície de Bethe para o isopreno. Duas regiões se destacaram: uma região dominada pelas regras de seleção ópticas de transições eletrônicas dos processos de absorção, e a outra região, foi observado uma forte dependência angular em que o momento linear dos elétrons incidentes torna-se significativo. A Superfície de Bethe e as regras de somas são resultados experimentais inéditos na literatura. Os valores absolutos de seção de choque e a Superfície de Bethe podem contribuir para um entendimento completo das excitações eletrônicas da molécula isopreno induzidas por colisões de partículas carregadas. É esperado que estes valores absolutos possam ser úteis como referências em cálculos teóricos e experimentais para o espectro eletrônico do isopreno.

Les nanotubes de carbone (NTCs), en raison de leurs propriétés exceptionnelles et d’une utilisation potentielle dans un grand nombre d'applications, constituent surement la classe la plus étudiée des nanomatériaux. Les NTCs fonctionnalisés, qui peuvent être facilement manipulés et modifiés par liaison covalente ou fonctionnalisation non covalente, apparaissent comme de nouveaux outils dans le domaine des biotechnologies et en biomédecine. En effet, les NTC ont des propriétés optiques, électroniques et mécaniques qui peuvent être exploitées dans des applications biologiques ou biomédicales. Les nanoparticules magnétiques métalliques (NPMMs) de la série 3d ainsi que leurs alliages présentent d'excellentes propriétés magnétiques contrairement à leurs homologues oxydes, qui peuvent être exploitées en biomédecine et pour l'enregistrement magnétique ultra-haute densité. Les nano-matériaux confinés dans les NTCs peuvent présenter des propriétés et des comportements différents par rapport aux matériaux massifs. Divers effets de confinement provenant de l'interaction entre les matériaux confinés et les cavités internes des nanotubes de carbone offrent des possibilités de réglage ou la conception de nouveaux nanocomposites. Cette thèse est consacrée à l’étude d’une nouvelle approche pour le développement de matériaux nanocomposites NPMMs@NTC et de leurs propriétés. Des NPMMs de taille et forme contrôlée de Co et de Fe ont été synthétisées avec de nouveaux ligands aromatiques comme stabilisants. Ces MMNPs ont ensuite été introduites de manière sélective dans la cavité de NTCs du fait d’interactions attractives/répulsives entre les nanotubes de carbone multi-parois fonctionnalisés et les NPMMs. Nous nous sommes ensuite intéressés à la protection de ces nanoparticules de l’oxydation par l’air. Les nanoparticules de fer confinées ont ainsi été revêtues par du polyisoprène. Pour ce faire, la surface des nanoparticules de Fe a été modifiée avec un catalyseur de polymérisation par échange de ligand, puis la polymérisation de l'isoprène a été réalisée à l'intérieur du canal des NTCs. La protection de l'oxydation par le polyisoprène a été évaluée par des mesures magnétiques après exposition à l'air. De façon tout à fait surprenante, cette étude a montré que les nanoparticules de fer les plus résistantes à l’oxydation étaient celles obtenues après échange de ligand et sans polymérisation. Dans ce cas seulement les propriétés des nanoparticules originales sont maintenues après mise à l’air. Enfin, des nanostructures (particules ou fils) magnétiques bimétalliques associant le Pt au cobalt ou au fer ont été obtenues et confinées dans les NTCs. Leurs structures chimiques ordonnées ont également été étudiées par des études de recuit thermique. Le travail développé dans cette thèse ouvre de nouvelles perspectives pour la production de nouveaux nanocomposites MMNPs@NTC résistants à l’oxydation. / Carbon nanotubes (CNTs), because of their unique properties and potential use in a variety of applications, are probably the most studied class of nanomaterials. Functionalized CNTs, which can be easily manipulated and modified by covalent or non-covalent functionalization, appear as new tools in biotechnology and biomedicine. Indeed, CNTs have optical, electronic and mechanical properties that can be exploited in biological or biomedical applications. Metallic magnetic nanoparticles (MMNPs) of the 3d series and their alloys exhibit excellent magnetic properties unlike their oxide counterparts, which can be exploited in biomedicine and ultra-high density magnetic recording. When confined in CNTs nano-materials can have different properties and behaviors compared to bulk materials. Various confinement effects resulting from the interaction between the confined materials and the internal cavities of CNTs provide opportunities for regulating or designing new nanocomposites. This thesis is devoted to the study of a new approach for the development of nanocomposite materials MMNPs@CNTs and their properties. MMNPs of controlled size and shape of Co and Fe were synthesized with novel aromatic ligands as stabilizers. These MMNPs were then selectively introduced into the cavity of CNTs due to repulsive/attractive interactions between the functionalized multi-walled CNTs and the MMNPs. We were then interested in the protection of these nanoparticles from oxidation by air. Thus, confined iron nanoparticles have been coated with polyisoprene. To do this, the surface of the Fe nanoparticles has been modified with a polymerization catalyst by ligand exchange; then, polymerization of isoprene was conducted inside the channel of CNTs. The protection from oxidation by the polyisoprene was evaluated by magnetic measurements after exposure to air. Quite surprisingly, this study showed that the iron nanoparticles the more resistant to oxidation were those obtained after ligand exchange and without polymerization. In this case only, the original properties of the nanoparticles are maintained after venting. Finally, magnetic bimetallic nanostructures (particles or rods) combining Pt and cobalt or iron were obtained and confined in CNTs. Their chemical structure orderings were also studied by thermal annealing studies. The work developed in this thesis opens up new perspectives for the production of new MMNPs@NTC nanocomposites resistant to oxidation.