La présent étude examine aspect de l'écologie chimique de la Pyrale du maïs (Ostrinia nubilalis, Hübner, Lepidoptera: Crambidae). L’isolement reproducteur des phérotypes et leur spécialisation à la plante hôte ont reçu une attention particulière. Toutes les expériences ont été conçues pour avoir des informations pertinents sur le plan écologique des signaux chimiques libérés ou perçu par la Pyrale du maïs pendant la période de reproduction. La plupart des travaux en cadre de cette thèse dans des conditions naturelles et en tenant compte de tous les traits comportementaux de la Pyrale. Premièrement, le paysage chimique du champ de maïs a été étudié pour connaître les signaux chimiques rencontrés par une femelle de Pyrale du maïs qui est à la recherche d’une plante hôte. Les mélanges des volatiles qui composent l'environnement olfactif du champ de maïs a été identifié et leurs rôles discutés selon la biologie et le comportement d’oviposition de la Pyrale du maïs.Deuxièmement, en tenant compte de la périodicité du comportement de la Pyrale du maïs nous avons étudié les modifications circadiennes des profils des volatiles libérés par les plantes individuelles du maïs et par le champ du maïs.Troisièmement, le fidélité d’hôte plantes de la Pyrale du maïs a été étudié. Les volatiles libérés par différentes plantes hôtes au moment de vol d’oviposition ont été identifiés et le comportement de ponte a été étudié dans le tunnel du vol.Quatrièmement, les signaux chimiques impliqués dans l'isolement reproducteur des phérotypes de la Pyrale du maïs a été étudié. Nous nous sommes concentrés sur la phéromone mâle produite par les pinceaux androconiaux et sur leur rôle dans le comportement de cour. / The present PhD study investigates the aspect of chemical ecology in the European corn borer (ECB, Ostrinia nubilalis Hübner, Lepidoptera: Crambidae): pherotypes reproductive isolation and host plant specialisation.All the experiences were designed to have ecologically relevant information about the chemical signals released or perceived by ECB moth during the reproduction period. Most of the work was conducted close to natural conditions and taking into account all the behavioural traits of ECB.First we investigated what can be the chemical landscape of maize field for host-seeking ECB moth. The whole volatile blends that make up the olfactory environment of maize field biotope was identified according to the ECB oviposition behaviour (Paper I). Secondly taking into account the diel periodicity of ECB behaviour we studied the diel changes of volatile profiles released from maize plant and from maize field (Paper II). Thirdly, we studied the process of host fidelity within the ECB host plants. The volatiles released from different host plants at the time of ECB oviposition flight were identified and the oviposition behaviour was studied in wind tunnel to evidence the host plant preferences of ovipositing females (Paper III). Fourthly, we address the question on assortative mating in ECB pherotypes and we investigated the chemical signals involved in the reproductive isolation in ECB pherotypes. We focused on the male pheromone produced by hairpencils and on courtship behaviour (Paper IV).

Norway spruce (Picea abies) responds to stress by biosynthesis of chemical substances, which can deter invading insects or pathogens. Some of these substances are volatile and can be emitted to the surroundings while others are accumulated within the tree. Information about the susceptibility of individual plants to infestation, their volatile emissions and chemical defence is of interest, for example, in selecting plants for tree breeding programs. The first part of this research focused on volatiles emitted by Norway spruce plants. Collection of headspace volatiles by SPME and subsequent separation and identification with GC-MS was used to investigate Norway spruce plants of different ages and stress conditions as well as trapping semiochemicals like nepetalactone emitted by the spruce shoot aphids. It was even possible to analyse the emission of single needles in vivo and obtain spatial localisation of the stress reaction to methyl jasmonate or spruce spinning mites. Seedlings of different ages showed differences in chemical composition of emitted volatiles, with the pine weevil repellent, (4S)-(-)-limonene, one of the main compounds. Wounded phloem of conventional plants emitted high amounts of monoterpenes while the phloem of mini plants emitted (3Z)-hexenal and (3Z)-hexen-1-ol. In addition, a method to separate and identify the four diastereomers of nepetalactone by GC-MS and characteristic m/z-fragments was accomplished. The second part of the research deals with the chemical response of Norway spruce roots to inoculation with Heterobasidion annosum. Terpene concentrations increased after inoculation or wounding but the composition was mainly associated with clone identity and not to susceptibility or treatment. In contrast, inoculation with H. annosum induced a treatment-specific alteration of phenol composition. The constitutive phenol composition differed between more and less susceptible clones. The phenols astringin and astringin dimers (piceasides) as well as the terpene α-longipinene may be suitable markers of low susceptibility for P. abies to Heterobasidion. / QC 20110314

Doctor of Philosophy / Department of Human Nutrition / Delores H. Chambers / Vegetables are popular among consumers because of their versatility of preparation, unique sensory characteristics, and exceptional health benefits. Trends such as organic farming and breeding to increase nutrition and functional health components have increased interest in understanding the flavor of vegetables, such as leafy greens. A lexicon of thirty-two flavor attributes was created to help describe the flavor of fresh leafy vegetables. This lexicon includes five “green” attributes; mouth feel characteristics such as pungent, bite, tooth-etch, and heat/burn; fundamental tastes including bitter and umami; seven terms that describe unique flavors related to specific vegetables such as cabbage, celery, lettuce, spinach, parsley, beet, and radish leaves; and a group of other terms including citrus, piney, woody, water-like, musty/earthy, floral, sulfur, metallic, soapy, petroleum-like, and overall sweet. In addition, our study encompassed a series of sensory tests which will aid in better understanding the effects of several production variables on the sensory characteristics of pac choi and tomato. Variables evaluated were production systems (i.e. organic and conventional), fertilizer amount (i.e. high, low, and no fertilizer), environment (i.e. field and high tunnel), maturity level (i.e. 2.5, 4.5, and 6.5-week old plants at the time of harvest), and shelf life (i.e. 1, 4, 9, 18 days of refrigerated storage). Samples were grown at the Kansas State University Horticulture Research Center located in Olathe, Kansas. Highly trained descriptive panelists from the Sensory Analysis Center at Kansas State University evaluated the samples. There do not appear to be major sensory differences between organic and conventional products specific to the crops and seasons studied. Furthermore, when differences were present, they generally were quite small and showed no clear trends or patterns favoring one production system over the other even after refrigerated storage. However, it is suggested that differences in flavor and volatile composition between organic and conventional pac choi may be more evident at early stages of growth.

Ce travail porte sur l'identification de la structure et des mécanismes de formation de quelques produits de Maillard non volatils, l'objectif principal étant de mieux connaître le rôle précurseur de la glutamine. Contrairement aux molécules volatiles, nos connaissances sur les composés non volatils sont assez peu étendues. De plus, la glutamine, de structure proche de celle de l'asparagine, possède deux atomes d'azote susceptibles de participer à la réaction de Maillard : l'α-amine et l'ammoniac issu de la lactamisation. Dans ce contexte, nous avons recherché, isolé et caractérisé les produits de Maillard non volatils susceptibles de se former lors du traitement thermique d'aliments riches en glutamine et en ammoniac. A l'aide de différents outils analytiques (HPLC, fluorescence, spectrométrie de masse, RMN

Les composés soufrés volatils (CSV) sont des composés majeurs de l'arôme des fromages. Même présents à de très faibles concentrations, ils contribuent de manière significative à leur qualité aromatique et à leur typicité, du fait notamment de leur faible seuil de détection et de leur forte réactivité. Jusqu'à présent, les études portant sur la production de CSV étaient axées essentiellement sur le catabolisme de la méthionine, sans inclure l'implication potentielle de la cystéine dans leur production. Cette étude a donc eu pour principal objectif d'étudier dans quelle mesure la cystéine pourrait contribuer à la production de CSV par les levures et les bactéries de la flore d'affinage. La mise au point d'une technique de piégeage dans un système fermé, et de capture in situ de l'H2S produit par le catabolisme de la cystéine, nous a permis d'effectuer une sélection de souches les plus aptes à dégrader la cystéine. Cette technique a donc été utilisée pour quantifier la production d'H2S de vingt souches de levures et dix-sept souches de bactéries. Cinq souches de levures et quatre souches de bactéries ont été ainsi sélectionnées, et nous avons donc étudié leur capacité à produire des CSV à partir i) de la cystéine, ii) de la méthionine ou iii) de mélanges méthionine-cystéine. En ajoutant de la cystéine, aucun nouveau CSV n'a été produit par les levures, et seulement des traces de CSV ont été quantifiées chez les bactéries. Avec l'ajout de méthionine, deux voies de dégradation de la methionine ont été mises en évidence chez les souches de levures : une produisant du méthional/méthionol, l'autre du DMDS/DMTS. Deux nouveaux composés soufrés volatils ont également été détectés : la 2-méthyl-tétrahydrothiophène-3-one et le 1,3-oxothiane. Concernant les bactéries, elles produisent sur cystéine seule ou méthionine seule les CSV majeurs du catabolisme de la méthionine (DMDS, DMTS, DMQS et des thioesters). En ce qui concerne les mélanges de méthionine-cystéine, la production de CSV est plus ou moins réduite selon la concentration de cystéine ajoutée. Cet effet correspond certainement à une dégradation réduite de la méthionine consécutive à l'ajout de cystéine. Bien que cet effet demeure souche dépendant, des modifications du profil des CSV produits ont été observées dans tous les cas. Chez les bactéries, nous avons obtenu une production accrue des polysulfures DMTS et DMQS, parallèlement à la diminution de la production de thioesters. Chez les levures, on observe une diminution de la concentration de méthional/méthionol et de thioesters, mais sans augmentation de la production des polysulfures. Une faible concentration des formes solubles et réactives de l'H2S (HS- et S2-) dans le milieu de culture acide utilisé pour les levures pourrait expliquer ce résultat. Des essais de flairage ont montré que l'addition de faibles concentrations de cystéine, en présence de méthionine, assure la production de notes aromatiques globalement équilibrées et proches de celles d'un fromage à pâte molle croûte lavée bien affiné. Ainsi, dans un contexte fromager, nous pouvons raisonnablement supposer que l'H2S produit par le catabolisme de la cystéine ne participerait pas à la modification du profil de CSV en début d'affinage, à cause du caractère acide du caillé pendant cette période. Toutefois, l'augmentation du pH, résultat du développement des levures déacidifiantes, peut augmenter la réactivité de l'H2S qui, avec la production simultanée de méthanethiol par le catabolisme de la méthionine des bactéries d'affinage, pourrait ainsi favoriser un meilleur équilibre entre les polysulfures et les thioesters. Ainsi, la co-production de ces molécules soufrées par les levures et les bactéries d'affinage pourrait favoriser le développement d'un arôme équilibré de type fromage affiné.

Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.

In this study poplar trees have been examined under different stress conditions. Apart from the detailed descriptions above two main conclusions might be drawn: i) A small plant like Arabidopsis thaliana is highly susceptible to stress situations that might become life-threatening compared to a tree that has extremely more biomass at its disposal. Such an organism might be able to compensate severe stress much longer than a smaller one. It seems therefore reasonable that a crop like Arabidopsis reacts earlier and faster to a massive threat. ii) In poplar both tested stress responses seemed to be regulated by hormones. The reactions to abiotic salt stress are mainly controlled by ABA, which also has a strong impact upon cold and drought stress situations. The term commonly used for ABA is “stress hormone” and is at least applicable to all abiotic stresses. In case of herbivory (biotic stress), jasmonic acid appears to be the key-player that coordinates the defence mechanism underlying extrafloral nectary and nectar production. Thus the presented work has gained a few more insights into the complex network of general stress induced processes of poplar trees. Future studies will help to understand the particular role of the intriguing indirect defence system of the extrafloral nectaries in more detail. / In dieser Arbeit wurden Pappelbäume unter verschiedenen Stressbedingungen untersucht. Zusammenfassend und zusätzlich zu den obigen Beschreibungen lassen sich zwei Schlussfolgerungen ziehen: i.) Eine kleine Pflanze wie Arabidopsis ist viel empfindlicher für Stresssituationen, die möglicherweise lebensbedrohlich werden könnten, im Gegensatz zu einem Baum mit wesentlich grösserer Biomasse . Solch ein Organismus kann schwerwiegendem Stress viel länger kompensieren als ein kleinerer Organismus. Es erscheint daher sinnvoll, dass eine Pflanze wie Arabidopsis viel früher und schneller auf eine massive Bedrohung reagiert. ii.) In Pappeln scheinen beide untersuchten Arten von Stressreaktion durch Hormone reguliert zu werden. Die Reaktionen auf abiotischen Salzstress werden hauptsächlich durch ABA kontrolliert, welches auch einen starken Einfluss auf Kälte- und Trockenstressszenarien hat. Üblicherweise wird für ABA der Ausdruck "Stress-Hormon" verwendet, was zumindest für abiotischen Stress zutreffend ist. Im Fall von Herbivorie (biotischer Stress) scheint Jasmonsäure die Schlüsselrolle zu spielen, die die Abwehrmechanismen koordiniert, die den extrafloralen Nektarien und der Nektarproduktion zu Grunde liegt. Demzufolge hat die vorliegende Arbeit ein paar neue Einsichten in das komplexe Netzwerk der Stress-induzierten Prozesse der Pappel ermöglicht. Zukünftige Studien werden dazu beitragen die besondere Rolle des faszinierendem indirektem Abwehrmechanismus der extrafloralen Nektarien en detail zu verstehen.

Tendo em vista a importância dos compostos bioativos (CBAs) para a promoção da saúde, foram desenvolvidos, a partir de cruzamentos do tomate cereja com espécies selvagens, os tomates laranja (rico em &#946;-caroteno) e roxo (rico em antocianinas), por meio da técnica de introgressão de alelos. Diante disso, o objetivo deste trabalho foi caracterizar o perfil de compostos bioativos e voláteis dos tomates enriquecidos e avaliar a estabilidade e metabolização de flavonoides do tomate roxo durante digestão in vitro e em modelo animal. Os tomates foram caracterizados quanto ao conteúdo de compostos fenólicos totais; capacidade antioxidante por DPPH e ORAC; ácidos orgânicos; açúcares solúveis; perfil de carotenoides por CLAE/DAD; flavonoides por CLAE/DAD e LC/ESI/MS/MS e compostos voláteis por CG/MS. Avaliou-se ainda a estabilidade dos flavonoides da casca do tomate roxo por simulação da digestão in vitro, utilizando o Simulator of the Human Intestinal Microbial Ecosystem (SHIME), bem como a formação de AGCC por GC-MS, e excreção em ratos Wistar, com posterior identificação dos compostos fenólicos por LC/Q-TOF/MS. O tomate roxo apresentou aumento no conteúdo de fenólicos totais, capacidade antioxidante e vitamina C, com destaque para casca. A rutina foi o principal flavonol identificado em todos os frutos, e na casca do tomate roxo foi encontrado alto teor de petunidina (p-coumaroil)-rutinosídeo-hexosídeo, além da superexpressão de outros flavonoides como a quercetina-3-O-rutinosídeo e kaempferol. Não houve alteração no perfil de flavonoides do fruto laranja. Este, por sua vez, apresentou acúmulo de &#946;-caroteno, importante pró-vitamina A, ao passo que o tomate roxo também teve seus conteúdos de &#946;-caroteno e licopeno aumentados. Os frutos apresentaram perfil de compostos voláteis diferentes entre si, o que foi relacionado à degradação dos diferentes CBAs característicos de cada um. O extrato fenólico da casca de tomate roxo, submetido à digestão in vitro, se manteve estável na primeira porção, relativo às condições estomacais. Contudo, o conteúdo de flavonoides apresentou redução significativa (p<0,05) nas porções que simulam as condições do duodeno e do colón, com a formação de catabólitos pela ação da microbiota intestinal e/ou pela degradação química espontânea. Foi observado o aparecimento de novos ácidos fenólicos não presentes inicialmente na matriz, dentre eles o ácido 3-O-metilgálico e o ácido homovanílico, supostamente derivados da degradação da petunidina e da quercetina, respectivamente. Houve aumento na produção total de AGCC, com excessão do butirato. Na urina dos animais foram detectados diversos outros compostos fenólicos derivados do metabolismo de fase II, dentre eles o ácido hipúrico e o 3-O-metilcatecol. Nas fezes foram identificados cerca de metade dos compostos presentes na fermentação in vitro. Dessa forma, o melhoramento convencional pode ser uma alternativa para o enriquecimento, com CBAs, de alimentos amplamente consumidos pela população, como o tomate. Além disso, durante a passagem pelo trato gastrointestinal, os flavonoides presentes na casca do tomate roxo sofrem intensa degradação pela microbiota intestinal, com formação de catabólitos com reconhecido potencial benefício à saúde. / Considering the importance of bioactive compounds (BACs) for health promotion, the orange (&#946;-carotene-rich) and purple (anthocyanin-rich) tomatoes were developed from cherry tomato interspecific crossing with wild species, using the technique of allele introgression. The objective of this work was to characterize the profile of bioactive and volatile compounds of enriched tomatoes, and to evaluate the stability and metabolism of purple tomato\'s flavonoids during in vitro and in vivo digestion. The tomatoes were characterized by its content of total phenolic compounds; antioxidant capacity (DPPH and ORAC); organic acids; soluble sugars; carotenoids (HPLC/DAD); flavonoids (HPLC/DAD and LC/ESI/MS/MS) and volatile compounds (GC/MS). The stability of the flavonoids from purple tomato peel was assessed by using the Simulator of the Human Intestinal Microbial Ecosystem (SHIME), as well as the formation of AGCC by GC-MS, and metabolism and excretion in Wistar rats, with subsequent identification of phenolic compounds by LC/Q-TOF/MS. The purple tomato showed an increase in the total phenolic content, antioxidant capacity and vitamin C, with highlight for the peel. The rutin was the main flavonol identified in all fruits, and it was found high content of petunidin (p-coumaryl)-rutinoside-hexoside in the purple tomato peel, in addition to overexpression of other flavonoids such as quercetin-3-O-rutinoside and kaempferol. There was no change in the flavonoid profile of the orange fruit. This one, in turn, presented accumulation of &#946;-carotene, important pro-vitamin A, while the purple tomato also showed an increase in its &#946;-carotene and lycopene contents. The fruits presented different volatile compounds profile among them, which was related to the degradation of the different BACs composition of each one. In the in vitro digestion, the phenolic extract of the purple tomato peel remained stable in the first portion, relative to the stomach conditions. However, the content of flavonoids presented a significant reduction (p<0.05) in the portions simulating the duodenum and colon, with the formation of catabolites by the action of intestinal microbiota and/or spontaneous chemical degradation. It was observed the appearance of new phenolic acids that was not initially present in the matrix, among them 3-O-methylgalic acid and homovanilic acid, supposedly derived from the degradation of petunidin and quercetin, respectively. There was an increase in the total production of SCFAs, with the exception of butyrate. In the urine of the animals several other phenolic compounds derived from phase II metabolism were detected, among them hippuric acid and 3-O-methylcatechol. About half of the compounds present in the in vitro fermentation were identified in the feces. Conventional breeding may be an alternative for the enrichment, with BACs, of foods that are widely consumed by the population, such as tomatoes. In addition, during the passage through the gastrointestinal tract, the flavonoids present in the purple tomato peel are severely degraded by the intestinal microbiota, with formation of catabolites with recognized potential health benefit.

Na busca por compostos voláteis para utilização no manejo comportamental de Diaphorina citri Kuwayama (Hemiptera: Liviidae), a resposta destes insetos foi avaliada frente às substâncias liberadas por plantas de laranja, Citrus sinensis (L.) Osbeck, variedade \'Pêra\', enxertadas sobre limão-cravo, C. limonia Osbeck, sadias vs sintomáticas para Huanglongbing (HLB). Voláteis destas plantas, bem como seus extratos foram testados em olfatômetro \'Y\' e analisados por GC-MS. Somente fêmeas foram atraídas, tanto para os voláteis quanto para os extratos, e preferencialmente os de plantas doentes. Foram encontrados 47 compostos em extratos de plantas sadias e doentes, dos quais 11 [hexanal; &alpha;-tujeno; &alpha;-pineno; sabineno; &beta;-mirceno; &alpha;-terpineno; limoneno; linalol; composto 37 (não identificado); &beta;-elemeno e &beta;-copaeno] presentes em maior quantidade nos extratos de plantas doentes, sendo que 3 desses compostos (sabineno, linalol e &beta; -elemeno) foram majoritários nos extratos de ambas as plantas, doentes e sadias. Esses três compostos, bem como uma substância padrão para atração (salicilato de metila), foram testados em diferentes concentrações e misturas em laboratório, casa-de-vegetação e campo. O efeito destas substâncias foi dependente de sua concentração e, embora limoneno tenha alterado a resposta comportamental das fêmeas, apenas salicilato de metila e linalol foram atraentes. Em laboratório, a mistura desses dois compostos apresentou efeito sinérgico na atração de fêmeas e, em casa-de-vegetação, a adição de linalol junto a plantas de citros aumentou a atratividade das mesmas para insetos adultos, sugerindo importante participação desses compostos no processo de seleção hospedeira pelo inseto. Estes resultados acrescentam novas informações para a busca de um atraente para D. citri visando o manejo comportamental do inseto vetor das bactérias Liberibacter, associadas ao HLB, a mais importante doença dos citros no mundo. / With the aim of searching for volatile compounds to use in behavioral management of Diaphorina citri Kuwayama (Hemiptera: Liviidae), the response of these insects was assessed against the substances released by sweet orange [Citrus sinensis (L.) Osbeck], variety \'Pera\', grafted on Rangpur (C. limonia Osbeck), healthy and Huanglongbing (HLB) symptomatic plants. Plant volatiles as well as plant extracts were tested in Y-tube olfactometer assays and analyzed by GC-MS. Only females were attracted to plant volatiles and extracts and they preferred those from HLB-infected plants. A total of 47 compounds was found in the extracts from healthy and infected plants, from which 11 [hexanal; &alpha;-thujene; &alpha;-pinene; sabinene; &beta;- myrcene; &alpha;-terpinene; limonene; linalool; compound #37 (not identified); &beta;-elemene; and &beta;-coapene] were present in higher amounts in infected plant extracts. Three of these volatiles (sabinene, linalool and &beta;-elemene) represented major compounds in both infected and healthy plant blend extracts. These three compounds, as well as a standard substance used for attraction (methyl salicylate), were tested in different concentrations and mixtures in laboratory, greenhouse and field. The effect of these substances was dependent on its concentration and, although limonene changed female behavioral response, only methyl salicylate and linalool were attractive. In the laboratory, the mixture of these two compounds showed a synergistic effect in attracting females and, in greenhouse, the addition of linalool to citrus plants increased the attractiveness of plants to adult insects, suggesting an important role for these compounds in the host selection process by the insect. These results provide novel information about attractants to D. citri with the aim of developing a behavioral management approach of the insect vector for Liberibacter, bacteria associated to HLB, the most important citrus disease worldwide.

Dans ce travail, une configuration laminaire stratifiée est utilisée afin d’étudier les caractéristiques de la pyrolyse et de l’oxydation du charbon pulvérisé dans un mélange de flux réactif à la fois dans les conditions atmosphériques conventionnelles et dans des conditions de combustion enrichie en oxygène. Deux diagnostics optiques, la spectroscopie d’émission de flamme et la mesure de l’émission spontanée sont utilisés pour caractériser la structure de la flamme. Les profiles de concentration de trois radicaux excités, OH*, CH* and C*2 sont mesurés et analysés.Des simulations 1-D utilisant la cinétique détaillée y compris des sous-mécanismes de OH*, CH* and C*2 et de combustion de charbon sont effectuées et comparées avec des données expérimentales. La comparaison qualitative a montré que la configuration numérique actuelle était appropriée pour la prédiction des émissions de OH*, CH* and C*2. Les résultats prédits par l’approche numérique diffèrent avec les modifications apportées aux sous-modèles de charbon et aux paramètres cinétiques. Le modèle de pyrolyse et les matières volatiles semblent jouer des rôles plus importants. / In the present work, a laboratory-scale laminar strained configuration is used to investigate the characteristics of pulverized coal devolatilization and oxidation in a mixture of CH4/O2/N2 reactive flow both in conventional air conditions and in oxygen-enriched combustion conditions. Two optical diagnostics, Flame Emission Spectroscopy and measurement of spontaneous emission, are employed for the characterization of flame structure. The spatial concentration evolution of three excited radicals, OH*, CH*and C*2 , are measured and analyzed.1-D simulations using detailed gas-phase kinetics including OH*, CH*, and C*2 sub-mechanisms and coal combustion submodels are performed and compared with experimental data. Qualitative comparison with experiments showed that the current numerical configuration was suitable for the prediction of OH*, CH* and C*2 emission. The predicted results differed with changes to the coal sub-models and kinetic parameters. The devolatilization model and volatile matters seem to play more important roles.