Heavy-ion collisions are a powerful tool to study hot and dense QCD matter, the so-called Quark Gluon Plasma (QGP). Since heavy quarks (charm and beauty) are dominantly produced in the early stages of the collision, they experience the complete evolution of the system. Measurements of electrons from heavy-flavour hadron decay is one possible way to study the interaction of these particles with the QGP. With ALICE at LHC, electrons can be identified with high efficiency and purity. A strong suppression of heavy-flavour decay electrons has been observed at high $p_{m T}$ in Pb-Pb collisions at 2.76 TeV. Measurements in p-Pb collisions are crucial to understand cold nuclear matter effects on heavy-flavour production in heavy-ion collisions. The spectrum of electrons from the decays of hadrons containing charm and beauty was measured in p-Pb collisions at $\\sqrt = 5.02$ TeV. The heavy flavour decay electrons were measured by using the Time Projection Chamber (TPC) and the Electromagnetic Calorimeter (EMCal) detectors from ALICE in the transverse-momentum range $2 < p_ < 20$ GeV/c. The measurements were done in two different data set: minimum bias collisions and data using the EMCal trigger. The non-heavy flavour electron background was removed using an invariant mass method. The results are compatible with one ($R_ \\approx$ 1) and the cold nuclear matter effects in p-Pb collisions are small for the electrons from heavy-flavour hadron decays. / Colisões de íons pesados relativísticos é uma ferramenta poderosa para se estudar o plasma de quarks e glúons (QGP). Quarks pesados ({\\it charm} e {\\it beauty}) são produzidos nos estágios iniciais da colisão e participam da evolução completa do sistema. Medidas de elétrons provenientes de quarks pesados é uma das possíveis formas de se estudar a interação destas partículas com o QGP. Utilizando o detetor ALICE do LHC, elétrons podem ser identificados com alta eficiência e boa pureza. Uma forte supressão de elétrons provenientes de quarks pesados foi observada em alto $p_$ em colisões de Pb-Pb a 2.76 TeV. Medidas do mesmo observável em colisões p-Pb são cruciais para se entender os efeitos da matéria nuclear fria na produção de tais partículas. O espectro de elétrons provenientes de hádrons que contêm {\\it charm} ou {\\it beauty} foi medido em colisões p-Pb a $\\sqrt = 5.02$ TeV. Os elétrons foram identificados utilizando o {\\it Time Projection Chamber} (TPC) e o {\\it Electromagnetic Calorimeter} (EMCal) do detetor ALICE, no intervalo de momento transversal de $2 < p_ < 20$ GeV/c. As medidas foram realizadas utilizando dois diferentes conjunto de dados: colisões de mínima tendenciosidade ({\\it minimum bias (MB)}) e colisões tomadas utilizando o trigger do EMCal. Os elétrons de fundo foram removidos utilizando um método de massa invariante. Os resultados são compatíveis com a unidade ($R_ \\approx$ 1) e os efeitos da matéria nuclear fria são pequenos para elétrons provenientes de quarks pesados.

Heavy-ion collisions are a powerful tool to study hot and dense QCD matter, the so-called Quark Gluon Plasma (QGP). Since heavy quarks (charm and beauty) are dominantly produced in the early stages of the collision, they experience the complete evolution of the system. Measurements of electrons from heavy-flavour hadron decay is one possible way to study the interaction of these particles with the QGP. With ALICE at LHC, electrons can be identified with high efficiency and purity. A strong suppression of heavy-flavour decay electrons has been observed at high $p_{m T}$ in Pb-Pb collisions at 2.76 TeV. Measurements in p-Pb collisions are crucial to understand cold nuclear matter effects on heavy-flavour production in heavy-ion collisions. The spectrum of electrons from the decays of hadrons containing charm and beauty was measured in p-Pb collisions at $\\sqrt = 5.02$ TeV. The heavy flavour decay electrons were measured by using the Time Projection Chamber (TPC) and the Electromagnetic Calorimeter (EMCal) detectors from ALICE in the transverse-momentum range $2 < p_ < 20$ GeV/c. The measurements were done in two different data set: minimum bias collisions and data using the EMCal trigger. The non-heavy flavour electron background was removed using an invariant mass method. The results are compatible with one ($R_ \\approx$ 1) and the cold nuclear matter effects in p-Pb collisions are small for the electrons from heavy-flavour hadron decays. / Colisões de íons pesados relativísticos é uma ferramenta poderosa para se estudar o plasma de quarks e glúons (QGP). Quarks pesados ({\\it charm} e {\\it beauty}) são produzidos nos estágios iniciais da colisão e participam da evolução completa do sistema. Medidas de elétrons provenientes de quarks pesados é uma das possíveis formas de se estudar a interação destas partículas com o QGP. Utilizando o detetor ALICE do LHC, elétrons podem ser identificados com alta eficiência e boa pureza. Uma forte supressão de elétrons provenientes de quarks pesados foi observada em alto $p_$ em colisões de Pb-Pb a 2.76 TeV. Medidas do mesmo observável em colisões p-Pb são cruciais para se entender os efeitos da matéria nuclear fria na produção de tais partículas. O espectro de elétrons provenientes de hádrons que contêm {\\it charm} ou {\\it beauty} foi medido em colisões p-Pb a $\\sqrt = 5.02$ TeV. Os elétrons foram identificados utilizando o {\\it Time Projection Chamber} (TPC) e o {\\it Electromagnetic Calorimeter} (EMCal) do detetor ALICE, no intervalo de momento transversal de $2 < p_ < 20$ GeV/c. As medidas foram realizadas utilizando dois diferentes conjunto de dados: colisões de mínima tendenciosidade ({\\it minimum bias (MB)}) e colisões tomadas utilizando o trigger do EMCal. Os elétrons de fundo foram removidos utilizando um método de massa invariante. Os resultados são compatíveis com a unidade ($R_ \\approx$ 1) e os efeitos da matéria nuclear fria são pequenos para elétrons provenientes de quarks pesados.

Benzaldehyde (BZA), a biologically derived high-value molecule used in the flavour and fragrance industry for its characteristic almond-like aroma, has also found use in nutraceutical, pharmaceutical, cosmetics, agrochemical, and dye applications. Although, nature-identical BZA is most commonly produced by chemical synthesis, biologically derived BZA, whether by plant material extraction or via microbial biocatalysts, commands much higher prices. The bioproduction of high value molecules has often been characterized by low titers as results of substrate and product inhibition. The current work examined a variety of process strategies and the implementation of a solid-liquid bioreactor partitioning system with continuous integrated pervaporation to enhance the bioproduction of BZA using Pichia pastoris. Previous work on two-phase partitioning bioreactors (TPPBs) for the biotransformation of BZA using Pichia pastoris has had limitations due to long fermentation times and unutilized substrate in the immiscible polymer phase, contributing to complications for product purification. To reduce fermentation times, a mixed methanol/glycerol feeding strategy was employed and reduced the time required for high-density fermentation by 3.5 fold over previous studies. Additionally, because BZA and not the substrate benzyl alcohol (BA) had been found to be significantly inhibitory to the biotransformation reaction, a polymer selection strategy based on the ratio of partition coefficients (PCs) for the two target molecules was implemented. Using the polymer Kraton D1102K, with a PC ratio of 14.9 (BZA:BA), generated a 3.4 fold increase in BZA produced (14.4 g vs. 4.2 g) relative to single phase operation at more than double the volumetric productivity (97 mg L-1 h-1 vs. 41 mg L-1 h-1). This work also confirmed that the solute(s) of interest were taken up by polymers via absorption, not adsorption. BZA and BA cell growth inhibition experiments showed that these compounds are toxic to cells and it was their accumulation rather than low enzyme levels or energy (ATP) depletion that caused a reduction in the biotransformation rate. For this reason, the final strategy employed to enhance the bioproduction of benzaldehyde involved in situ product removal by pervaporation using polymer (Hytrel 3078) fabricated into tubing by DuPont, Canada. This aspect was initiated by first characterizing the custom-fabricated tubing in terms BZA and BA fluxes. The tubing was then integrated into an in situ pervaporation biotransformation and was shown to be effective at continuous product separation, using 87.4% less polymer by mass in comparison to polymer beads in conventional TPPB operation, and improved overall volumetric productivity by 214% (245.9 mg L-1 h-1 vs. 115.0 mg L-1 h-1) over previous work producing BZA. / Thesis (Master, Chemical Engineering) -- Queen's University, 2013-09-28 17:41:45.458

La souche Carnobacterium maltaromaticum LMA 28, isolée d’un fromage à pâte molle, possède des propriétés physiologiques non conventionnelles pour une bactérie lactique. Sa croissance en TSB-YE et en lait traduisent son exigence nutritionnelle en facteurs de croissance facilement assimilables et sa faible vitesse de production d’acide lactique à partir de glucose, lactose, fructose et saccharose. Le galactose n’est pas métabolisé et lors de l’hydrolyse du lactose n’est pas excrété dans le milieu de culture. Les caillés lactiques sont obtenus après des durées d’incubation non compatibles avec les cadences industrielles. De plus, ils présentent une texture très friable. La numération et l’identification de cette souche, en vue de suivre son comportement dans une matrice fromagère, ont été optimisées par la mise au point du milieu de culture sélectif CM, à l’aide de plan d’expériences, et par la technique de PCR. Le comportement de C. maltaromaticum LMA 28 a été comparé à ceux de deux souches lactiques d’intérêt technologique Lc. lactis DSM 20481 et S. thermophilus INRA 302, dans une large gamme de températures (3 à 37 °C) et de pH (5,2- 8,0). Des essais en co-culture, associant cette souche avec Lc. lactis DSM 20481 ou avec S. thermophilus INRA 302, ont montré que la production d’acide lactique était due à la croissance de la souche lactique traditionnelle. Cependant C. maltaromaticum LMA 28, souche lente, n’est pas inhibée par cette acidification. L’aptitude fromagère de C. maltaromaticum LMA 28 a été testée lors de deux fabrications de fromages à pâte molle. Inoculée à différents niveaux de population, elle a été mise en évidence à tous les stades de la fabrication. Présente à une concentration très faible dans le lait de fabrication, elle devient une flore lactique dominante après l’affinage et le stockage en réfrigération. Cette aptitude technologique est en relation avec son caractère psychrotrophe et sa faculté à se développer activement à des pH alcalins. Son « alimentarité », testée par la production d’amines biogènes, a montré des niveaux nuls ou très faibles en tyramine et en histamine, comme avec S. thermophilus INRA 302 et avec Lc. lactis DSM 20481. L’optimisation de sa production de flaveurs maltées a été abordée sur milieu TSB-YE et sur lait, supplémentés avec de la leucine, de l’isoleucine ou de la valine. La production de 3-méthylbutanal est la plus importante. Les analyses sensorielles des fromages contenant des niveaux de population importants (108-109 ufc.g-1) de C. maltaromaticum LMA 28 n’ont pas permis de mettre en évidence cet arôme. Présente dans de nombreux fromages français AOC ou non AOC, cette espèce opportuniste, de statut GRAS, pourrait être considérée comme un auxiliaire de fabrication intéressant, car elle permet un ralentissement du vieillissement des fromages, en évitant notamment l’apparition de flaveurs désagréables. Cette flore lactique psychrotrophe pourrait être retenue comme flore bactérienne d’affinage / The C. maltaromaticum LMA 28 bacteria strain, isolated from soft cheese, was observed to possess non conventional lactic bacteria physiological properties. Its growth in TSB YE medium and milk was found to be characterised by the requirements for easily assimilated growth nutrients and a low kinetic rate of lactic acid production from glucose, lactose, fructose and sucrose. In addition, it was found to not metabolise galactose or not excrete it during the hydrolysis of lactose. In the process of milk fermentation, it not only took an unusually long duration but produced products of fragile texture. In order to eventually determine the behaviour of this strain in the process of cheese-making, a selective culture medium CM was developed using an experimental design and PCR techniques for its isolation and identification. The behaviour of C. maltaromaticum LMA 28 was compared with that of two strains of lactic bacteria of technological interest namely Lc. lactis DSM 20481 and S. thermophilus INRA 302, within a wide temperature range (3 to 37°C) and of pH (5.2 – 8.0). Tests carried out in co-culture associating this strain with Lc. lactis DSM 20481 or with S. thermophilus INRA 302 showed that the lactic acid production was due mainly to the growth of the traditional lactic strain. In the process, the C. maltaromaticum LMA 28 slow strain was observed not to be inhibited by acidification. The cheese-making potential of C. maltaromaticum LMA 28 was evaluated in the process of two soft cheese manufactures. Inoculated at various levels of population, it was observed to be present at all manufacturing stages. Generally present at very weak concentrations in the starting milk, it becomes a dominant lactic flora following ripening and refrigeration storage. This technological aptitude is in relation with its psychrotrophic character and its ability to actively develop in alkaline medium. Its “alimentarity”, tested by its ability to produce biogenic amines, showed zero or very low levels in tyramine and histamine, as in the case of S. thermophilus INRA 302 and Lc. lactis DSM 20481. The optimization of its malted flavour production capacity was carried out on a TSB-YE medium and on milk supplemented with leucine, isoleucine or valine. In this process the production of 3-méthylbutanal was observed to be the most abundant product while cheese containing high levels (108-109 ufc.g-1) of C. maltaromaticum LMA 28 did not exhibit this flavour. This notwithstanding, the presence of this species of GRAS status in many French AOC and non AOC cheeses could be considered as an interesting auxiliary in cheese manufacturing process since it tends to slow down the aging process and thereby retard the development of unpleasant flavours. In this respect this strain of psychotrophic lactic bacteria could be retained as a flora for cheese ripening process

Les désintégrations B->l l sont supprimées d'hélicité et se produisent à travers des courants neutres changeant la saveur. Elles sont donc extrêmement rares dans le modèle standard (MS). La physique au-delà du MS pourrait donc modifier substantiellement la valeur des rapports d'embranchement prédits par le MS. Ces prédictions étant très précises, mesurer leur valeurs constitue un test incontournable du MS.Les travaux présentés dans cette thèse ont contribué à l'établissement de la première évidence de la désintégration Bs->mu mu avec LHCb. Une méthode statistique a ete développée pour extraire et combiner les limites sur les rapports d'embranchement et calculer la signifiance des signaux. A partir de ces acquis statistiques, une méthode originale a été conçue pour re-optimiser les catégories dans lesquelles les candidats sont classés améliorant ainsi la sensibilité de l'analyse de 14%. D'autre part, une étude sur la phénoménologie des interférences entre le mélange de saveur des mésons Bs et leur désintégration a mis en évidence une subtile dépendance de l'analyse avec le modèle physique considéré. La prise en compte de cette dépendance permet de contraindre plus fortement la nouvelle physique. Enfin une méthode de reconstruction topologique inclusive des évènements a été développée et testée, notamment pour reconstruire les candidats Bs->tau tau avec tau->pi pi pi nu. / The B->l l decays are helicity suppressed and process through flavour changing neutral currents. They are extremely rare in the standard model (SM). Thus physics beyond SM could modify their branching ratio up to an observable level. As the theoretical predictions are very precise, these modes are golden channels to probe the SM.The works presented in this thesis have contributed to the establishment of the first evidence of the Bs->mu mu decay. A statistical method has been built to extract and combine limits on the decays branching fraction and to compute signals significance. On the basis of this work, an original method was developed to re-optimised the categories used to classified the candidates which improved the analysis sensitivity by 14%. A study of the interplay between the flavour mixing of the Bs and its decay demonstrated that the analysis results are model dependent. Accounting for this dependency allows to improve constraints on new physics. Finally, an inclusive topological reconstruction was developed and tested in particular to reconstruct Bs->tau tau candidates with tau->pi pi pi nu.

O objetivo desta pesquisa foi identificar os voláteis importantes para o aroma da carne de frangos suplementados com diferentes concentrações de beta-ácidos do lúpulo. Para isso, 1440 frangos de corte Cobb 500 foram alimentados ad libitum durante 42 dias com dietas basais suplementadas com 0 (controle negativo), 30, 60 e 120 mg kg-1 de &beta;- ácidos do lúpulo. Após 42 dias de experimento, os animais foram abatidos e o músculo peitoral maior (peito do frango) foi retirado, separado do tecido conjuntivo, da pele e da gordura subcutânea. Os filés de peito foram imediatamente congelados a -80 °C até o momento das análises. Nos filés foi determinado o perfil de ácidos graxos por cromatografia gasosa acoplada a detector de ionização em chama. E a carne dos animais suplementados com 30 mg kg-1 de &beta;-ácidos foi a que apresentou a maior quantidade dos ácidos graxos insaturados de cadeia longa araquidônico (C20:4-n6) e docosaexaenoico (C22:6-n3), cujas propriedades antioxidantes e anti-inflamatórias são benéficas para saúde humana. Para a caracterização dos voláteis da carne assada foi desenvolvido e otimizado um procedimento de extração dos voláteis da carne por microextração em fase sólida de headspace (HS-SPME) e cromatografia gasosa acoplada à espectrometria de massa (GC-MS). Para isso, foram testados cinco tipos de fibras comerciais de SPME quanto a sua capacidade de extração dos voláteis da carne assada de frango e, para fibra que apresentou maior capacidade de extração (CAR/PDMS), foram otimizadas as condições de temperatura e tempo de extração por meio de delineamento composto central rotacional. As condições ótimas de extração foram: temperatura de extração de 81°C e tempo de extração de 45 min. Foram identificados 70 compostos voláteis na carne assada de frango por GC-MS majoritariamente aldeídos, alcanos, álcoois, ésteres e pirazinas. A análise de componentes principais (PCA) foi capaz de separar as amostras em função da suplementação com beta ácidos, o que indica que os diferentes níveis de suplementação podem originar diferentes voláteis na carne assada. O tratamento controle negativo (0 mg kg-1 de &beta;-ácidos) foi caracterizado principalmente por aldeídos e ácidos como octanal, decanal, benzaldeido e ácido n-hexanóico, o tratamento com 30 mg kg-1 de &beta;-ácidos foi caracterizado por pirazinas (2, 6 - dimetil prirazina e 3- etil, 2, 5 dimetil pirazina), o tratamento com 60 mg kg-1 de &beta;-ácidos foi caracterizado por uma maior quantidade de álcoois, aldeídos e furanos (hexanal, 1-octen-3 ol e pentilfurano), enquanto que o tratamento com 120 mg kg-1 de &beta;-ácidos foi caracterizado pela presença docomposto 2- metil pentanal.<br /> / The aim of this research was to identify volatiles that are important for the aroma of chicken meat supplemented with different concentrations of hops &beta;-acids. To carry out this research, 1440 Cobb 500 broilers were fed ad libitum during 42 days with basal diets supplemented with 0 (negative control), 30, 60, 120 and 240 mg kg-1 of hops &beta;-acids. After 42 days, the animals were slaughtered and the pectoralis major muscle (chicken breast) was removed, separated from the conjunctive tissue, the skin, and the subcutaneous fat. The breast fillets were immediately frozen at -80° C until the time of analysis. The fatty acid profile in the steaks was determined by gas chromatography with flame ionization detector (GC-FID). The meat of the animals supplemented with 30 mg kg-1 of &beta;-acids presented the highest amount of long-chain unsaturated fatty acids such as arachidonic acid (C20:4-n6) and docosaexaenoico (C22:6-n3), which have antioxidant and anti-inflammatory properties benefical to human health. For the characterization of the roasted meat volatiles, an extraction procedure was developed and optimized by headspace solid-phase microextraction (HS-SPME) and gas chromatography coupled to mass spectrometry (GC-MS). Six different types of SPME commercial fibers were tested regarding their ability to extract volatiles from chicken roasted meat, and to the fiber that showed the highest extraction capacity (DVB/CAR/PDMS), temperature and time of extraction were optimized through central composite design. The optimum extraction conditions were: extraction temperature of 81 °C and extraction time 45 minutes. It was possible to characterize 70 volatiles in the volatile fraction of roasted chicken meat by GC-MS, The majority of them were aldehydes, alkanes, alcohols, esters and pyrazines. The Principal Component Analysis (PCA) was able to separate the samples according to the supplementation with hops &beta;-acids, which indicates that different levels of supplementation may yield different volatile compounds on roasted chicken meat. The negative control treatment (0 mg kg-1 of &beta;-acids) was characterized mainly by aldehydes and acids like octanal, decanal, benzaldehyde and n-hexanoic acid, the treatment with 30 mg kg-1 of &beta;-acids was characterized by pyrazines (2,6 - dimethyl pyrazine, and 3-ethyl, 2,5- dimethyl pyrazine, the treatment with 60 mg kg-1 of &beta;-acids was characterized by a major quantity of alcohols, aldehydes and furans (hexanal, 1-octen-3-ol and pentylfuran), whereas the treatment with 120 mg kg-1 of &beta;-acids was characterized by the presence of 2 the compound 2-methyl pentanal.

O objetivo desta pesquisa foi identificar os voláteis importantes para o aroma da carne de frangos suplementados com diferentes concentrações de beta-ácidos do lúpulo. Para isso, 1440 frangos de corte Cobb 500 foram alimentados ad libitum durante 42 dias com dietas basais suplementadas com 0 (controle negativo), 30, 60 e 120 mg kg-1 de &beta;- ácidos do lúpulo. Após 42 dias de experimento, os animais foram abatidos e o músculo peitoral maior (peito do frango) foi retirado, separado do tecido conjuntivo, da pele e da gordura subcutânea. Os filés de peito foram imediatamente congelados a -80 °C até o momento das análises. Nos filés foi determinado o perfil de ácidos graxos por cromatografia gasosa acoplada a detector de ionização em chama. E a carne dos animais suplementados com 30 mg kg-1 de &beta;-ácidos foi a que apresentou a maior quantidade dos ácidos graxos insaturados de cadeia longa araquidônico (C20:4-n6) e docosaexaenoico (C22:6-n3), cujas propriedades antioxidantes e anti-inflamatórias são benéficas para saúde humana. Para a caracterização dos voláteis da carne assada foi desenvolvido e otimizado um procedimento de extração dos voláteis da carne por microextração em fase sólida de headspace (HS-SPME) e cromatografia gasosa acoplada à espectrometria de massa (GC-MS). Para isso, foram testados cinco tipos de fibras comerciais de SPME quanto a sua capacidade de extração dos voláteis da carne assada de frango e, para fibra que apresentou maior capacidade de extração (CAR/PDMS), foram otimizadas as condições de temperatura e tempo de extração por meio de delineamento composto central rotacional. As condições ótimas de extração foram: temperatura de extração de 81°C e tempo de extração de 45 min. Foram identificados 70 compostos voláteis na carne assada de frango por GC-MS majoritariamente aldeídos, alcanos, álcoois, ésteres e pirazinas. A análise de componentes principais (PCA) foi capaz de separar as amostras em função da suplementação com beta ácidos, o que indica que os diferentes níveis de suplementação podem originar diferentes voláteis na carne assada. O tratamento controle negativo (0 mg kg-1 de &beta;-ácidos) foi caracterizado principalmente por aldeídos e ácidos como octanal, decanal, benzaldeido e ácido n-hexanóico, o tratamento com 30 mg kg-1 de &beta;-ácidos foi caracterizado por pirazinas (2, 6 - dimetil prirazina e 3- etil, 2, 5 dimetil pirazina), o tratamento com 60 mg kg-1 de &beta;-ácidos foi caracterizado por uma maior quantidade de álcoois, aldeídos e furanos (hexanal, 1-octen-3 ol e pentilfurano), enquanto que o tratamento com 120 mg kg-1 de &beta;-ácidos foi caracterizado pela presença docomposto 2- metil pentanal.<br /> / The aim of this research was to identify volatiles that are important for the aroma of chicken meat supplemented with different concentrations of hops &beta;-acids. To carry out this research, 1440 Cobb 500 broilers were fed ad libitum during 42 days with basal diets supplemented with 0 (negative control), 30, 60, 120 and 240 mg kg-1 of hops &beta;-acids. After 42 days, the animals were slaughtered and the pectoralis major muscle (chicken breast) was removed, separated from the conjunctive tissue, the skin, and the subcutaneous fat. The breast fillets were immediately frozen at -80° C until the time of analysis. The fatty acid profile in the steaks was determined by gas chromatography with flame ionization detector (GC-FID). The meat of the animals supplemented with 30 mg kg-1 of &beta;-acids presented the highest amount of long-chain unsaturated fatty acids such as arachidonic acid (C20:4-n6) and docosaexaenoico (C22:6-n3), which have antioxidant and anti-inflammatory properties benefical to human health. For the characterization of the roasted meat volatiles, an extraction procedure was developed and optimized by headspace solid-phase microextraction (HS-SPME) and gas chromatography coupled to mass spectrometry (GC-MS). Six different types of SPME commercial fibers were tested regarding their ability to extract volatiles from chicken roasted meat, and to the fiber that showed the highest extraction capacity (DVB/CAR/PDMS), temperature and time of extraction were optimized through central composite design. The optimum extraction conditions were: extraction temperature of 81 °C and extraction time 45 minutes. It was possible to characterize 70 volatiles in the volatile fraction of roasted chicken meat by GC-MS, The majority of them were aldehydes, alkanes, alcohols, esters and pyrazines. The Principal Component Analysis (PCA) was able to separate the samples according to the supplementation with hops &beta;-acids, which indicates that different levels of supplementation may yield different volatile compounds on roasted chicken meat. The negative control treatment (0 mg kg-1 of &beta;-acids) was characterized mainly by aldehydes and acids like octanal, decanal, benzaldehyde and n-hexanoic acid, the treatment with 30 mg kg-1 of &beta;-acids was characterized by pyrazines (2,6 - dimethyl pyrazine, and 3-ethyl, 2,5- dimethyl pyrazine, the treatment with 60 mg kg-1 of &beta;-acids was characterized by a major quantity of alcohols, aldehydes and furans (hexanal, 1-octen-3-ol and pentylfuran), whereas the treatment with 120 mg kg-1 of &beta;-acids was characterized by the presence of 2 the compound 2-methyl pentanal.

The food industry could potentially benefit from using pervaporation, a membrane process, to concentrate flavours. This research aimed to investigate its application for concentrating flavours in dairy process streams. Pervaporation experiments were carried out at a range of operating conditions, using hydrophobic membranes. The feed mixtures were either aqueous model solutions of dairy flavour compounds (acids, esters and ketones), complex model mixtures containing flavour compounds plus non-volatile dairy components, or real dairy products. Flavour compound enrichment factors ranged from below one to above 30, with esters and ketones being concentrated more effectively than acids. Thus, the flavours could be partially fractionated based on their chemical structure. The permeation of acids was reduced by approximately 50% when the feed pH was increased to near their p Ka values. For flavour compounds with lower molecular weights than approximately 1 20 g mol- I , permeation was controlled mainly by sorption i n the membrane; for larger compounds it was controlled mainly by diffusion through the membrane. The mass transfer of each flavour compound increased with temperature, following an Arrhenius-like relationship. The activation energy was a function of each compound's heat of sorption, its molecular weight, and the elastic modulus of the membrane. The activation energy was also related to the Arrhenius preexponential factor. Thus, fluxes could be estimated through empirical correlations. The non-volatile feed composition was an important factor influencing the pervaporation performance. Milk protein isolate (4% w/v) or lactose (6% or 1 2% w/v) bound with the flavour compounds in the feed, thus lowering the enrichment of sorption-controlled compounds. Milk fat (up to 38% w/v, in the form of cream ) reduced the enrichment of all the flavour compounds tested. Esters and ketones became unavailable for pervaporation as they partitioned into the fat phase; acids remained mainly in the aqueous phase, but their permeation was reduced because the added cream increased the feed pH. Experiments with real dairy products showed that pervaporation could be used to concentrate diacetylin starter distillate, and to selectively recover short-chain esters from ester cream. Of these two products, starter distillate is the more promising for use as a pervaporation feed stream.

Flavour is a factor that has a large influence on meat quality. Pastoral flavour that results from the grazing of pasture is an undesirable characteristic of meat flavour for consumers more accustomed to meat produced by grain and concentrate feeding systems. In New Zealand there is a reliance on grazing systems for sheep meat production, however the resulting meat flavour is one factor that impedes the increase of sheep meat exports to discerning markets. Correlation of chemical analyses to sensory evaluations of sheep meat has identified that a high concentration of indole and skatole in the fat is associated with pastoral flavours. Indole and skatole are formed in the rumen from the microbial fermentation of tryptophan. New Zealand pasture is high in protein, which is both highly soluble and rapidly degraded in the rumen. As such, pasture diets provide a rich and ready source of tryptophan for the formation of indole and skatole in the rumen. Condensed tannins are known to slow the degradation of protein in the rumen. Therefore, one of the objectives of this study was to establish if dietary condensed tannin can reduce the ruminal biogenesis of indole and skatole and consequently, ameliorate pastoral flavour in sheep meat. White clover usually comprises up to 30% of the botanical composition of pastures in New Zealand, is highly degradable in the rumen and likely to result in a high availability of tryptophan in the rumen for conversion to indole and skatole. Therefore, another objective of this study was to determine if feeding white clover gave a significant increase in the formation of indole and skatole in the rumen compared to perennial ryegrass and if this has an effect on pastoral flavour in meat. These hypotheses were tested using a series of in vitro rumen fermentations that incorporated the use of fresh forages (Chapter 3 and 6). In vivo experiments were utilised to assess rumen formation of indole and skatole with different forages (Chapter 4) and to assess effects of dietary condensed tannin (CT; Chapter 5 and 7). Meat and fat samples from lambs used in Chapters 5 and 7 underwent sensory evaluation to determine if forage or CT treatments were having an effect on the fat odour or meat flavour. From the in vitro and in vivo experiments of (Chapter 3, 4, 6 and 7) it was calculated that the formation of indole and skatole with perennial ryegrass is generally only 6-41% of that formed with white clover. A higher concentration of indole and skatole was also observed in the blood plasma of lambs that were fed white clover compared to those that were fed perennial ryegrass (Chapter 7) and white clover gave an overall more intense flavour in the meat. Comparison of forages fermented in vitro (Chapter 3) showed that with forage legumes of a higher CT concentration, such as Lotus pedunculatus (98 gCT kg-1 DM) and Dorycnium rectum (122 gCT kg-1 DM), the indole and skatole formed was only 7-21% of that formed with white clover. With forages of an intermediate CT concentration such as sulla (Hedysarum coronarium) and Lotus corniculatus the indole and skatole concentration formed was 53-68% of that of white clover. From in vitro rumen fermentation of mixtures of white clover and Lotus pedunculatus it was concluded that the CT in Lotus pedunculatus was not reacting with the protein in white clover. Fermentation of fresh white clover in the presence of an increasing concentration of added CT extract showed that at a higher CT, indole and skatole formation were reduced to low levels. It was inferred that this was due to optimal protein binding and the availability of free condensed tannin to bind other sources of protein, including rumen microbes. However, in vivo dosing with a CT extract resulted in only a small reduction in rumen indole and skatole concentration. This indicated that when CT was dosed into the in vivo rumen of lambs fed fresh forages the CT probably passed from the rumen before adequate protein release from the forage had taken place. Thus, in the grazing situation it will be optimal to provide CT in planta to maximise protein binding and this, in combination with the high CT concentration needed (approximately 80 gCT kg-1 DM), makes Lotus pedunculatus or Dorycnium rectum the prime candidates for further grazing trials into pastoral flavour amelioration using CT forages. Grazing Lotus corniculatus (40 gCT kg-1 DM) in a field experiment resulted in a lower rumen and blood plasma and fat concentration of indole and skatole in comparison to the grazing of perennial ryegrass/white clover pasture. However, a change in the pastoral odour of the fat was not perceived by the sensory panel when comparing fat samples from lambs that had grazed Lotus corniculatus and perennial ryegrass/white clover pasture. The concentration of skatole in the body fat was less variable in the lambs that had grazed Lotus corniculatus and resulted in no lambs with a high outlying concentration (>100 ng g-1) of indole and skatole. This finding holds some potential for reducing pastoral flavour for consumers sensitive to high indole and skatole concentration in the fat. When condensed tannin was dosed to lambs that were fed white clover or perennial ryegrass in the form of a grape seed extract the intermittent supply of CT slightly reduced indole and skatole formation in the rumen and reduced the plasma concentration of indole and skatole. Flavour assessment of meat from the lambs fed white clover or perennial ryegrass with or without CT suggested that CT reduced the intensity of pastoral flavours. However, there were minimal effects on indole and skatole concentration in the body fat. It was possible that other pastoral flavour related compounds derived from the degradation of amino acids, in addition to indole and skatole that were measured, were having an effect on the meat flavour. It was concluded that dietary condensed tannin is able to reduce the formation of indole and skatole in the rumen and can alter the sensory attributes of sheep meat including reducing pastoral flavours. A higher CT concentration present within the forage plant (approximately 80 g kg-1 DM) will be best to minimise indole and skatole formation in the rumen and reduce pastoral flavours in the meat. Further research is required to confirm this in the grazing situation. Feeding white clover results in a greater rumen biogenesis of indole and skatole compared to perennial ryegrass and therefore, may be the primary contributor to pastoral flavours when ruminants graze conventional pastures. Further research is required to evaluate the flavour attributes that result from feeding white clover to meat producing ruminants in the New Zealand grazing situation.

Heating milk to high temperatures such as 140 ºC, as used in ultra high temperature (UHT) processing, causes physical and chemical changes in the milk. The production of a cooked flavour is a major change which reduces consumer acceptance of the UHT milk. It has been correlated with the formation of volatile sulphur compounds (VSCs) that result from milk proteins, principally the whey proteins β-lactoglobulin, containing the the sulphur amino acids cystine, cysteine and methionine. The VSCs in milk, whose concentrations are in the parts per billion to parts per million range, are highly reactive, easily oxidised, and sensitive to heat during thermal processing and analysis; this makes them a challenge to analyse. A sensitive method based on gas chromatography with pulsed flame photometric detection coupled with headspace sampling by solid phase microextraction (SPME/GC/PFPD) was developed to detect these compounds in commercial UHT milk and to investigate their production and disappearance during heating and storage. The SPME/GC/PFPD procedure was optimised using different extraction time (15 min, 30 min, & 60 min) – temperature (30 oC, 45 oC & 60 oC) combinations with CAR/PDMS fibre to obtain maximum sensitivity. A short extraction time (15 min) at low temperature (30 oC) was chosen to provide high sensitivity for detecting all VSCs in UHT milk without introducing artefactual VSCs. The extraction method and GC run time (16 min) make this method simple and fast. Nine VSCs were detected in commercial indirectly processed UHT milk, skim and whole. These are hydrogen sulphide (H2S), carbonyl sulphide (COS), methanethiol (MeSH), dimethyl sulphide (DMS), carbon disulphide (CS2), dimethyl disulphide (DMDS), dimethyl sulphoxide (DMSO), dimethyl sulphone (Me2SO2) and dimethyl trisulphide (DMTS). An additional unknown compound was detected but could not be identified by GC/MS because its concentration was below the detection limit of the MS detector. The concentrations of H2S, DMS and DMTS were higher than their threshold values indicating their importance in milk flavour, especially cooked flavour. Several attempts have been made to reduce the cooked flavour in UHT milk. In the current research, the use of hydrogen peroxide (H2O2) to oxidise the VSCs and thereby reduce cooked flavour was investigated. H2O2 is used as a milk preservative and is generally recognised as safe (GRAS) in USA. Several concentrations of H2O2 (0.001%, 0.005%, 0.01%, 0.02% & 0.03%) were added to milk to assess its effects on VSCs and on whey proteins denaturation in UHT milk. H2O2 effectively reduced the concentration of all VSCs, except DMDS which was increased, presumably by oxidation of MeSH. H2S was completely oxidised or reduced below its threshold value. Low concentrations of H2O2 (0.001% & 0.005%) had no effect on, or decreased, the extent of denaturation of β-lactoglobulin when added after or before processing, respectively. Some UHT plants use severe heating conditions, leading to high levels of denaturation of whey proteins, particularly β-Lg, the main source of the VSCs in milk. Correlations between heat severity, β-Lg denaturation and individual VSC generation were investigated in milk batch-heated at 80 oC and 90 oC, and UHT milk processed at 120-150 oC. In accordance with previous reports, β-Lg was more heat-sensitive than α-La. Only five VSCs were detected. The concentrations of H2S and MeSH correlated well with denaturation of β-Lg and α-La. DMS concentration correlated well with β-Lg in UHT milk but not in the batch-heated milk. CS2 did not show a good correlation with heat intensity and appeared to plateau out after a certain level of heating. Conversely, COS and MeSH seemed to require a certain minimum amount of heat before generation commenced; this corresponded to denaturation of β-Lg above 49% and 89% respectively at 80 oC. The higher concentrations of DMS and H2S in UHT milk compared with batch-heated samples having similar degrees of denaturation suggested other possible sources for their production and the importance of the heat severity in generating them. For example, at high heat intensity, S-methylmethionine and thiamine could be sources of DMS and H2S respectively. Furthermore, in whole milk as used in this work, milk fat globule membrane proteins are another source of VSCs. The outcome of this study will help UHT manufacturers to understand the production and disappearance of the VSCs in commercial UHT milk and how to adjust the processing conditions to avoid generation of cooked flavour. Additionally, the promising results of using low concentrations of H2O2 to oxidise the VSCs will provide the industry with another means of reducing cooked flavour. Before H2O2 use is implemented in UHT processing, future studies are required to evaluate all of its effects, including sporicidal effects. Overall, this study makes a contribution to finding a solution to the cooked flavour problem in UHT milk, thereby increasing market share of this milk in countries such as Australia, the UK and North America where cooked flavour is the main barrier to its consumer acceptance.