Dans ce projet, la bactérie du rumen des bovins Actinobacillus succinogenes souche 130Z est utilisée pour fermenter le lactose et le lactosérum pour en produire de l'acide succinique qui a des larges applications industrielles. Le but de ce travail est de déterminer les conditions optimales de fermentation afin de produire l'acide succinique à des grandes concentrations et avec des bonnes valeurs de rendement et de productivité. Les paramètres à optimiser en mode de fermentation batch sont les concentrations initiales du lactose (25, 50 et 75 g/1) et d'extrait de levure (7,5, 10 g/1), et le taux de C02 (0.16, 0.32 et 0.80 vvm) injecté dans le milieu de fermentation. Par la suite, produire l'acide succinique dans ces conditions optimales en mode fed batch à partir du lactose et du lactosérum. En mode de fermentation batch, les résultats obtenus montrent que les concentrations optimales d'extrait de levure et du lactose sont respectivement 7.5 et 25 g/1 et le taux de COT le plus adéquat pour la production de l'acide succinique est 0.32 wm. Tout d'abord, il n'y a pas de différences pour les deux concentrations de levure étudiées. En ce qui concerne la concentration initiale du lactose, et pour les différents taux de CO2 étudiés, les valeurs de rendement et de productivité obtenues pour une concentration initiale du lactose égale à 25 g/1 sont supérieures à celles de 50 et 75 g/1. En effet, des concentrations initiales de lactose supérieures à 25 g/1 exercent une inhibition sur la croissance bactérienne et par conséquent la consommation du lactose et la production de l'acide succinique. La concentration maximale d'acide succinique obtenue à partir de 25 g/1 du lactose, 7.5 g/1 d'extrait de levure et 0.32 vvm de CO2 est égale à 18.7 g/1, les valeurs de rendement et de productivité sont respectivement 76% et 1.52 g/l/h. Dans les mêmes conditions que la fermentation du lactose, la fermentation batch du lactosérum (concentration initiale 33.5 g/1) a donné 13.86 g/1 d'acide succinique, un rendement de 61% et une productivité de 0,97 g/l/h. Les valeurs des rapports massiques AS/AA et AS/AF (2.43 et 3.96 respectivement) obtenus au cours de la fermentation batch du lactosérum sont inférieurs à ceux obtenus dans le cas du lactose (8.47 et 14.6 respectivement). Ceci montre que la fermentation du lactosérum favorise le développement de la biomasse, et la production des sous-produits acides de la fermentation (acides acétique et formique) par rapport à la fermentation du lactose. Les résultats de la fermentation fed batch du lactose et du lactosérum montrent que l'acide succinique a pu être produit à des grandes concentrations (environ 55 et 50.5 g/1 respectivement) comparativement à la fermentation batch. Dans le cas du lactosérum, la fermentation fed batch a permis une augmentation de rendement et de la productivité (67% et 1.28 g/l/h à 24h). Mais dans le cas du lactose, les valeurs de rendement et de la productivité sont similaires à celle de la fermentation batch (70% et 1.52g/l/h à 24h). Comme dans le cas de la fermentation batch, plus de biomasse et de sous-produits de fermentation sont produits en fermentation fed batch du lactosérum par rapport à ceux du lactose. Les différents acides organiques (acide succinique, acétique et formique) testés seuls ou en combinaison exercent une inhibition de la croissance bactérienne contre les deux souches E. coli et L. ivanovii. À faible concentration C4 (1.1, 0.8 et 0.35 mg/ml d'acide succinique, acétique et formique respectivement), le mélange (AS+AA+AF) a permis d'inhiber efficacement la croissance bactérienne par rapport aux associations deux à deux (AS+AA, AS+AF et AA+AF). Le mélange d'acides a permis 73 et 92 % d'inhibition à 12h pour E. coli et L. ivanovii respectivement. Ceci permet de conclure qu'il ya un effet synergique entre les trois acides organiques testés.

Este trabalho, propõe nova tecnologia para tratamento de efluentes gerados pelas indústrias de laticínios. Atualmente este tipo de efluente, quando tratado, utiliza o processo biológico para reduzir a carga orgânica, contudo, este método, algumas vezes, não garante a remoção completa dos compostos orgânicos. Assim, é sugerido a utilização de argila bentonitica sódica para a adsorção da lactose como tratamento terciário do efluente da indústria de laticínios. A comprovação deste evento assim como sua quantificação foi realizada através de duas técnicas distintas: análise térmica e difração de raios-X. Os resultados obtidos foram positivos, pois comprovou-se não só a adsorção como também a absorção do material orgânico, no caso, a lactose na argila avaliada. Verificou-se a capacidade da argila bentonitica de Wyoming ab-adsorver até 50% da lactose. Assim, este trabalho oferece alternativa para o tratamento terciário do efluente das indústrias de laticínios. / This work considers new technology for effluent treatment generated by the dairy industries. Currently this type of effluent, when treated, uses the biological process to reduce the organic load, however, this method, some times, does not guarantee the complete removal of organic composites. Thus, the sodium bentonite use is suggested for the adsorption of the lactose as tertiary treatment of the effluent one of the dairy industry. The evidence of this event as well as its quantification was carried through two distinct techniques: thermal analysis and x-ray diffraction. The gotten results had been positive, therefore the adsorption not only proved the absorption of the organic material, in the case, the lactose in the evaluated clay. It was verified capacity of the Wyoming bentonite of to ab-adsorption up to 50% of the lactose. Therefore, this work offers alternative for the tertiary effluent treatment of the dairies industries.

Cette thèse concerne le développement d’approches spectroscopiques infrarouge et Raman exaltées de surface: la spectroscopie infrarouge exaltée de surface (SEIRAS) combinée avec une cellule de perfusion et la spectroscopie Raman exaltée de surface (SERS) couplée avec l’électrochimie. Dans le cadre du premier projet, différentes protéines ont été étudiées : lactose perméase (LacY), complexe I et IM30. Nous avons déterminé le pKa de Glu325 dans LacY sauvage et dans différents mutants portant des mutations dans le centre actif de translocation des protons. Sauvage complexe I a été oxydé avec différents agents oxydants et réduit avec NADH. Spectres différentiels correspondants ont été analysés. Des changements conformationnels dans la protéine IM30, induits par la présence des ions Mg2+, ont été observés.Dans le cadre du deuxième projet, une cellule spectroélectrochimique contenant une grille d’or a été adaptée pour étudier des protéines redox actives. Cette grille d’or sert à la fois de substrat SERS et d’électrode de travail. Cyt c, Hb et Mb ont d'abord été utilisés pour valider la configuration, puis l'approche a été étendue pour étudier une protéine membranaire. / This thesis concerns the development of surface-enhanced infrared and Raman spectroscopic approaches: surface-enhanced infrared absorption spectroscopy (SEIRAS) combined with perfusion cell and surface-enhanced Raman spectroscopy (SERS) combined with electrochemistry. Within the first project different proteins were studied: Lactose Permease (LacY), complex I and IM30.The pKa of Glu325 in LacY WT and in different mutants carrying mutations in the proton translocation active center was determined. WT complex I was oxidized with different oxidizing agents and reduced with NADH. Corresponding redox-induced conformational changes were studied. The evidence was given that Mg2+ ions induce conformational changes in the protein IM30.Within the second project the spectroelectrochemical cell containing gold grid electrode was adopted for the studies of redox active proteins. This gold grid serves both as working electrode and as SERS active substrate. First Cyt c, Hb and Mb were used to validate the setup and then the approach was extended to study a membrane protein.

Este trabalho, propõe nova tecnologia para tratamento de efluentes gerados pelas indústrias de laticínios. Atualmente este tipo de efluente, quando tratado, utiliza o processo biológico para reduzir a carga orgânica, contudo, este método, algumas vezes, não garante a remoção completa dos compostos orgânicos. Assim, é sugerido a utilização de argila bentonitica sódica para a adsorção da lactose como tratamento terciário do efluente da indústria de laticínios. A comprovação deste evento assim como sua quantificação foi realizada através de duas técnicas distintas: análise térmica e difração de raios-X. Os resultados obtidos foram positivos, pois comprovou-se não só a adsorção como também a absorção do material orgânico, no caso, a lactose na argila avaliada. Verificou-se a capacidade da argila bentonitica de Wyoming ab-adsorver até 50% da lactose. Assim, este trabalho oferece alternativa para o tratamento terciário do efluente das indústrias de laticínios. / This work considers new technology for effluent treatment generated by the dairy industries. Currently this type of effluent, when treated, uses the biological process to reduce the organic load, however, this method, some times, does not guarantee the complete removal of organic composites. Thus, the sodium bentonite use is suggested for the adsorption of the lactose as tertiary treatment of the effluent one of the dairy industry. The evidence of this event as well as its quantification was carried through two distinct techniques: thermal analysis and x-ray diffraction. The gotten results had been positive, therefore the adsorption not only proved the absorption of the organic material, in the case, the lactose in the evaluated clay. It was verified capacity of the Wyoming bentonite of to ab-adsorption up to 50% of the lactose. Therefore, this work offers alternative for the tertiary effluent treatment of the dairies industries.

FundaÃÃo de Amparo à Pesquisa do Estado do Cearà / O ensaio foi realizado no Setor de Suinocultura do Centro de CiÃncias AgrÃrias do Departamento de Zootecnia da Universidade Federal do CearÃ, com o objetivo de avaliar o desempenho zootÃcnico, os indicadores do metabolismo do nitrogÃnio, o bem-estar animal e o custo de produÃÃo de leitÃes no prÃodo de creche, submetidos a dietas à base de sorgo-soja enriquecidas com caseÃna + lactose isoladas. O experimento teve a duraÃÃo de 42 dias, sendo dividido em duas fases experimentais, a saber: fase 1(21-42 dias) e fase 2 (42 a 63 dias). Foram utilizados 40 animais de linhagem comercial, desmamados com idade aproximada de 21 dias, apresentando um peso mÃdio de 4,76kg. O delineamento experimental utilizado foi em blocos ao acaso, com 4 tratamentos e 5 repetiÃÃes, apresentando 2 animais por repetiÃÃo. Foi realizado um desdobramento fatorial 2X2, sendo 2 cereais energÃticos (milho e sorgo) e 2 suplementos lÃcteos (leite desnatado em pà e caseÃna + lactose). A comparaÃÃo entre as mÃdias foi realizada pelo teste de Duncan a 5%. As dietas experimentais foram isoenergÃticas, isoprotÃicas e isonutrientes para lisina e met+cis. Na fase 1 foi utilizado 21 % de PB e 3350 kcal de EM ⁄ kg. e na fase 2, 18,5 % de PB e 3250kcal de EM ⁄ kg. As dietas experimentais foram em nÃmero de 4 por fase, da seguinte forma: T1 (milho +LDP), T2 (milho+caseÃna +lactose), T3 (sorgo+LDP) e T4 (sorgo+caseÃna+lactose). Foi concluÃdo que a substituiÃÃo do milho pelo sorgo granÃfero e a inclusÃo da lactose + caseÃna à viÃvel quanto ao desempenho zootÃcnico. A utilizaÃÃo do sorgo e da caseÃna+lactose nas dietas para leitÃes desmamados nÃo ocasionou diferenÃas significativas para os indicadores do metabolismo do nitrogÃnio nas duas fases experimentais. Os tratamentos nÃo influenciaram os indicadores do bem-estar animal. NÃo foram registradas interaÃÃes significativas (P>0,05) entre os alimentos energÃticos e os alimentos lÃcteos, nas fases 1 e 2 do perÃodo de creche, para o desempenho zootÃcnico e para os indicadores do bem-estar animal. A melhor resposta econÃmica para a produÃÃo de leitÃes no perÃodo de creche foi obtida com a dieta contendo sorgo + caseÃna +lactose (T4). / The research was developed in the Division of Swine Pro duction, Department of Animal Science, Agricultural Science Center, Federal Un iversity of CearÃ, with the objective of evaluating the animal performance, the occurrence diarrhea, the nitrogen metabolism indicators, animal well-being, and the production cost of piglets submitted to diets containing sorghum-soybean me al and isolated casein+lactose. The assay had the duration of 42 days and it was divided in two phases: 1 (21-42 days of age) and 2 (42-63 days of age ) during the nursery period. The experiment used a total of 40 piglets of a commercial line, weaned at 21 days of age (average weight of 4,76 kg). The exper iment followed a randomized blocks design, with 4 treatments, 5 repetitio ns and 2 animals per repetition, unfolded in a factorial 2 x 2 design, comp osed by two energetic feeds (corn and sorghum) and two milk products (dried skim milk a nd casein + lactose). Mean values were compared through the Duncan's tests 5 %. The diets were isoenergetics, isoproteics and isonutritives for lysine and methionine + cystine. In phase 1, a level of 21% crude protein (CP) and 3350 kcal ME was used and in phase 2, a level of 18,5 % crude protein (CP) and 32 50 kcal ME was used. The experimental diets were in number of 4 for phase: T 1 (corn+ dried skim milk), T 2 (corn + casein + lactose), T 3 (sorghum + dried skim milk) and T 4 (sorghum + casein + lactose). The use of sorghum and casein + lactose in weaned pig diets did not cause significant differences for nitrogen met abolism indicators, in both phases of assay. The treatments did not influence the w ell-being indicators. Related to animal performance and well-being no signi ficant interactions were registered (P>0,05) among the factors, during phases 1 a nd 2 of the nursery xxi period. The best economical answer for production of pi glets in the nursery period was obtained with the diet containing sorghum + casein + lactose (T4).

Orientador: Carlos de Oliveira Paiva Santos / Coorientadora: Selma Gutierrez Antonio / Banca: Marlus Chorilli / Banca: Vinícius Danilo Nonato Bezzon / Banca: Flavio Machado de Souza Carvalho / Banca: Alexandre Urbano / Resumo: O refinamento de estruturas cristalinas pelo método de Rietveld (MR) consiste em ajustar um modelo estrutural a uma medida de difração. Essa é uma ferramenta eficiente para identificação e quantificação de estruturas polimórficas presentes em fármacos e excipientes. Uma forma avançada do método é o refinamento sequencial por Rietveld (RSR) que visa, a partir de um conjunto de difratogramas de uma mesma amostra, estudar o comportamento do material em função de uma variável externa (e.g. temperatura, pressão, tempo ou ambiente químico). No presente trabalho, com o objetivo de estudar as transições polimórficas e as expansões/contrações dos parâmetros de cela unitária (PCU) dos insumos farmacêuticos: espironolactona (SPR), lactose monoidratada (LACMH) e lactose anidra (LACA), empregou-se o RSR em medidas obtidas em diferentes temperaturas. O RSR foi eficiente para que os PCU fossem refinados até temperaturas próximas ao ponto de fusão dos materiais. Após o RSR, a partir da análise matemática dos PCU obtidos, foram propostas funções que regem a tendência desses parâmetros quando submetidos à variação de temperatura. Com essas funções modelaram-se os PCU em uma outra modalidade de refinamento, o refinamento paramétrico por Rietveld (RPR), assim, os PCU seguem a modelagem imposta pelas equações obtidas via RSR. O RPR mostrou-se mais eficiente nas análises, o que evitou perda de fases ou problemas de ajustes, resultando assim em informações mais precisas do sistema. Embora o RSR e R... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The crystal structural refinement by the Rietveld method (MR) consists of fitting a structural model to a diffraction measure. This is an efficient tool for identification and quantification of polymorphic structures present in drugs and excipients. An advanced way to use this method is the Sequential Rietveld Refinement (RSR), which aims, from a set of data of the same sample, to study the behavior of the material as a function of an external variable (e.g. temperature, pressure, time or chemical environment). In the present work, with the objective of studying the polymorphic transitions and the expansions / contractions of the unit cell parameters (PCU) of the pharmaceutical ingredients: spironolactone (SPR), lactose monohydrate (LACMH) and anhydrous lactose (LACA), the RSR in measurements obtained at different temperatures. The RSR was efficient so that the PCU were refined to temperatures close to the melting point of the materials. After the RSR, from the mathematical analysis of the obtained PCU, functions were proposed that govern the trend of these parameters when submitted to the temperature variation. With these functions the PCU were modeled in another modality of refinement, the Parametric Rietveld Refinement (RPR), thus, the PCU follow the modeling imposed by the equations obtained via RSR. The RPR was more efficient in the analyzes, which avoided loss of phases or problems of adjustments, resulting in more accurate information of the system. Although RSR and RP... (Complete abstract click electronic access below) / Doutor

Carbon-bonded alumina filters and their binders, lactose, tannin and CarboresP, were investigated by Raman spectroscopy. Special emphasis was placed on the pyrolysis study of the binders. In situ measurements were performed on the tannins gallic acid, ellagic acid and tannic acid to determine the pyrolysis temperatures and products. Furthermore, the binder samples fired in a reducing atmosphere in a coke bed were analyzed by Raman spectroscopy and their transition from an amorphous carbon system to nanocrystalline graphite was observed. The influence of different binders on the carbon-bound alumina filters was studied, as well as the influence of different additives. However, no significant difference was observed between samples with different binder compositions or with additives. In addition, Raman measurements on the spinel MgAlON indicate an increased disorder of the structure due to the incorporated nitrogen.

No / The current work was undertaken to assess suitability of liquid crystalline phase for engineering of lactose crystals and their utility as a carrier in dry powder inhalation formulations. Saturated lactose solution was poured in molten glyceryl monooleate which subsequently transformed into gel. The gel microstructure was analyzed by PPL microscopy and SAXS. Lactose particles recovered from gels after 48 h were analyzed for polymorphism using techniques such as FTIR, XRD, DSC and TGA. Particle size, morphology and aerosolisation properties of prepared lactose were analyzed using Anderson cascade impactor. In situ seeding followed by growth of lactose crystals took place in gels with cubic microstructure as revealed by PPL microscopy and SAXS. Elongated (size approximately 71 mum) lactose particles with smooth surface containing mixture of alpha and beta-lactose was recovered from gel, however percentage of alpha-lactose was more as compared to beta-lactose. The aerosolisation parameters such as RD, ED, %FPF and % recovery of lactose recovered from gel (LPL) were found to be comparable to Respitose(R) ML001. Thus LC phase (cubic) can be used for engineering of lactose crystals so as to obtain particles with smooth surface, high elongation ratio and further they can be used as carrier in DPI formulations.

Orientador: Dirlei Antonio Berto / Banca: Jacinta Diva Gomes Ferrugem / Banca: José Roberto Sartori / Banca: Silvia Maria Alves Gomes / Banca: Valdomiro Shigueru Miyada / Resumo: Para avaliar os efeitos da suplementação dietética de maltodextrina em substituição a lactose para leitões dos 21 aos 51 dias de idade, foram utilizados 120 animais, distribuídos em um delineamento experimental de blocos ao acaso com arranjo fatorial 2x4 (duas dietas: simples e complexa e níveis de maltodextrina substituindo a lactose: 0,0%; 33,5%; 66,5% e 100,0%). Foram avaliados o consumo diário de ração (CDR), o ganho diário de peso (GDP) e a conversão alimentar (CA) em dois períodos pósdesmame (0-15 dias e 0-30 dias). Não houve interação entre os níveis de maltodextrina e as dietas para as variáveis de desempenho. Os leitões que consumiram as dietas complexas apresentaram maior GDP (P = 0,016) no período de 0 a 15 dias e melhor CA nos períodos de 0 a 15 dias (P = 0,010) e de 0 a 30 dias (P = 0,020) pós-desmame. Não foram observados efeitos dos níveis de maltodextrina sobre o CDR e GDP nos dois períodos e na CA no período de 0 a 15 dias. O aumento do nível de maltodextrina na dieta dos leitões determinou efeito quadrático na CA no período de 0 a 30 dias (Ŷ = 1,530000 + 0,002287X + 0,000022X2; R2 = 0,64). As rações contendo somente maltodextrina em sua composição proporcionaram melhor resultado econômico. A maltodextrina pode substituir totalmente a lactose nas dietas pré-iniciais e iniciais, simples ou complexas, sem afetar o desempenho de leitões dos 21 aos 51 dias de idade. / Abstract: One hundred and twenty piglets were used to evaluate the effects of dietary supplementation of maltodextrin as a replacement of lactose for weaned piglets from 21 to 51 days of age, in a randomized complete block design, according to a 2x4 factorial (two diet types: simple or complex; and levels of maltodextrin as a replacement of lactose: 0.0%, 33.5%, 66.5% and 100,0%). The daily feed intake (DFI), daily weight gain (DWG) and feed conversion (FC) were measured. No interaction between maltodextrin levels and diet type was observed. The pigs fed complex diets showed higher DWG from 0 to 15 days (P = 0.016) and better FC from 0 to 15 days (P = 0.010) and from 0 to 30 days (P = 0.020) post-weaning period. No effect of maltodextrin levels on DWG or DFI was observed from 0 to 15 days or from 0 to 30 days; on FC from 0 to 15 days. Maltodextrin showed a quadratic effect on FC from 0 to 30 days (Ŷ = 1.53000 + 0.002287X + 0.000022X2; R2 = 0.64). Diets containing only maltodextrin provided the best economical results. The maltodextrin can fully replace lactose in simple or complex pre-starter or starter diets without affecting performance weanling pigs from 21 and 51 days of age. / Doutor

Cette thèse porte sur le problème fondamental du mottage des poudres suite aux mécanismes de transition de phase. Le projet vise à étudier l'impact des facteurs intrinsèques (structure moléculaire des matériaux, propriétés physiques et/ou physicochimiques, etc.) ou des facteurs environnementaux (conditions de stockage ou paramètres de procédé) sur la stabilité de la structure des poudres. Plus précisément, notre étude a mis en évidence le rôle prépondérant du phénomène de cristallisation et des transitions entre les différents polymorphes du lactose. L'accent a été mis sur le rôle des phénomènes de cristallisation et de la transition de phase dans l'apparition du mottage des poudres de lactose. Deux cas ont particulièrement retenu notre attention: (1) des poudres de lactose monohydrate contenant une fraction de particules amorphes et (2) des échantillons de poudre anhydre composés des anomères α et β du lactose. Dans les deux cas, le mottage a été induite par l'exposition des échantillons à l'air humide, soit dans un dispositif de sorption dynamique de vapeur (SPS), soit par des tests accélérés utilisant deux appareils conçus et réalisés dans notre laboratoire (CLAIR & OLAF). Nos résultats ont montré que, dans les deux cas, la principale cause de prise en masse était la formation de lactose monohydrate, qui est la forme la plus stable parmi tous les polymorphes de lactose. Cependant, les mécanismes élémentaires, les étapes limites et la cinétique du processus de transformation étaient différents dans chaque cas. Les paramètres les plus déterminants étaient l’humidité relative et la température alors que la pression n’a pas eu d’effet significatif. La résistance mécanique des échantillons mottés était étroitement liée au taux et à la cinétique de cristallisation. Enfin, des simulations numériques basées sur la méthode des éléments discrets (DEM) de la résistance mécanique des échantillons mottés ont été réalisées. Le modèle permet de décrire le comportement des échantillons mottés soumis à des contraintes mécaniques de compression ou de traction. / This PhD study focuses on the fundamental problem of powder caking due to phase transition mechanisms. The project aims to study the impact of intrinsic factors (molecular structure of materials, physical and/or physicochemical properties, etc.) or environmental factors (storage conditions or process parameters) on the stability of the structure of powders. More precisely, our study has highlighted the preponderant role of the crystallization phenomenon and the transitions taking place between the different polymorphs of lactose. Emphasis was placed on the role of crystallization phenomena and phase transition on the advent of lactose powder caking. Two cases attracted particular attention: (1) lactose monohydrate powders containing a fraction of amorphous particles and (2) anhydrous powder samples composed of ð and anomers of lactose. In both cases, the caking was induced by exposure of the samples to moist air, either in a Dynamic Vapor Sorption device (SPS) or in accelerated caking tests using two home-made equipment (CLAIR & OLAF). Our results showed that in both cases, the main cause of caking was the formation of lactose monohydrate, which is the most stable form among all lactose polymorphs. However, the elementary mechanisms, the limiting steps and the kinetics of the transformation process were different in each case. The more influencing parameters were the relative humidity and the temperature whereas the pressure has no significant effect. The yield stress of caked samples was closely linked with crystallization extent and kinetics. Finally, numerical simulations based on Discrete Element Method (DEM) of mechanical resistance of caked samples were performed using the "beam model". The model allows describing the behavior of the caked samples subjected to compressive or tractive mechanical stresses.