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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
181

Efeito de diferentes níveis protéicos e do ácido linoléico conjugado no desempenho, custos de produção e qualidade de carne de frangos de corte / Effect of different protein and conjugated linolenic acid levels in performance, production costs and meat quality of broilers

Thiago de Campos Previero 23 October 2009 (has links)
O presente trabalho teve como objetivo estudar os efeitos da suplementação de ácido linoléico conjugado (CLA), associada à redução do nível de proteína bruta (PB) da dieta de frangos de corte. No primeiro ensaio, o período experimental transcorreu dos 21 aos 41 dias, quando 1440 machos da linhagem Ross, com mesmo peso inicial, foram distribuídos em delineamento inteiramente casualizado, em esquema fatorial 3x3, sendo três níveis de CLA (0%, 0,5% e 1,0%) e três níveis de PB (19%, 17%, 15%). Houve redução do ganho de peso e aumento da conversão alimentar apenas em função do decréscimo de PB e ambos os fatores elevaram o índice econômico mensurado. Os rendimentos de carcaça inteira e peito diminuíram proporcionalmente a PB da dieta. Houve interação entre CLA e PB para o tamanho do fígado, ambos os fatores elevaram a gordura abdominal. Em relação aos parâmetros analisados em amostras de peito, o pH elevou-se proporcionalmente, em relação a PB, as intensidades de vermelho e amarelo foram modificadas ou pela PB, ou pelo CLA e para a luminosidade houve interação. Quanto ao perfil de ácidos graxos, a PB elevou somente o ácido esteárico e o CLA aumentou os ácidos graxos saturados e reduziu os monoinsaturados. Houve incorporação crescente dos isômeros de CLA, em função da maior inclusão do produto nas dietas com 19% ou 17% de PB. Nas dietas com 15% de PB, ocorreu um limite máximo para a incorporação do CLA. No segundo experimento, utilizando 144 aves Ross e mesmo delineamento e modelo experimental, houve efeito quadrático da PB para o balanço de nitrogênio e interação entre CLA e PB para a digestibilidade da PB dietária. / The objective of this research was to study the effects of the conjugated linoleic acid, known as CLA, associated with reduction of crude protein (CP) level in broiler diets. At first assay, the period of experiment was conducted from 21 to 41 days, when 1440 male broilers from Ross line, with the same weight initial, were allocated in accordance to a completely randomized design, with factorial model 3x3, corresponding in 3 CLA inclusions levels (0%, 0,5% and 1,0%) and 3 CPs levels (19%,17%,15%). Weight gain reduction and increased feed conversion were only related to decrease of CP inclusion and both of factors, CP and CLA inclusion levels, elevated the economic index parameters. Carcass and breast meat yields decreased due to the reduction of CP addition in diets. The interaction between CLA and CP factors modified in liver size, and both elevated the abdominal fat percents. In relation to parameters analyzed in breast samples, the pH elevated proportionally to CP inclusion, the redness and yellowness were modified by CP or CLA addition and interaction of both were detected to luminosity parameter. About fatty acid composition, the addition of CP only elevated the stearic acid and CLA inclusion improved the saturated fatty acid levels and reduced the monounsaturated fatty acid levels. An improvement on incorporation of CLA isomers was verified due to more inclusion of this product in 19% or 17% CPs diets. In the case of 15% CPs diets, the incorporation of CLA isomers had a maxim limit. In the second assay, using 144 Ross line broilers with the same design and model, a quadratic effect for nitrogen balance was verified due to CP diets and an effect of interaction between CLA and CP inclusion was found to digestibility of dietary CP.
182

Efeito do tratamento de cama e de estratégias nutricionais sobre índices produtivos e qualidade de carne em frangos de corte / Poultry litter treatment and nutritional strategies effects on productive indexes and meat quality in broiler chicks

Joyce de Jesus Mangini Furlan 11 August 2017 (has links)
Objetivou-se avaliar os efeitos do uso de sulfato de alumínio, da densidade de alojamento e de estratégias nutricionais sobre índices produtivos, econômicos e qualidade de carne na produção de frangos de corte. Foram conduzidos dois experimentos, nos quais: Experimento I (EI) Objetivou-se avaliar os efeitos das doses de sulfato de alumínio [Al2(SO4)3 18 H2O] - (0, 200, 400 e 600 g/m2) no tratamento da cama aviária e da taxa de lotação (8 e 9 aves/m2). Foi avaliadas na cama, a amônia volatilizada, pH, teor de matéria-seca e nitrogênio, além do desempenho das aves, rendimento de carcaça, cortes (peito e coxa-sobrecoxa), ocorrência de lesão de peito e pododermatite e qualidade da carne (pH, cor, perdas totais por cozimento, maciez objetiva e análise sensorial). No Experimento II (EII) os objetivos foram avaliar os efeitos da inclusão dietética de fitase (1.000 FTU/kg de ração) e da redução do nível de proteína bruta (um ponto percentual) nas dietas de frangos criados em cama tratada ou não com sulfato de alumínio (1.568 g/m2). Além das análises citadas anteriormente, objetivou-se avaliar o aspecto microbiológico das carcaças de frango e propor uma estimativa econômica do poder fertilizante da cama aviária. Foi realizada a análise da viabilidade econômica do uso do sulfato de alumínio, da fitase e da redução do nível proteico da dieta na produção avícola. (EI) As doses de sulfato de alumínio e as taxas de lotação influenciaram as características da cama, reduzindo os valores de pH e minimizando a quantidade de amônia volatilizada. A melhor dose de sulfato de alumínio foi de 400 g/m2 independente da lotação adotada. As doses de sulfato de alumínio avaliadas não influenciaram o desempenho das aves, que foi afetado negativamente pelo aumento da densidade. Observou-se efeito significativo da interação sulfato de alumínio × taxa de lotação (P = 0,0094) sobre o rendimento de carcaça. O teste afetivo mostrou que o sulfato de alumínio não influenciou a aceitabilidade dos consumidores pela carne de frango. A análise economica demonstrou que a margem bruta aumentou quando a lotação foi de nove aves/m2 já que o peso do lote é maior. (EII) A aplicação do sulfato de alumínio na cama aviária reduziu os valores de pH e consequentemente a amonia volatilizada. Além disso, a baixa PB e a fitase reduziram o pH e a amônia também. O sulfato de alumínio (1.568 g/m2) reduz a emissão de amônia e as perdas de N da cama. Valorar o dejeto avícola como fertilizante orgânico permite uma melhor decisão com relação às quantidades a serem aplicadas na lavoura, promovendo benefícios econômico e ambiental. A inclusão dietética de fitase (1.000 FTU/kg de ração) influenciou características de cor da carne e melhorou sua maciez segundo a percepção de consumidores não treinados. O uso de 1.568 gramas de sulfato de alumínio por m2 diminui a margem de comercialização, onerando os custos de produção. Além disso, pode-se concluir que as diferentes estratégias nutricionais não apresentaram diferenças nas margens de comercialização, indicando a viabilidade econômica na utilização de ferramentas nutricionais para manutenção do impacto ambiental da produção avícola. / The aim of this study was to evaluate the effects of the use of aluminum sulfate, stocking density and nutritional strategies on productive, economic indexes and meat quality on poultry industry. Therefore, two experiments were conducted. Experiment I (EI) the aim of study was to evaluate the effects of aluminum sulfate doses [Al2(SO4)3·18H2O] - (0, 200, 400 e 600 g/m2) to treated poultry litter and bird densities (8 and 9 birds/m2). It was evaluated volatilized ammonia, pH values, dry matter and nitrogen content from poultry litter. Furthermore, it was evaluated live performance, carcass, breast, drumstick and thigh yield, prevalence of breast skin lesions and foot-pad dermatitis, and chicken meat quality (pH, color, shear force, cook loss and sensorial analysis). Experiment II (EII) aims evaluate the effects of aluminum sulfate to treat litter (0 or 1.568 g/m2), including phytase (1,000 FTU/kg of feed) in the diet and diets with low-crude protein (one percentage point of reduction). This study aims to evaluate the Microbiological Plate Counts on carcasses was evaluated and propose a method to value the manure in relation to its potential as fertilizer too. The economic analysis was also performed, considering the use of aluminum sulphate, phytase and diets with low-crude protein in the production of broiler chickens. The economic analysis the marketing margin increased when the density was 9/m2 because the sold broilers weight was higher. (EI) Aluminum sulfate doses and the stocking density influence poultry litter characteristics, lowering the pH values and reducing the amount of volatilized ammonia. The best dose of aluminum sulphate was 400 g/m2 regardless of the density adopted. The use of aluminum sulfate doses evaluated did not influence the broiler performance, which was negatively affected by the increase in the density. A significant effect of the interaction (P = 0.0094) was verified for carcass yield. The affective test showed that aluminum sulfate didnt influence consumers acceptability for chicken meat. The economic analysis showed that the contribution margin increased when the stocking was 9 birds/m2 since the lot weight is higher. (EII) Application of alum to the litter lowered pH values and consequently ammonia volatilization, moreover the low crude protein and phytase reduced this traits too. Aluminum sulfate (1.568 g/m2) reduces ammonia emissions and consequently nitrogen losses from litter. Valuing poultry manure as organic fertilizer allows the better decision in relation to the quantity to be applied to the crop, promoting economic and environmental benefits. It was concluded that the inclusion of phytase (1,000 FTU/kg of feed), influences chicken meat color characteristics, and improved meat tenderness in the perception of untrained panelists. The use of 1,568 grams of aluminum sulphate per m2 decreased the marketing margin, inflating production costs. In addition, it can be concluded that different nutritional strategies did not present differences in the margins of commercialization, indicating the economic feasibility in the use of nutritional tools to maintain the environmental impact of poultry production.
183

Determinação da energia interfacial de emulsões de agua em oleo pesado / Determination of interfacial energy of water in heavy oil emulsions

Karcher, Viviane 08 December 2008 (has links)
Orientador: Antonio Carlos Bannwart / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica e Instituto de Geociencias / Made available in DSpace on 2018-08-12T08:12:48Z (GMT). No. of bitstreams: 1 Karcher_Viviane_M.pdf: 1731022 bytes, checksum: 355de3e34591ff15d14ab367330328f8 (MD5) Previous issue date: 2008 / Resumo: Durante a produção de petróleo, é comum o aparecimento de água sob a forma de gotas finamente dispersas no óleo. A água pode ser oriunda de métodos de recuperação avançada e/ou do próprio reservatório (água conata). O cisalhamento turbulento produzido durante o escoamento destes fluidos através de dutos ou dispositivos, como bombas, ou até mesmo no reservatório, pode causar a formação de emulsões de água em óleo (A/O). Para os óleos pesados,estas emulsões permanecem estáveis por um período longo devido à presença de agentes emulsificantes naturais no petróleo cru. Por essa razão, a separação dessas emulsões necessita de equipamentos específicos, o que contribui para o aumento do custo do processo. O objetivo deste estudo é investigar as propriedades interfaciais de emulsões A/O compostas por água e petróleo pesado brasileiro. Para tanto, um aparato experimental foi construído com o objetivo de calcular a energia interfacial dessas emulsões. As emulsões A/O foram geradas através de um aparelho homogeneizador rotativo imerso em um vaso calorimétrico. Dois métodos foram empregados: o método calorimétrico, baseado no balanço de energia da emulsificação, e o método padrão, baseado na medida do tamanho e distribuição das gotas através da técnica de microscopia óptica. As incertezas nas medidas experimentais, em ambos os métodos, foram estudadas a fim de avaliar a viabilidade de cada um. Como principais resultados deste estudo, as magnitudes relativas dos termos do balanço de energia durante a emulsificação foram obtidas. O comportamento reológico destas emulsões também foi estudado. / Abstract: In petroleum production operations, water is commonly present within the oil phase as a finely dispersed phase. This situation originates from enhanced oil recovery methods and/or the presence of connate water inside the own reservoir. The turbulent shear associated with fluid flow during of heavy crude transportation through pipelines may cause the formation of water-in-oil emulsions (W/O). These remain stable for a long time, due the presence of naturally emulsifying agents in the crude oil phase. Therefore, emulsion separation requires specific equipments which contribute to increase the processes costs. The main purpose of this study is to investigate the interfacial properties of W/O emulsions composed by water and a Brazilian heavy crude oil. For that purpose an experimental set-up was built in order to measure the interfacial energy of the emulsions. The W/O emulsions were prepared in a calorimeter vessel by using a rotating impeller. Two methods were used, namely, the calorimetric method based on the energy balance for the emulsification and the standard method of the droplet size and distribution by means of a digital microscope. The uncertainty in experimental measurements was determined for both methods, in order to evaluate their feasibility. The main result of this research is the determination of the relative magnitudes of the different terms in the energy balance during emulsification. Results for the rheological behavior of W/O emulsions are also reported. / Mestrado / Explotação / Mestre em Ciências e Engenharia de Petróleo
184

Regressão por vetores de suporte aplicado na determinação de propriedades físico-químicas de petróleo e biocombustíveis / Support vector regression applied to the determination of physicochemical properties of petroleum and biofuels

Filgueiras, Paulo Roberto, 1982- 26 August 2018 (has links)
Orientador: Ronei Jesus Poppi / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-26T02:05:14Z (GMT). No. of bitstreams: 1 Filgueiras_PauloRoberto_D.pdf: 5218504 bytes, checksum: f307cad15b41230e15e9d018c384a91d (MD5) Previous issue date: 2014 / Resumo: O petróleo é constituído por uma mistura complexa de composição química heterogênea. Sua completa avaliação envolve cerca de 700 ensaios físico-químicos, consumindo de 10 a 70 litros de amostra em aproximadamente 1 ano de análises. Visando reduzir tempo e quantidade de amostra, nesta Tese, métodos espectroscópicos aliados à Regressão por Vetores de Suporte (SVR) foram aplicados na determinação de algumas propriedades físico-químicas de petróleos e biocombustíveis. Diferentes abordagens para otimização e interpretação dos modelos SVR foram desenvolvidas: técnica para determinar as variáveis mais importantes na construção dos modelos, estimativa de intervalos de confiança nas previsões e avaliação de tendências nos resíduos. Foram realizadas quatro aplicações com diferentes técnicas instrumentais. A primeira aplicação foi direcionada a interpretação dos modelos SVR construídos a partir de espectros de infravermelho médio (MIR) na determinação da gravidade API, viscosidade cinemática e teor de água em petróleos. Na segunda aplicação foi desenvolvido um método para estimar o intervalo de confiança de modelos SVR aplicados a espectros de Ressonância Magnética Nuclear de próton (RMN de 1H) na determinação das temperaturas equivalentes a 10%, 50% e 90% de volume destilado de petróleo. Na terceira aplicação foi desenvolvido um método para selecionar variáveis espectrais e otimizar os parâmetros do modelo SVR simultaneamente por algoritmo genético, aplicado a espectros de Ressonância Magnética Nuclear de carbono 13 (RMN de 13C) na determinação de saturados, aromáticos, resinas e asfaltenos (SARA) em petróleos. Na última aplicação, procurou-se selecionar variáveis espectrais utilizando o método de sinergismo de intervalos, aplicado a espectros de infravermelho próximo (NIR) para quantificar biodiesel de gordura animal em mistura com biodiesel de soja e diesel B20. Os resultados apontam o SVR como excelente ferramenta para calibração multivariada aplicada a dados complexos como petróleo e biocombustíveis / Abstract: Crude oil is composed by a complex mixture of heterogeneous chemical composition. Its full evaluation involves about 700 physicochemical experiments, consuming about 10-70 liters of sample in there about 1 year of analysis. In order to reduce time and amount of sample, in this Thesis, spectroscopic methods combined with Support Vector Regression (SVR) were applied in determination of physicochemical properties of petroleum and biofuels. Different approaches for optimization and interpretation of SVR models were developed: techniques to determine the most important variables in the model development, determination of confidence intervals in predictions and assessment of trends in residuals. Four applications with different instrumental techniques were performed. The first application was directed to interpretation of SVR models built from mid infrared (MIR) spectra to determination of the API gravity, kinematic viscosity and water content in petroleum. In the second application, it was developed a method to estimation of the confidence interval of SVR models applied in spectra of proton nuclear magnetic resonance (1H NMR) for the determination of equivalent temperatures to 10%, 50% and 90% of distillate volume in petroleum. In the third application it was developed a method for spectral variables selection and optimization the SVR model parameters simultaneously by genetic algorithm, applied to nuclear magnetic resonance spectra of carbon 13 (13C NMR) in determination of saturates, aromatics, resins and asphaltenes (SARA) in petroleum. In the last application, it was proposed a method for spectral variables selection using the synergism of intervals, applied to near-infrared (NIR) spectra to quantify biodiesel from animal fat in blend with biodiesel from soybean and diesel B20. The results indicate the SVR as an excellent tool for multivariate calibration applied to complex dataset such as petroleum and biofuels / Doutorado / Quimica Analitica / Doutor em Ciências
185

Aplicações da mobilidade iônica acoplada a espectrometria de massas como uma técnica analítica para o estudo de misturas complexas e separação de isômeros / Applications of ion mobility mass spectrometry as an analytical technique for the study of complex mixtures and isomers separations

Lima, Maíra Fasciotti Pinto, 1987- 21 August 2018 (has links)
Orientador: Marcos Nogueira Eberlin / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-21T09:34:26Z (GMT). No. of bitstreams: 1 Lima_MairaFasciottiPinto_M.pdf: 3076235 bytes, checksum: bc4b63f365634b0b6e2e36e84cb49537 (MD5) Previous issue date: 2012 / Resumo: Esta dissertação apresenta uma breve introdução sobre a técnica de mobilidade iônica acoplada a espectrometria de massas (Capítulo 1) e a discussão de resultados aplicados a três subprojetos distintos. A técnica de TWIM-MS é uma técnica de separação na qual a separação em dos íons ocorre em uma cela de mobilidade iônica e é baseada em parâmetros como a seção de choque, carga, polarizabilidade, que é a capacidade de um íon ter sua densidade eletrônica distorcida pela interação com o gás de mobilidade, além de, obviamente, da estrutura tridimensional dos íons em fase gasosa. Sobre o Capitulo 2, objetivo do trabalho em petroleômica foi desenvolver e otimizar um método para a identificação de compostos polares presentes em amostras de petróleo e seus derivados como diesel e gasolina, que fosse capaz de diferenciar amostras distintas com relação essas composições, verificando quais respostas esta técnica pode fornecer nos estudos petroleômicos. Puderam ser identificadas as classes N, O2 e NO, com excelente resolução com a técnica de TWIM-MS. Entretanto, acredita-se que algumas outras classes ainda podem ser elucidadas. O CO2 se mostrou ser o melhor gás de mobilidade a ser utilizado para a resolução destas classes. A técnica de TWIM-MS também se mostrou adequada para a caracterização de gasolina e seus aditivos, entretanto mais amostras de diesel aditivado devem ser investigadas, para se descobrir porque os aditivos não puderam ser detectados através da técnica de ESI-TWIM-MS. Com relação ao estudo das estruturas em fase gasosa dos isômeros do Corrol (Capítulo 3), podese observar que o corrorin tem a estrutura tridimensional mais compacta entre todos os isômeros, enquanto NCC4 e corrol são os isômeros com maiores seções de choque e maiores drift times. Mesmo que o norrole tenha os maiores valores previstos de CCS, seu menor momento de dipolo resulta em interações mais fracas com o gás de mobilidade, e um drift time menor do que o esperado é obtido. Uma melhor resolução entre os isômeros de corrol foi alcançada usando CO2 como gás de mobilidade. Além disso, estes isômeros podem ser diferenciados monitorando íons característicos resultantes de suas fragmentações. Em conclusão, mostrou-se que a diferenciação por TWIM-MS destas estruturas pode ser conseguida através do monitoramento das diferenças entre as suas mobilidades relativas e também pelos espectros distintos de MS/MS obtidos para cada isômero. Já o Capítulo 4, visou avaliar a separação de 4 dissacarídeos isoméricos, em que se observou que a utilização de mais gases polarizáveis, tais como o CO2 na análise realizada com o Synapt G2 permite uma resolução quase na linha de base, o que não foi possível utilizando N2 como gás de mobilidade e nem na primeira geração do equipamento comercial Synapt, mesmo usando CO2 como gás de mobilidade / Abstract: This dissertation presents a brief introduction of the technique of Ion Mobility Mass Spectrometry (Chapter 1) and also the discussion of results applied to three distinct subprojects. The technique of Traveling Wave Ion Mobility Mass Spectrometry, is a separation technique in which the separation of the ions occurs in a mobility cell and is based on parameters such as collision cross-section, charge, polarizability (the capacity of an ion to have its electronic density distorted by interaction with the drift gas) and the three dimensional structure (shape) of ions in the gaseous phase. The main goal of the work performed in petroleomics (Chapter 2), was to develop and optimize a method for the identification of polar compounds present in oil samples and its derivatives, such as diesel and gasoline. The applied method was able to differentiate oil samples based on some polar components. Classes N, O2 and NO could be identified with proper resolution with TWIM-MS technique. However, it is believed that some other classes may be elucidated. CO2 was shown to be the best drift gas to be used for the separation of these classes. The technique of TWIM-MS also proved to be suitable for the characterization of gasoline and its additives, however, more samples of additive diesel must be investigated to find out why the additives could not be detected by the technique of ESI-TWIM-MS. During the study of tridimensional structures in the gaseous phase of five Corrole isomers (Chapter 3), it was observed that significant differences in shape and charge distributions for the protonated molecules lead to contrasting gas phase mobilities, most particularly for corroin, the most "confused¿ isomer. Accordingly, corroin was predicted by DFT and collisional cross section calculations to display the most compact tridimensional structure. NCC4 and corrole, on the other hand were found to be the most planar isomers. Better resolution between the corrole isomers was achieved using the more polarizable and massive CO2 as the drift gas and contrasting labilities towards CID, allowed the prompt differentiation of some isomers. Chapter 4 aimed to evaluate the separation of four isomeric disaccharides, where it was observed that the use of more polarizable gases, such as CO2, in the analysis performed with a Synapt G2 allows almost a baseline resolution for some isomeric pairs. This was not possible using N2 as drift gas with the Synapt G2, and not with the Synapt G1 using either N2 or CO2 / Mestrado / Quimica Analitica / Mestra em Química
186

Aplicações de mobilidade iônica acoplada a espectrometria de massas para separação e caracterização de isômeros / Ion mobility mass spectrometry applications to isomer separation and characterization

Lalli, Priscila Micaroni 09 November 2012 (has links)
Orientador: Marcos Nogueira Eberlin / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-21T09:31:28Z (GMT). No. of bitstreams: 1 Lalli_PriscilaMicaroni_D.pdf: 7058193 bytes, checksum: bda550a8e643bbf3d082b69bfd94c04e (MD5) Previous issue date: 2012 / Resumo: A espectrometria de mobilidade iônica separa íons de diferentes tamanhos ou formatos (seção de choque) em fase gasosa de acordo com o tempo que levam para atravessar uma câmara preenchida com gás sob a influência de um campo elétrico fraco. O acoplamento dessa técnica à espectrometria de massas (IM-MS) resulta em uma ferramenta extremamente versátil, pois adiciona uma nova dimensão aos dados de MS com informação sobre a estrutura tridimensional das espécies. Assim, a IM-MS tem sido muito utilizada para o estudo conformacional de proteínas, separação de isômeros e análise de misturas complexas. Neste trabalho, investigamos novas aplicações da IMMS, focando na separação de isômeros. Na primeira parte, mostramos que a IM-MS é capaz de separar isômeros posicionais de piridil porfirina mono ou multi substituída com [Ru(bpy)2Cl]+. Os isômeros substituídos em meta mostraram ser mais compactos do que os substituídos em para. Entretanto, os isômeros di-substituídos em cis e trans possuem seção de choque muito parecida e não puderam ser separados. Na segunda parte, mostramos a separação e caracterização de protômeros (espécies protonadas ou desprotonadas em sítios distintos). Apesar da protonação (ou desprotonação) em sítios diferentes não alterar significativamente a seção de choque da espécie, ela pode resultar em íons com distribuição de cargas contrastantes, o que leva a formação de heterodímeros entre os íons e as moléculas do gás (CO2) com forças e tempo de vidas contrastantes, assim assegurando a resolução desses protômeros por IM-MS. Na terceira parte do trabalho, investigamos o potencial da técnica para o detalhamento composicional e estrutural de compostos presentes em petróleo através da análise de cortes de destilação de alto ponto de ebulição / Abstract: Ion mobility mass spectrometry separates ions with different size or shape (collision cross section) in the gas phase according to the time they take to travel through a cell filled with gas under the influence of a low electric field. The coupling of this technique to mass spectrometry (IM-MS) results in an extremely versatile tool, since it adds a new dimension to MS data with information about the species¿ threedimensional structure. Therefore, IM-MS has been extensively used for protein conformation studies, isomer separations and analysis of complex mixtures. In this work, we investigate new applications of IM-MS, focusing on isomer separation. In the first part, we show that IM-MS is able to separate positional isomers of pyridilporhyrins mono or multi-substituted wih [Ru(bpy)2Cl]+. The meta substituted isomers were shown to be more compact than the para substituted isomers. On the other hand, cis and trans di-substituted isomers display very similar collision cross sections and could not be separated. In the second part of this work, we show the separation and characterization of protomers (species protonated or deprotonated in different sites). Although protonation (or deprotonation) in different sites does not change significatly the species collision cross section, it may result in ions with contrasting charge distribution, which leads to the formation of heterodimers between ions and gas molecules (CO2) with contrasting strengths and life times, therefore allowing the resolution of these protomers by IM-MS. In the third part of this work, we investigate the potencial of this technique for the compositional and structural detailing of compounds present in crude oil by the analysis of high boiling point distillation cuts / Doutorado / Quimica Analitica / Doutora em Ciências
187

Effects of low crude protein, amino acid fortified diets and neutral detergent fiber on finishing pig performance

Soto Gonzalez, Jose Alfredo January 1900 (has links)
Doctor of Philosophy / Department of Animal Sciences and Industry / Michael D. Tokach / Eleven experiments using 5,434 growing-finishing pigs were performed in addition to the development of a model to predict dietary NE that yields the greatest economic benefit. Two experiments were conducted to determine the effect of dietary phytogenics on growth and carcass performance of growing-finishing pigs. The addition of the combination of two phytogenics products (EOM 1+2) to diets improved ADFI, HCW, and carcass ADG. However, there was no evidence for treatment differences for growth or carcass performance in a second study. Two experiments were conducted to determine the effects of feeding high SID Trp:Lys ratios with and without Ractopamine HCl (RAC) on growth and carcass characteristics of finishing pigs. In Exp. 1, whereas increasing SID Trp:Lys ratio above 20% improved growth and carcass performance when diets contained RAC, pigs fed SID Trp:Lys ratios above 20% in diets without RAC had reduced growth and carcass performance. Contrary in Exp. 2, pigs fed increasing SID Trp:Lys in diet containing RAC did not provide further performance benefits. Three experiments were conducted to determine the optimum dietary SID Lys and CP concentrations in finishing pigs over 100 kg. The SID Lys requirement to obtain 100% of maximum response was 0.55 to 0.63% depending on the response variable. Growth and carcass performance was maximized in diets containing at least 12% dietary CP. Four experiments were conducted to determine the effects of SBM concentration and whether dEB, choline, or K are the reasons that performance is reduced when pigs over 100 kg BW are fed low CP diets. Performance was reduced as SBM concentration was reduced in the diet. Choline, K, and dEB do not appear to be the reason that performance is reduced when SBM concentration is decreased in low CP diets fed to pigs over 100 kg BW. A Microsoft Excel®-based model to predict the value of dietary NE that yields the greatest economic return to the production system was developed. Furthermore, a meta-analysis was conducted to incorporate the impact of NDF on carcass yield in the model.
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Glicerina bruta como suplemento energético para vacas leiteiras em pastejo de azevém / Gross glycerin as an energy supplement for dairy cows in a annual ryegrass production system

Fraga, Denize da Rosa 23 December 2016 (has links)
This thesis was developed with the objective of evaluating the effect of supplementation with 10% crude glycerin in the total dry matter (DM) of the diet for lactating cattle in a annual ryegrass (Lolium multiflorum) pasture production system on the metabolic profile, milk composition and production. The experiment was conducted at the Regional Rural Development Institute in Augusto Pestana, RS, Brazil, with 18 Holstein cattle, in a block design (according to lactation days) in a simple cross-over procedure, during three periods of 14 days. The diets were composed of annual ryegrass grazing and supplementation with corn silage and concentrate, with or without addition of 10% crude glycerin based on total dry matter. Samples of diet, urine, milk and blood were collected and evaluated. It were evaluated too milk production and leftover food in the trough. The data were submitted to analysis of variance and the treatment effect compared by the T test through the SAS statistical program. Values of P<0.05 were considered significant and tendency were considered when P<0.10. It was verified that the inclusion of 10% of crude glycerin in diet DM of lactating cows reduces the elimination of urea through milk and increases blood glucose levels, and does not have a deleterious effect on milk production and cows’ feed consumption. The addition of 10% DM of glycerin to the diet hasn’t effect on milk production and composition of Holstein cows in different lactation periods with different levels of protein in the diet. It was concluded that the inclusion of 10% crude glycerin in diet DM of lactating cows on annual ryegrass pasture reduces the level of milk nitrogen urea. This could be due to the decrease in urea blood levels by the increase of nutritional efficiency, provided by glycerin energy supply, for its energy and potential contribution in increasing blood glucose levels, without interfering in the productive performance and composition of the milk. / Esta tese foi desenvolvida com o objetivo de avaliar o efeito da suplementação com 10% de glicerina bruta na matéria seca (MS) total da dieta, para vacas em lactação, mantidas em sistema de produção em pastagem de azevém (Lolium multiflorum), sobre o perfil metabólico, composição e produção do leite. O experimento foi conduzido no Instituto Regional de Desenvolvimento Rural, em Augusto Pestana, RS, Brasil, com 18 vacas da raça holandesa, em um delineamento com blocos (conforme o perfil da lactação) em esquema de reversão simples dos animais (Cross-over), em três períodos de 14 dias. As dietas foram constituídas de pastejo em azevém e suplementação com silagem de milho e concentrado, acrescido ou não da adição de 10% de glicerina bruta com base na matéria seca (MS) total. Foram coletadas e analisadas amostras de alimentos, urina, leite e sangue. Foram avaliadas também sobras de alimento no cocho e produção de leite. Os dados foram submetidos à análise de variância e o efeito de tratamento comparado pelo teste T através do programa estatístico SAS. Valores de P<0.05 foram considerados significativos e como tendência quando P<0.10. Verificou-se que a inclusão de 10% de glicerina bruta na MS da dieta reduz à eliminação de ureia via leite e aumenta os níveis sanguíneos de glicose, não tendo efeito deletério sobre a produção de leite e consumo de alimento dos animais. A adição de 10% da MS de glicerina a dieta não apresenta efeito sobre a produção e composição do leite de vacas da raça holandesa, em diferentes períodos de lactação. Conclui-se que a inclusão de 10% de glicerina bruta na MS da dieta de vacas em lactação, em pastejo de azevém, diminui o nível de nitrogênio ureico no leite em função da melhora da eficiência nutricional, pelo seu aporte energético e potencial em aumentar os níveis de glicose sanguínea, sem interferir no desempenho produtivo e na composição do leite.
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Formation, stabilité et cassage des mousses non aqueuses : Contribution à l'étude des mousses pétrolières / Formation, stabilization and breaking of non aqueous foams : Contribution to the understanding of crude oil foams

Blazquez Egea, Christian 29 September 2014 (has links)
Les mousses rencontrées dans l’industrie pétrolière comptent parmi les mousses les plus complexes et problématiques. Lors de la production du pétrole brut, la présence de mousses stables peut entraîner de gros problèmes dans les équipements de traitement en surface à cause de la dépressurisation et de la nucléation de bulles provenant du gaz naturellement dissous dans le fluide de réservoir. Cette mousse peut rapidement occuper la moitié du volume des séparateurs et provoquer des dommages opérationnels graves, liés à des difficultés de contrôle des niveaux, à l’entraînement de liquide dans la ligne gaz et à l’entraînement de gaz dans la ligne liquide. Le contrôle de ces mousses pétrolières constitue donc un véritable enjeu, et les diverses solutions proposées sont basées sur l’utilisation de moyens physiques (chauffage, utilisation d’internes spécifiques) mais surtout sur l’utilisation d’additifs antimousses ou démoussants et plus particulièrement de silicones PDMS. Cependant, il n’existe pas encore d’optimisation possible de ces traitements du fait du manque d’études détaillées sur le comportement de ces systèmes complexes. L’objectif principal de ce travail a donc été de contribuer à la compréhension des mécanismes de formation, de stabilisation et de rupture des mousses non aqueuses et plus particulièrement des mousses de pétrole brut. Dans un premier temps, nous avons développé une nouvelle méthodologie expérimentale permettant de former des mousses représentatives des mousses pétrolières afin de comparer quantitativement différents systèmes moussants à base de pétroles bruts ainsi que l’efficacité de différentes familles d’additifs chimiques. Ensuite, nous avons étudié les cinétiques de cassage et développé un modèle de type sigmoïde permettant de décrire les courbes expérimentales de manière satisfaisante, et ouvrant la voie à une analyse quantitative de ces systèmes. Grâce à ce type de modélisation, il est possible de comparer l’efficacité des additifs chimiques en tant que démoussants et/ou antimousses et donc d’optimiser le choix du meilleur additif requis.Enfin ces développements permettent de proposer une première analyse de l’influence des caractéristiques physico chimiques de ces systèmes complexes sur leurs propriétés de moussage. / Crude oil foams are present in most steps of the oil industry, being one of the most complex and problematic non aqueous foams. During the crude oil exploitation, the presence of stable foams may cause major problems on surface equipment because of the depressurisation between the reservoir and the wellhead and the nucleation of the bubbles from the natural gas solubilised in the reservoir oil. These foams can fill up rapidly the half of the volume of the separators and cause serious damages due to the loss of the level control capacity, by dragging gas to the liquid line or liquid to the gas line, which leads to a reduction of the efficiency of the operation. The control of these foams is therefore a real issue. Several methods are used to control the foam based on its physical destruction (by mechanical devices, heating, special design of the unit internals...) but, by far, the most common method is the chemical destruction by adding different chemical compounds (called defoamers and antifoamers), particularly PDMS silicones. However, there is still no possible optimization of these treatments because of the lack of detailed studies on the behaviour of these complex systems. With this work we wanted to contribute to the understanding of the formation, stabilization and breaking mechanisms of this kind of non-aqueous foams. With this in mind, our first objective was the development of a new experimental methodology that allows to form crude oil foams which are representative of the oilfield foams, in order to compare the different foamy systems as well as the efficiency of different families of chemical additives. After that, we used a sigmoid model which describes in a satisfactory way the experimental curves of foam breaking. Besides, this kind of modelling allows to compare the efficiency of the different chemical additives in terms of defoaming and antifoaming effects, leading to the optimal selection of the additive in each case. Finally, these developments allow us to propose a first analysis of the influence of the physicochemical characteristics of these complex systems on their foaming properties.
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Going Beyond the Analysis of Common Contaminants: Target, Suspect, and Non-Target Analysis of Complex Environmental Matrices by High-Resolution Mass Spectrometry

Huba, Anna Katarina 14 November 2016 (has links)
The advancements in the field of analytical chemistry, and especially mass spectrometry, have been redefining the field of contaminant detection. While more traditional analysis was sufficient to screen for a small number of well-known compounds, new techniques such as high-resolution mass spectrometry, have enabled a fairly comprehensive screening for previously unknown contaminants. This is enormously beneficial with respect to the analysis of water, air, or soil quality in a society that continuously introduces novel anthropogenic compounds into the environment. This dissertation, thus, focused on the analysis of the uncharacterized portion of compounds in two types of complex environmental matrices (i.e., crude oil and wastewater). First, targeted and non-targeted analyses were used in order to characterize a crude oil weathering series. Traditional techniques were used for the analysis of well-known oil components and led to the confirmation of biodegradation and photo-degradation trends. An ultrahigh-resolution mass spectrometric analysis was carried out in conjunction with several visualization plots in order to search for unknown compounds. While the study successfully detected a drastic increase in oxygenated components (likely ketones, quinones, and carboxylic acids), it also revealed severe limitations in the state of the art non-targeted crude oil analysis. Some of these limitations were explored in an in-depth atmospheric pressure ionization study of model petroleum compounds, and the dependence of ionization efficiency on numerous factors (e.g., size, heteroatom content, and methylation level) was shown. Since disregarding these intrinsic limitations leads to severely biased conclusions, these results provide crucial information for future crude oil characterization studies. Lastly, suspected and non-targeted analyses were used to evaluate contamination levels in wastewater-impacted interrelated water samples. A significant number of persistent compounds were tentatively identified, which represents an area of environmental concern that needs to be addressed further. Overall, this dissertation successfully applied non-targeted (in addition to targeted) analysis in order to screen for non-characterized compounds in crude oil and wastewater affected water samples. By doing so, the great potential of the growing field of non-targeted screening in order to expand the range of contaminants to include previously unknown and emerging compounds was highlighted.

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