L'objectif de cette thèse était d’évaluer quelques Metal-Organic Frameworks (MOFs), choisis en fonction de leur taille de pores, de leur volume poreux et de leur stabilité thermique, en adsorption et séparation des hydrocarbures. Pour étudier le comportement général des MOFs nous avons choisi des MOFs avec des centres métalliques insaturés, des MOFs à charpente anionique et des ZIFs neutres et avons étudié leur sélectivité en séparation de trois familles d'hydrocarbures, à savoir alcanes, alcènes, aromatiques. Les MOFs à centre métallique insaturé se comportent généralement comme des zéolithes polaires, les ZIFs comme des zéolithes apolaires et/ou comme des tamis moléculaires. Les adsorbants les plus prometteurs sont testés sur des séparations d’intérêt industriel telles que la séparation des isomères de xylène, la séparation des paraffines linéaires, monobranchées et di-branchées et l’adsorption sélective du thiophène en vu de l’évaluation de ces adsorbants en désulfuration des essences. / The aim of this thesis was to evaluate several Metal Organic Frameworks (MOFs), selected based on criteria of pore size, pore volume and thermal stability, in adsorption and separation of hydrocarbons. For studying the general behavior of MOFs in hydrocarbon adsorption, we have chosen MOFs with open metal sites, MOFs with anionic frameworks and neutral ZIFs. The MOFs with open metal sites behave similar to polar zeolites, the ZIFs behave like apolar zeolites and/or like molecular sieves. Finally we selected the most interesting MOFs and tested them in several separations with industrial interest: xylene isomers, paraffin isomers and selective adsorption of thiophene for the purpose of fuel desulfuration.

This research addresses and illuminates a little understood region of miscible polymer mixtures and demonstrates a new means of separating wax from such blends. The method, termed Deformation Induced Phase Segregation potentially eliminates need of toxic processing solvents for wax removal or recovery in these types of blends. Previous theories of polymer combinations address them exclusively as solutions or as blends, two independent classes having very different behaviors. This study provides bridge connecting these two classes by identifying crossover points between them and the behaviors exhibited therein. The blends of this form were found to be semi-miscible, forming a homogenous phase in the melt but a two-phase system in the solid, with the rheological behavior influenced by the polymer's molecular weight and architecture. It also demonstrates practical promise of this regime by introducing a mechanical compression process to separate the wax phase from such a type of blend. This process potentially permits production of ultra-high molecular weight polyethylene (UHMwPE) films and fibers by melt processing, thereby obviating need of otherwise essential but expensive and environmentally unfriendly toxic solvents.

Mycobacteriosis is a common disease of laboratory zebrafish (Danio rerio). Different infection patterns occur in zebrafish depending on mycobacterial species. Mycobacterium marinum and M. haemophilum produce virulent infections associated with high mortality, whereas M. chelonae is more wide spread and not associated with high mortality. Identification of mycobacterial infections to the species level provides important information for making management decisions. Observation of acid-fast bacilli in histological sections or tissue imprints is the most common diagnostic method for mycobacteriosis in fish, but only allows for diagnosis to the genus level. Mycobacterial culture, followed by molecular or biochemical identification is the traditional approach for species identification, but recently it has been shown that DNA of diagnostic value can be retrieved from paraffin blocks. Type of fixative, time in fixative before processing, species of mycobacteria, and severity of infection were investigated as parameters to determine if the hsp gene PCR assay (primer set HS5F/hsp667R) could detect and amplify mycobacterial DNA from paraffin-embedded zebrafish. Whole zebrafish were experimentally infected with either M. chelonae or M. marinum, and then preserved in 10% neutral buffered formalin or Dietrich's fixative for 3, 7, 21 and 45 days. Subsequently, fish were evaluated by H&E and Fite's acid-fast stains to detect mycobacteria within granulomatous lesions. The PCR assay was quite effective, and obtained PCR product from 75% and 88% of the M. chelonae and M. marinum infected fish, respectively. Fixative type, time in fixative, and mycobacterial species showed no statistical relationship with the efficacy of the PCR test. Regarding natural transmission, zebrafish are capable of contracting mycobacterial infections by feeding on infected fish tissue, but other natural routes have not been clearly elucidated. Free living amoebae have been shown to be vectors for mycobacteria and their virulence is enhanced when residing in these protozoans. Paramecium caudatum are commonly used as a first food for zebrafish, and I investigated this ciliate's potential to serve as a vector of Mycobacterium marinum and M. chelonae. The ability of live P. caudatum to transmit these mycobacteria to larval, juvenile and adult zebrafish was evaluated. Infections were defined by histologic observation of granulomas containing acid-fast bacteria in extraintestinal locations. In both experiments, fish fed paramecia containing mycobacteria became infected at a higher incidence than controls. Larvae (exposed at 4 days post hatch) fed paramecia with M. marinum exhibited an incidence of 30% (24/80) and juveniles (exposed at 21 days post hatch) showed 31% incidence (14/45). Adult fish fed gelatin diets containing bacteria within paramecia or mycobacteria alone for 2 wk resulted in infections when examined 8 wk after exposure: M. marinum OSU 214; in paramecia 47% (21/45; 3.5 x 10⁵ dose/fish/day), M. marinum CH in paramecia 47% (9/19; 3.6 x 10⁵ dose/fish/day), M. chelonae in paramecia 38% (5/13; 3.5 x 10⁵ dose/fish/day). I investigated the ability of mycobacteria to persist within paramecia, as this has previously been demonstrated in amoebae. Gram negative bacteria ingested by paramecia were processed within an hour. In contrast, I determined using GFP-labeled Mycobacterium marinum that mycobacteria can persist within paramecia digestive vacuoles. The concentration of M. marinum at 1 hour was similar to that at the time of ingestion. Twenty-four hours post-ingestion and later there was significant decline in M. marinum concentrations compared to time of ingestion, but M. marinum continued to persist inside digestive vacuoles for up to one week. My results demonstrate for the first time that Paramecium caudatum can act as a vector for mycobacteria. This provides a useful animal model for evaluation of natural mycobacterial infections and demonstrates the possibility of mycobacterial transmission in zebrafish facilities via contaminated paramecia cultures. / Graduation date: 2013 / Access restricted to the OSU Community at author's request from April 2, 2013 - April 2, 2015

This thesis reports a model to predict the auto-ignition time of single droplets of n-paraffin fuel mixtures using the method of continuous thermodynamics. The model uses experimental data for pure fuels to fit rate parameters for a single-step global chemical reaction equation; from this, correlations for rate parameters as a function of species molecular mass are derived, which are integrated to produce a continuous thermodynamics expression for mixture reaction rate. Experiments were carried out using the suspended droplet-moving furnace technique. The model was then tested and compared to experimental data for three continuous mixtures with known compositions: one ranging from ¬n-octane to n-hexadecane, the second ranging from n-dodecane to n-eicosane, and the third being a combination of the first two mixtures to produce a “dumbbell” mixture. Discrete and continuous mixture models of the ASTM standard distillation test were compared to design the experimental mixtures and provide the distribution parameters of the continuous mixtures intended to simulate them. The results of calculations were found to agree very well with measured ignition times for the mixtures.

This thesis reports a model to predict the auto-ignition time of single droplets of n-paraffin fuel mixtures using the method of continuous thermodynamics. The model uses experimental data for pure fuels to fit rate parameters for a single-step global chemical reaction equation; from this, correlations for rate parameters as a function of species molecular mass are derived, which are integrated to produce a continuous thermodynamics expression for mixture reaction rate. Experiments were carried out using the suspended droplet-moving furnace technique. The model was then tested and compared to experimental data for three continuous mixtures with known compositions: one ranging from ¬n-octane to n-hexadecane, the second ranging from n-dodecane to n-eicosane, and the third being a combination of the first two mixtures to produce a “dumbbell” mixture. Discrete and continuous mixture models of the ASTM standard distillation test were compared to design the experimental mixtures and provide the distribution parameters of the continuous mixtures intended to simulate them. The results of calculations were found to agree very well with measured ignition times for the mixtures.

Olefin/paraffin separation is a large potential market for membrane applications. Carbon molecular sieve membranes (CMS) are promising for this application due to the intrinsically high separation performance and the viability for practical scale-up. Intrinsically high separation performance of CMS membranes for olefin/paraffin separations was demonstrated. The translation of intrinsic CMS transport properties into the hollow fiber configuration is considered in detail. Substructure collapse of asymmetric hollow fibers was found during Matrimidﾮ CMS hollow fiber formation. To overcome the permeance loss due to the increased separation layer thickness, 6FDA-DAM and 6FDA/BPDA-DAM polyimides with higher rigidity were employed as alternative precursors, and significant improvement has been achieved. Besides the macroscopic morphology control of asymmetric hollow fibers, the micro-structure was tuned by optimizing pyrolysis temperature protocol and pyrolysis atmosphere. In addition, unexpected physical aging was observed in CMS membranes, which is analogous to the aging phenomenon in glassy polymers. For performance evaluation, multiple "proof-of-concept" tests validated the viability of CMS membranes under realistic conditions. The scope of this work was expanded from binary ethylene/ethane and propylene/propane separations for the debottlenecking purpose to mixed carbon number hydrocarbon processing. CMS membranes were found to be olefins-selective over corresponding paraffins; moreover, CMS membranes are able to effectively fractionate the complex cracked gas stream in a preferable way. Reconfiguration of the hydrocarbon processing in ethylene plants is possible based on the unique CMS membranes.

This thesis reports a model to predict the auto-ignition time of single droplets of n-paraffin fuel mixtures using the method of continuous thermodynamics. The model uses experimental data for pure fuels to fit rate parameters for a single-step global chemical reaction equation; from this, correlations for rate parameters as a function of species molecular mass are derived, which are integrated to produce a continuous thermodynamics expression for mixture reaction rate. Experiments were carried out using the suspended droplet-moving furnace technique. The model was then tested and compared to experimental data for three continuous mixtures with known compositions: one ranging from ¬n-octane to n-hexadecane, the second ranging from n-dodecane to n-eicosane, and the third being a combination of the first two mixtures to produce a “dumbbell” mixture. Discrete and continuous mixture models of the ASTM standard distillation test were compared to design the experimental mixtures and provide the distribution parameters of the continuous mixtures intended to simulate them. The results of calculations were found to agree very well with measured ignition times for the mixtures.

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-04-09T18:53:27Z No. of bitstreams: 1 CRISTIANE HENRIQUE DA SILVA - DISSERTAÇÃO PPG-CEMat 2014..pdf: 1882367 bytes, checksum: 61c1cc3ebbf9ac5089a587fe51bfa458 (MD5) / Made available in DSpace on 2018-04-09T18:53:27Z (GMT). No. of bitstreams: 1 CRISTIANE HENRIQUE DA SILVA - DISSERTAÇÃO PPG-CEMat 2014..pdf: 1882367 bytes, checksum: 61c1cc3ebbf9ac5089a587fe51bfa458 (MD5) Previous issue date: 2014-08-29 / Capes / Este trabalho apresenta um estudo sobre a influência da incorporação de argila bentonítica e carbonato de cálcio sobre as propriedades de um fluido de perfuração sintético n-parafina. Para tanto, a pesquisa utilizou argila bentonítica com tamanho de partícula de 45 µm e 75 µm e carbonato de cálcio com tamanhos de partículas nas faixas de 2-44 µm e 2-74 µm para analisar os efeitos da incorporação de sólidos. A análise da influência destes contaminantes foi realizada nas concentrações de 5%, 10% e 15% do volume da amostra de fluido (350 mL) considerados em massa. Para estudar a influência desses contaminantes foram determinadas, em laboratório, as propriedades: densidade, estabilidade elétrica, resistividade elétrica, comportamento de fluxo, viscosidade plástica, viscosidade aparente, limite de escoamento, força gel, volume de filtrado. Além desses ensaios, também foi realizada a caracterização dos contaminantes por meio da análise granulométrica e do teste de ângulo de contato. Os resultados obtidos demonstraram que o tipo de sólido contaminante exerce diferente influência sobre as propriedades do fluido, sendo a argila bentonítica responsável por maiores efeitos sobre as propriedades reológicas e o volume de filtrado, enquanto que, o carbonato de cálcio exerce maior influência sobre a densidade e a estabilidade elétrica. Mas, de maneira global a argila bentonítica exerce maior influência sobre todas as propriedades. Partículas mais finas causam maior efeito sobre as propriedades estudadas. Com relação aos teores dos contaminantes observou-se que o volume de filtrado é a propriedade que sofre maiores efeitos. Porém, o aumento ou a diminuição de uma ou outra propriedade não ocorre de maneira linear com relação ao aumento do teor de contaminante. / This work presents a study about the influence of the incorporation of bentonite clay and carbonate calcium in n-paraffin synthetic drilling fluids properties. Thus, the research uses bentonite clay with particle size of 45 µm and 75 µm, besides calcium carbonate with particle sizes in the ranges of 2-44 µm and 2-74 µm to simulate the effects of the solid incorporation. The analysis of the influence of such contaminants is performed in the concentrations of 5%, 10% and 15% of the volume of the fluid sample (350 mL) considered by mass. To study the influence of these contaminants the density, electrical stability, electrical resistivity, flow behavior, plastic viscosity, apparent viscosity, yield point, gel strength, and volume filtered properties of the n-paraffin synthetic fluids are measured in laboratory. In addition to these tests, the characterization of contaminants through granulometric analysis and contact angle test is also performed. The results show that the type of solid contaminant exerts different influence on the fluids properties. The bentonite clay is responsible for the greatest effect on the rheological properties and the volume of the filtrated, while the calcium carbonate is more influent on the density and electrical stability. However, globally the bentonite clay exerts greater influence on the all properties. Finer particles cause greater effect on the studied properties. With respect to the concentration of contaminants is observed that the volume of filtrated is the property that suffers the greatest effect. However, the increase or decrease of one or other property does not occur linearly with respect to increasing the amount of contaminant.

[pt] A deposição de parafinas em dutos traduz-se em perdas econômicas relevantes para a indústria. Dentre as formas de mitigação do fenômeno, encontram-se os inibidores de parafina, produtos químicos injetados continuamente e em baixas concentrações, cujo objetivo é eliminar ou reduzir a deposição. Tradicionalmente, a eficiência de inibição destes produtos para uma dada amostra de petróleo é avaliada em laboratório em equipamento denominado dedo-frio. No entanto, não há uma padronização para o projeto e uso destes equipamentos e procedimentos experimentais de teste. Também, ainda não há consenso entre fabricantes dos inibidores e operadoras de petróleo sobre a correlação entre a eficiência de inibição apresentada nos testes de dedo frio e aquela observada no campo. O presente trabalho teve como objetivo comparar resultados de deposição de parafina obtidos em dedo frio do tipo dinâmico com aqueles obtidos em duto circular em loop de teste, utilizando solução de teste com propriedades controladas, com e sem a presença de inibidor de parafina. No dedofrio do tipo dinâmico, um cilindro refrigerado imerso no óleo gira com velocidade angular constante, promovendo um escoamento do tipo Taylor-Couette, caracterizado por padrões de escoamento complexos e diferentes daqueles encontrados em dutos de transporte de petróleo. O trabalho teve como foco o estudo da influência de parâmetros hidrodinâmicos na deposição de parafinas, representados pelo número de Reynolds e tensão cisalhante adimensional sobre a superfície do depósito. Testes realizados com os fluidos modelo em regime laminar e turbulento mostraram boa correlação entre os resultados de inibição obtidos no dedo frio e no loop de teste, a despeito da diferença nos padrões de escoamento. Testes em regime turbulento resultaram em depósitos menores e menos porosos, tanto no dedo-frio quanto no loop. Foi também observada a redução da porosidade dos depósitos com a adição do inibidor,independentemente do tipo de equipamento e da condição operacional. Experimentos no dedo-frio com um segundo fluido, mais viscoso, foram conduzidos com o objetivo de avaliar a influência da viscosidade no processo de deposição, tendo como premissa a diminuição do coeficiente de difusão esperada para o fluido mais viscoso. Ao contrário do esperado, não foi observada variação sensível na deposição com a mudança da viscosidade do fluido. Efeitos positivos e negativos de inibição foram observados nos testes para o inibidor avaliado. Observou-se uma maior atuação do inibidor, seja positiva ou negativa, para experimentos em regime laminar. O presente estudo mostrou que o inibidor pode diminuir a massa total depositada aumentando, no entanto, a massa de parafina depositada. / [en] Wax deposition in pipelines is associated with relevant economic losses for the industry. Wax deposition inhibitors are among the options available to mitigate the problem, being continuously injected in the flow at low concentrations. Traditionally, the inhibition efficiency of these products for a particular oil sample is assessed in a laboratory equipment know as cold finger. However, a standard is still not available for the design and operation of cold fingers. Also, there is no consensus among operators and inhibitor suppliers as to the level of correlation between the inhibition efficiency found in the laboratory and that in the field. The objective of the present work was to compare wax deposition results obtained in a dynamic cold finger apparatus to those obtained in a pipe flow loop, employing a test solution with controlled properties, with and without inhibitor, In the dynamic cold finger, a cylinder immersed in the oil sample rotates at constant angular velocity producing a Taylor-Couette flow in the cylindrical oil container, which is characterized by complex flow patterns, that are distinct from those found in an oil pipeline. The investigation focused on the influence of the flow hydrodynamic parameters on the wax deposition, represented by the Reynolds number and the dimensionless shear stress imposed at the deposit surface. Tests conducted with model fluids in laminar and turbulent regimes displayed good correlation between the inhibition results obtained in the cold finger apparatus and in the test loop, despite the differences in flow patterns. Turbulent flow testes produced smaller and less porous deposits both, in the cold finger and in test loop. Also observed was a reduction in the deposit porosity in the presence of the inhibitor, independently of the equipment type and operational conditions. Experiments in the cold finger for a second more viscous fluid were conducted to assesses the influence of viscosity on the deposition process, and the expected decrease in the diffusion coefficient for the higher viscosity fluid. Contrary to what was expected, no significant variation was observed on the deposits with the viscosity change. Positive and negative inhibition effects were observed in the tests for the particular inhibitor tested. A more significant influence of the inhibitor, either positive or negative, was observed for tests in laminar flow conditions. The present study revealed that the inhibitor could decrease the total deposited mass while increasing the paraffin deposited mass.

Colorectal cancer (CRC) is a common malignancy which develops due to old age and lifestyle factors, low percent of patients afflicted by a genetic disorders. Half of all colorectal cancer patients are diagnosed after metastasis. The high rate of the late detection, emphasizes on the requirement of convenient and inexpensive diagnostic methods for comprehensive screening programs. The aim of this study was to discover proto-oncogenes mutation and assessment of tumor suppressor genes expression. Formalin fixed paraffin embedded (FFPE) histologically verified colorectal cancer samples were used. APC, KRAS and BRAF mutations were investigated using polymerase chain reaction (PCR) fragments and direct sequencing. Gene expression assessment of MLH1, MGMT and CDKN2A were achieved via quantitative polymerase chain reaction (qPCR). In the present study we could detect a novel transversion heterozygous mutation in APC gene codon 1365 in three patients. BRAF codon 600 mutation were detected in one patient. KRAS codon 12 mutation was discovered in one sample and also a novel transition mutation in codon 15 was detected in 6 patients. In 80% of cases, MLH1 and MGMT expression were undetectable, in remaining 20%, MLH1 expression were reduced, but MGMT showed both reduced and increased expression compared to control. In 100% of patients CDKN2A expression was undetectable. The rate of mutations in predetermined hotspot codons and amount of uncommon mutations into APC, BRAF and KRAS in Nepalese patients indicates the requirement of further investigation in CRC patients from that part of the world. Also, the expression rate of MLH1, MGMT, CDKN2A and deficiency of an information source emphasizes the necessity of whole genome CRC expression profiling data to comparison and conclusion. / <p>-</p> / -