La compréhension de la relation structure-propriété est un élément indispensable pour la conception et l'amélioration des matériaux, notamment ceux utilisés dans le domaine de l'emballage alimentaire. Afin de contribuer à la compréhension des phénomènes de transport dans le polylactide (PLA), les travaux de ce mémoire se sont portés sur la modulation de la microstructure du PLA en lien avec ses propriétés barrière aux gaz (oxygène, hélium) et aux composés organiques (esters éthyliques, sondes fluorescentes). La microstructure a été modulée i) par l'ajout de plastifiant (ATBC, PEG), ii) par la cristallisation selon trois procédés, le traitement thermique, la cristallisation induite par des composés organiques et le biétirage. Ces approches ont permis, respectivement, de faire varier le pourcentage de phase amorphe par rapport à la phase cristalline, la fraction de volume libre au sein de la phase amorphe, et la structure cristalline. L'augmentation de la cristallinité par recuit à partir du vitreux n'a pas conduit à une diminution systématique et importante des coefficients de transport des molécules de gaz (oxygène, hélium). Deux hypothèses principales ont ainsi été formulées pour expliquer ce comportement : la dédensification de la phase amorphe et la présence d'une phase amorphe mobile et d'une phase rigide. L'influence du biétirage sur les propriétés barrière aux gaz a été très limitée même au plus fort ratio d'étirage (4×4). Néanmoins cette technique a l'avantage de pouvoir réaliser des morphologies différentes.L'étude des coefficients de transport par plusieurs méthodes (sorption, perméation, diffusion par contact solide/solide) a mis en évidence la loi d'échelle ( ) dans le cas des molécules fluorescentes et a permis une première estimation du coefficient alpha. Une approche par Résonance Paramagnétique Electronique a permis de mettre en évidence des séparations de phase des systèmes plastifiés par ATBC et PEG. Cette méthode pourrait constituer un des moyens de sonder les hétérogénéités locales et les changements microstructuraux liés à l'interaction de molécules perméantes et de la matrice polymère, lors du transport. / The understanding of the relationship between structure and properties is fundamental for materials conception and improvement, in particular for those used in food packaging industry. To contribute to the understanding of the transport phenomena in polylactide (PLA), this study was focused on the adjustment of PLA microstructure modulation related to its gas (oxygen, helium) and organic compounds (ethyl esters, fluorescent molecules) barrier properties. The microstructure was modulated i) by adding plasticizers (ATBC, PEG), ii) by crystallizing according to 3 processes, thermal treatment, organic compounds induced crystallization and biaxially orientation. These approaches, respectively enabled to vary, the ratio of amorphous phase and crystalline phase, free volume fraction into amorphous phase and the crystalline structure. The increase in crystallinity degree, by annealing from cold state, did not result in a systematic and significant decrease of the gas molecules transport coefficient (oxygen, helium). Two main hypotheses were formulated to explain this behaviour: de-densification of amorphous phase and the presence of a mobile and a rigid amorphous phase. The influence of biaxially orientation on gas barrier properties was strongly limited even at the highest stretching ratio (4×4). Nevertheless several morphologies can be formed thanks to this technique.The transport coefficient study by several methods (sorption, permeation and diffusion by solid/solid contact) highlighted a scale law with the fluorescent molecules and allowed to a first estimation of the α coefficient. Thanks to Electronic Spin Resonance approach, phase separation of plasticized systems by ATBC and PEG were highlighted. This method could be one of the means to probe the local heterogeneities and the micro-structural changes related to the interaction of permeating molecules and polymer matrix during transport.

Landscape permeability is currently significantly decreasing mainly due to anthropogenic barriers - transportation infrastructure and sub/urban development. The construction of these barriers has various environmental impacts on animals that differ among taxa. Ensuring a certain degree of permeability of the landscape is crucial for the survival of many species of organisms. Effective tools for the planning protection and restoration of the permeability of the landscape are series of models, whose theoretical framework and practical use are described in this thesis. The practical part deals with the modeling of changes in landscape permeability in the southern hinterlands of Prague. The effectiveness of the implemeted mitigation measures is also evaluated. Keywords: landscape fragmentation, landscape permeability, ecoducts, mitigation measures, suburbanization

La partie supérieure de la Formation Khuff est un réservoir représentant le plus grand champ gazier mondial, d'âge Permien supérieur à Trias inférieur. Il est formé de la succession de calcaires, de dolomies et de sulfates. Sa production est principalement contrôlée par des intervalles d'épaisseur généralement inférieure à 10 m, totalement dolomitisés, appelés super-drains ou super-K, connectés sur plusieurs dizaines de kilomètres.Les objectifs de l'étude sont (1) de définir la mise en place et l'extension des super-drains dans un cadre stratigraphique, (2) de comprendre la diagenèse contrôlant leurs propriétés réservoirs et (3) de comparer la mise en place des corps dolomitiques stratiformes précoces ou tardifs liés aux failles à ceux d'un analogue à l'affleurement, à savoir les formations calcaréo-dolomitiques d'âge Jurassique supérieur en Provence.Pour les atteindre, des analyses sédimento-diagénétiques (sédimentologiques, pétrographiques et géochimiques) ont été entreprises sur les deux objets d'études du réservoir de subsurface et de l'analogue réservoir d'affleurement. Pour ce dernier, une modélisation en 3D de corps diagénétiques liés aux failles a été réalisée. Les principaux résultats sont que :- les localisations des super-drains ont été contrôlées par la dynamique sédimentaire de séquences à basse fréquences (SBF) et à haute fréquence (SHF) ;- des super-drains sont localisés au sommet des SBF sous les discontinuités d'émersions et à la limite des fronts de dolomitisation de reflux différé. / The upper part of the Khuff Formation includes the biggest gas reserves in the world, from Upper Permian to Lower Triassic age. It is composed by the succession of limestone, dolomite and sulfate. The gas production is mainly driven by layers typically thinner than 10 m, fully dolomitised, and called super-drains or super-K and connected over several dozen kilometers.The goals of this study are (1) to define the formation and the extension of super-K layers in a stratigraphic framework, (2) to understand the diagenesis controlling their reservoir properties and (3) to compare the creation of early stratabound and late fault-related dolomite bodies with an outcrop analogue, from the limestone and dolomite formations from Provence from Upper Jurassic age.To reach this goal, sedimento-diagenetic analyses (sedimentological, petrographical and geochemical) have been carried out on studied objects, the subsurface reservoir and the outcrop analogue reservoir. For the latter, 3D modelling of fault-related dolomite bodies have been realised. The main results are:- the locations of super-K have been controlled by the sedimentary dynamics of low frequency sequences (SBF) and high frequency sequences (SHF) ;- some super-K are located at the top of SBF under emersion unconformities and at the rim of dolomitisation fronts associated to postponed reflux. The reflux was made of brines, coming from synsedimentary dolomite bodies associated with marine transgressions that followed the emersions. This model is corroborated by an outcrop analogue, which is a dolomite reservoir underlying a long lasting emersion unconformity;

Les déchets liés à l'élevage intensif ont un impact environnemental reconnu du fait de leur composition riche en en matière organique et minérale. Il apparait opportun de promouvoir des procédés de traitement permettant de maitriser l'impact environnemental de ce retour au sol, voire d'ouvrir de nouvelles valorisations au travers de la récupération d'énergie ou de l'exportation de co-produits (azotés et phosphatés notamment). Ce travail entre dans cette démarche en proposant de compléter les étapes de digestion anaérobie de ces déchets par des étapes de séparation sur membranes perm-sélectives. Les essais ont été réalisés sur unités pilotes de laboratoire en utilisant des digestats réels de diverses origines prélevés sur sites. Pour l'étape de clarification par ultrafiltration, la conduite d'une séparation en mode tangentiel est obligatoire au regard de la concentration des suspensions à traiter. La viscosité des suspensions, d'autant plus importante que la suspension est concentrée, apparait comme un paramètre déterminant pour le choix du protocole opératoire. Dans tous les cas, l'opération d'ultra-filtration (UF) permet une rétention conséquente (de 80 à 90%) de la fraction organique encore présente dans les digestats, à l'inverse, la rétention de la fraction minérale soluble est restée négligeable comme attendu. Le seuil de coupure de la membrane d'UF n'est pas apparu déterminant sur cette rétention. Malgré le mode tangentiel de séparation, l'opération de filtration induit une accumulation de composés au voisinage de la membrane qui diminue significativement la perméabilité du milieu filtrant. Cette chute de perméabilité apparaît d'autant plus importante que la suspension présente une concentration en demande chimique en oxygène (DCO) élevée. Ce critère apparaît alors comme le facteur limitant pour atteindre un facteur de concentration volumique (FCV) élevé (réduction des volumes). La surface membranaire à développer est directement liée à la perméabilité membranaire, elle-même dépendante de la concentration de la suspension à traiter donc de la nature du digestat et du FCV à atteindre. Le coût opérationnel de l'opération apparaît directement lié à l'énergie nécessaire pour assurer le mode tangentiel de filtration. Pour l'étape de concentration des sels d'intérêts, la rétention des composés minéraux solubles par osmose inverse haute pression dépasse 90% quels que soient les ions ciblés ou l'origine du digestat. A l'inverse, cette rétention est dépendante de l'ion ciblé et de l'origine du digestat pour les opérations de nano-filtration et d'osmose inverse basse pression. Dans tous les cas, la rétention de la fraction organique résiduelle est importante (>90%) permettant une décoloration du perméat très poussée (elle dépend toutefois du seuil de coupure de la membrane et du FCV choisi). La perméabilité membranaire diminue d'autant plus que la conductivité électrique (CE) de la solution à traiter est importante du fait de la pression osmotique et de l'accumulation de composés solubles au voisinage de la barrière membranaire. Cette conductivité, dépendante du digestat initial et du FCV choisi, apparaît alors comme le paramètre déterminant pour le dimensionnement de l'unité. Sur le plan énergétique, l'énergie liée à la mise sous pression des unités NF/OI est dominante par rapport à la circulation tangentielle du rétentat. Ce travail a permis de confirmer l'intérêt des séparations membranaires pour le traitement des digestats, afin d'une part, d'obtenir une eau de qualité permettant sa réutilisation ou son rejet dans le milieu naturel et d'autre part de récupérer et de concentrer des composés d'intérêt dans les différents rétentats. Ce travail a fait l'objet d'un soutien financier de l'ANR dans le cadre du programme BIOENERGIE 2010 (projet DIVA). / Intense spreading of livestock wastes are recognized to be detrimental to the environment due to their content of organic matter and mineral fraction. Then, it would appear to be necessary to promote greens treatments processes. In fact, anaerobic digestion allows the production of biogas (extremely useful source of renewable energy), whilst digestate should be a highly valuable biofertilizer This work enters in this approach by proposing to complete anaerobic digestion steps by the use of perm-selective membrane separation process. The first step is a clarification step by ultrafiltration, following by a soluble mineral concentration step by nanofiltration, low pressure and/or high pressure reverse osmosis (LPRO, HPRO). The tests were performed in a laboratory-scale pilot unit using real digestates. For clarification step, a cross-flow mode separation is obligate in view of suspended solid concentrations and viscosity which appeared as a determining factor for the choice of operative protocol. In any case, the ultra-filtration operation allows a high organic retention rate (of 80 to 90%). Conversely, soluble mineral retention remained at negligible as expected. The cut-off of ultrafiltration membrane is not a determining factor for this retention. Despite the cross-flow mode separation filtration induces a compound accumulation on the membrane which decreases significantly the permeability of filtering media. This permeability drop appears greater when suspension presents a high COD concentration. This criterion appears as a limiting factor to achieve a high volumic concentration factor (VCF). Membrane surface to develop is then directly related to the membrane permeability which depends on the digestate origin and VCF. The operational cost is linked directly to the energy required to ensure cross-flow mode. The retention of soluble mineral compounds by HPRO exceeds 90% whatever the target ions or the origine of digestate are. However, for NF and LPRO steps, this rejection depends on the target ions or the origine of digestate. In any case, organic retention is important (more than 90%) which allows significant discoloration of permeate. The, the more the electronic conductivity (EC) is, the more permeability decreases of suspension is important, due to an osmotic pressure and soluble compound accumulation on the membrane that increases with EC. This conductivity depends on initial digestate and, of course, of the chosen VCF target, which appears as decisive parameter for unit dimensioning. On the efficient energy, energy linked to separation step chosen is dominant in the absence of cross-flow mode of retentate. This work has allowed to confirm the potential interest of membrane separation to (i) obtain a final effluent: named fresh or new water and (ii) and (ii) to allow the production of liquid fertilizers.This work is financially supported by the National French Agency (Bio-Energy Program 2010, DIVA Project) and by TRIMATEC competitiveness cluster.

O presente estudo teve como objetivo avaliar a produção de xilitol a partir de hidrolisado hemicelulósico de palha de arroz empregando células de Candida guilliermondii permeabilizadas com Triton X-100. Para a obtenção do hidrolisado hemicelulósico foram realizadas etapas de pré-tratamento da palha de arroz sob condições previamente otimizadas pelo grupo de pesquisa, incluindo um tratamento alcalino seguido de tratamento com ácido diluído. Inicialmente, foi avaliado o efeito do meio de permeabilização celular (meio semi-definido ou hidrolisado hemicelulósico) sobre a biotransformação de xilose em xilitol empregando hidrolisado hemicelulósico. Numa segunda etapa, foi avaliado o efeito de tampão fosfato de potássio e MgCl2.6H2O sobre o processo de biotransformação empregando hidrolisado não detoxificado e detoxificado com carvão ativado através de um planejamento experimental 22. As condições de biotransformação foram mantidas a 35 °C, pH 6,8, com uma suspensão celular de 10-12 g/L. Neste estudo ficou demonstrado que a biotransformação do hidrolisado empregando células permeabilizadas em meio semi-definido, mostrou uma produtividade volumétrica em xilitol (QP = 1,86 g/L.h) de 34,8 % superior à obtida com células permeabilizadas no próprio hidrolisado (QP = 1,38 g/L.h), enquanto os fatores de conversão de xilose em xilitol foram semelhantes (~0,57 g/g) independente do meio de permeabilização. Foi observado que a adição de tampão fosfato de potássio e/ou MgCl2.6H2O ao hidrolisado hemicelulósico (não detoxificado e detoxificado) não promoveu qualquer efeito sobre a biotransformação de xilose em xilitol, obtendo-se em média uma produtividade volumétrica de 2,0 g/L.h e um fator de conversão de 0,57 g/g. O impacto da permeabilização celular com Triton X-100 sobre a biotransformação de xilose em xilitol empregando hidrolisado hemicelulósico não detoxificado e sem qualquer adição de sais foi de um aumento de 40 % na produtividade volumétrica e de 32 % no fator de conversão de xilose em xilitol. As células permeabilizadas com Triton X-100 também mostraram elevada estabilidade. Os valores de produtividade volumétrica e fator de conversão de xilose em xilitol foram mantidos em 4 ciclos de 15 horas cada em bateladas repetidas, os quais apresentaram em média 1,93 g/L.h e 0,59 g/g, respectivamente. Estes resultados mostram que a permeabilização celular é uma potencial estratégia para a biotransformação de xilose em xilitol a partir de hidrolisado hemicelulósico de palha de arroz, pois além de aumentar os parâmetros da biotransformação, não promoveu queda da viabilidade celular e permitiu o reuso das células. / The present study aimed to evaluate the production of xylitol from hemicellulosic rice straw hydrolyzate using Candida guilliermondii cells permeabilized with Triton X-100. To obtain the hemicellulosic hydrolyzate, pre-treatment steps were performed on rice straw under conditions previously optimized by the research group, including an alkaline treatment followed by diluted acid treatment. Initially, the effect of the cellular permeabilization medium (semi-defined medium or hemicellulosic hydrolyzate) on the biotransformation of xylose in xylitol using a hemicellulosic hydrolyzate was evaluated. In a second step, the effect of potassium phosphate buffer and MgCl2.6H2O on the biotransformation process was evaluated using non-detoxified hydrolyzate and detoxified with activated charcoal through an experimental design 22. The biotransformation conditions were maintained at 35 °C, pH 6,8, with a cell suspension of 10-12 g/L. In this study, it was demonstrated that in the biotransformation of xylitol in xylitol by cells permeabilized in semi-defined medium using hemicellulosic hydrolyzate, the volumetric productivity in xylitol (QP = 1,86 g/L.h) was 34,8% higher than that obtained with cells permeabilized in hydroxylate (QP = 1,38 g/L.h), while xylose conversion factors in xylitol were similar (~ 0,57 g/g) independent of the permeabilization medium. It was observed that the addition of potassium phosphate buffer and / or MgCl2.6H2O to the hemicellulosic (non-detoxified and detoxified) hydrolyzate did not have any effect on the biotransformation of xylitol into xylitol, obtaining, on average, a volumetric productivity of 2,0 g/L.h and a conversion factor of 0,57 g/g. The impact of cell permeabilization with Triton X-100 on xylose biotransformation in xylitol using non-detoxified hemicellulosic hydrolyzate and without any addition of salts was a 40% increase in volumetric productivity and 32% in xylose conversion factor in xylitol. Cells permeabilized with Triton X-100 also showed high stability. The values of volumetric productivity and conversion factor of xylose in xylitol were maintained in 4 cycles of 15 hours each in repeated batch, which presented, on average, 1,93 g/L.h and 0,59 g/g, respectively. These results show that cellular permeabilization is a potential strategy for the biotransformation of xylitol in xylitol from hemicellulosic rice straw hydrolyzate, since in addition to increasing the parameters of biotransformation, it did not promote a decrease in cell viability and allowed reuse of the cells.

Human tissue transglutaminase (TG2) is a calcium-dependent multifunctional enzyme that natively catalyzes the post-translational modification of proteins, namely by the formation of isopeptide bonds between protein- or peptide-bound glutamine and lysine residues. This ubiquitously expressed enzyme plays important roles in cellular differentiation, extracellular matrix stabilization, and apoptosis, to name a few. However, its unregulated activity has been associated with many pathologies such as fibrosis, cancer, neurodegenerative disorders and celiac disease. Most of these disorders are associated with unregulated acyl-transferase activity. As such, the Keillor group has directed its efforts towards the development of TG2 inhibitors. Over the years, the Keillor group has synthesized large libraries of targeted covalent inhibitors against TG2. These compounds have undergone pharmacodynamic testing in order to examine their kinetic parameters of inhibition. Having gained knowledge of their enzyme kinetics, the logical next step was to consider their pharmacokinetic profiles. In the context of this thesis, we considered two important pharmacokinetic properties: membrane permeability and off-target reactivity. Firstly, we aimed to evaluate our inhibitors for their ability to permeate the cell membrane. In efforts to do so, we were able to adapt, optimize, and validate a parallel artificial membrane permeability assay (PAMPA) utilizing hexadecane as our artificial membrane. We were able to test a few of our own inhibitors and found that compounds NC9, VA4 and AA9 possess Log Pe values of -5.26 ± 0.01, -4.66 ± 0.04 and -6.5 ± 0.5 respectively. Secondly, we sought to investigate the susceptibility of our inhibitors to glutathione addition reactions under physiological conditions. We adapted and optimized a colorimetric assay using Ellman’s reagent (DTNB) and found that our inhibitors are minimally reactive with glutathione. The methods developed over the course of this work provide protocols that can be adopted for the characterization of future inhibitors in the Keillor group, along the process of developing TG2 inhibitors into drug candidates.

[pt] Em operações de perfuração, é importante ter uma estimativa do gradiente de fratura de determinada formação, como o objetivo de poder estimar o máximo peso da lama necessária para a próxima seção da formação rochosa, antes de colocar o revestimento. Por esse motivo, são realizados ensaios de Leak-Off para determinar a máxima pressão que a nova seção do poço pode sustentar sem fraturar ou perder fluido, sendo realizados durante a fase de perfuração do poço, nas formações imediatamente abaixo de cada sapata de revestimento. A finalidade deste estudo é realizar a simulação numérica deste ensaio usando um programa comercial de elementos finitos para calcular a pressão de Leak-Off, considerando a taxa de bombeamento como um dado de entrada do problema e a pressão na parede do poço como uma resposta. O trabalho abordará dois cenários: uma formação rochosa permeável e uma formação rochosa impermeável constituída de rocha de sal. Deste modo, para um estudo de uma análise real de um ensaio de Leak-Off em rocha permeável e rocha impermeável, torna-se necessário a utilização de modelos que considerem poroelasticidade e fluência, respectivamente. Para a caracterização do comportamento da rocha de sal foi usada uma lei de fluência de duplo mecanismo de deformação, que considera apenas os mecanismos de fluência: planar e indefinido. Os modelos estudados foram bidimensionais e analisados sobre a hipótese de deformação plana. A hipótese, de que a pressão de Leak-Off é atingida quando a tensão tangencial efetiva é igual a zero (calculada graficamente), foi considerada. Finalmente, foram simulados alguns casos para verificar os possíveis efeitos da alteração da permeabilidade e influência do fluido de pressurização no cálculo da pressão de Leak-Off em rocha permeável. / [en] In drilling operations, it is important to have an estimate of the fracture gradient of certain formation, in order to being able to estimate the maximum mud weight required for the next section of the rock formation, before casing is placed. For this reason, Leak-Off tests are conducted to determine the maximum pressure that the new section of the well can support without fracturing or losing fluid, being made during the drilling phase of the well in formations immediately below each casing shoe. The purpose this study is to perform the numerical simulation of this test using a commercial finite element program to calculate the Leak-Off pressure, considering the pumping rate as an input data of the problem and pressure at the borehole wall as the answer. The work will address two cases: a permeable rock formation and an impermeable rock formation composed of salt rock. Thus, for studying a real analysis of a Leak-Off test in permeable and impermeable rock, it becomes necessary to use models that consider poroelasticity and creep, respectively. For the characterization of salt rock it was used a creep law of dual mechanism of deformation, which considers only the dislocation creep mechanisms: planar and undefined. The two-dimensional models were studied and analyzed under the assumption of plane strain. The hypothesis that the Leak-Off pressure is reached when the effective tangential stress is zero (estimated graphically), was considered. Finally, some cases were simulated to check the possible effects of changing the permeability and the influence of pressurized fluid in the calculation of Leak-Off pressure in the permeable rock.

Reconhece-se, por estudos prévios, as complexas heterogeneidades de fácies nos depósitos sedimentares siliciclásticos fluviais, presentes na exploração de hidrocarbonetos. Devido à amostragem, custosa e insuficiente, na indústria, os modelos geológicos construídos possuem alta incerteza associada. Visando auxiliar tanto a exploração quanto a recuperação, foram executados estudos de análogos de reservatório na Formação São Sebastião, na Bacia do Tucano Central. Para isso, com base na dinâmica de processos fluviais, integraram-se análises de micro (petrografia e diagênese) e mesoheterogeneidades (fácies e elementos arquiteturais) tridimensionalmente, junto à permoporosidade, culminando em modelos geológicos de elementos arquiteturais, fácies e permeabilidade. As características permoporosas da Formação São Sebastião estão sujeitas tanto a controles deposicionais (elementos arquiteturais) como a controles diagenéticos (petrofácies), os quais se correlacionam. Os elementos arquiteturais, portadores de características mais efetivas como reservatório são as barras unitárias, seguidas pelas compostas. Em mesoescala, ambas são representadas majoritariamente por cruzadas tabulares e acanaladas de diferentes dimensões. A mediana para permeabilidade das barras unitárias e compostas é de 6000 mD e 4500 mD, enquanto para porosidade é de 21,0 % e 16,9 %, respectivamente. Em contrapartida, as barreiras de permeabilidademais importantes são representadas pelos topos de barra contínuos que majoritariamente apresentam estruturas de marca ondulada e estruturas plano paralelas, em mesoescala, e petrofácies com alta concentração de micas. A mediana de permeabilidade dos topos de barra é 200 mD, já a de porosidade é 13,5%. Como barreiras de permeabilidades subordinadas, encontram-se os canais abandondados (pouco freqüentes nos afloramentos), em mesoescala, representados por estruturas de marcas onduladas e convolutas; e, em microescala, relacionadas a altas concentrações de micas e pseudomatriz. A mediana da permeabilidade nos canais abandonados é 50 mD e a da porosidade é 16,1 %. Os modelos geológicos gerados com os dados de permeabilidade e fácies apontaram para anisotropias de baixa permeabilidade nos topos de barra e canais abandonados. Os topos de barra possuem continuidade lateral maior que 200 m em alguns locais, resultando em grande impacto no fluxo dentro do reservatório. As anisotropias de alta permeabilidade podem ser observadas principalmente na base dos depósitos de barras. Essas anomalias estão relacionadas com arenitos médios a grossos, portadores de cruzadas tabulares. Deste modo, nos depósitos analisados, a permeabilidade é controlada principalmente pela granulometria e concentração de pseudomatriz e micas, com influência subordinada das estruturas sedimentares. Já a porosidade, também controlada pela concentração de pseudomatriz e micas, possui forte influência das estruturas sedimentares e seleção granulométrica, mas não tem correlação com a granulometria. / The complex facies heterogeneities in fluvial deposits are present in the oil and gas industry. Due to expensive and insufficient sampling, in this industry, geological models which are created to assist the hydrocarbon exploration contain many uncertainties. Aiming to assist in this situation, studies on outcrops reservoirs analogues were performed in Sao Sebastião Formation, in Central Tucano Basin. Based on fluvial sedimentology, micro (petrography and diagenesis) and mesoheterogeneities (facies and architectural elements) analyses were conducted. Porosity and permeability were likewise analyzed. The data obtained were used to create architectural, facies and permeability models. Porosity and permeability are mainly controlled by two correlated variables: depositional controls (architectural elements) and diagenetic controls (petrofacies). The architectural elements with the most effective characteristics as reservoir are the unit bars, followed by the compound bars. Both architectural elements are represented by small to large (0.2 m up to 1.5 m) planar and through cross strata. The median permeability of unit bars is 6000mD, and the median of compound bars is 5000mD. The median porosity of unit bars is 21.0%, and the median of compound bar is 16.9%. On the other hand, the most important permeability barriers are the continuous bar tops, they are represented in mesoscale by climbing ripples structures and horizontal bedding. Bartops have shown a high mica assembly in microscale analyses. The median permeability of this element is 200mD, and the median porosity is 13.5%. The abandoned channels are subordinated permeability barriers in São Sebastiao Formation. In mesoscale they are mainly represented by climbing ripples structures and convolute bedding. In microscale they are related to high mica and pseudomatrix content. The permeability median of abandoned channels is 50 mD, and the median porosity is 16.1%. The geological models created also pointed out to bar tops and abandoned channels as permeability barriers. The bar tops can reach 200 m or more of lateral continuity, representing the highest flux barrier inside the reservoir. The positives anisotropies of permeability are linked to medium to coarse sandstones with planar cross strata. Therefore, in Sao Sebastiao Formation the permeability is controlled primarily by grain size, pseudomatrix and mica content. Sedimentary structures also impact the permeability subordinately. The porosity is handed likewise by the pseudomatrix and mica content, but also by the sedimentary structures and grain sorting. Nevertheless, porosity is not correlated with grain size.

The study explored the relationships between role centrality, work-family culture, work-family balance and work-family conflict. Additionally, it examined the incorporation of work-family culture into border permeability as used in work-family border theory. A total of 103 participants from five organisations completed the questionnaires. Participants were employed in administrative, professional/skilled/specialist, supervisory or management positions. Data were analysed using Pearson’s Product Moment correlation and Simple Regression. Significant results were obtained between role centrality, home centrality and workfamily balance as well as work-family conflict. These were in support of Clark (2000) work-family border theory. However, work centrality produced insignificant relationships. Work-family culture produced significantly strong relationships and predictability on work-family balance and conflict. The study findings highlight a need for expansion of border theory to include work-family culture as an aspect of border permeability.

ABSTRACT Vascular permeability and angiogenesis are crucial events in the rodent and human uterus in early pregnancy and are regulated by vascular endothelial growth factor (VEGF) and prostaglandins liberated from arachidonic acid by cyclooxygenase 2 (COX2). These events coincide with the typical morphological features of the receptive uterus and are regulated by synchronized release of ovarian hormones (oestrogen and progesterone). However, administration of follicle stimulating hormone (FSH) and human chorionic gonadotropin (hCG), commonly used in assisted reproduction, affect the synchrony of the hormonal milieu, particularly by increasing oestrogen levels. This causes detrimental changes to the uterine morphology and affects vascular permeability at the site of implantation. In the present study, the expression of COX2 and VEGF was compared between control and hyperstimulated rat uteri during the peri-implantation period using immunohistochemistry and Western blot analysis. While in control pregnant rats COX2 and VEGF immunolocalization occurred in the luminal epithelial cells and stroma on consecutive days, strong immunolocalization of COX2 and VEGF occurred in the luminal epithelial cells but was inhibited in the stroma of the hyperstimulated rats. This appears to have resulted in the suppression of stromal decidualization and vascular permeability. Western blot analysis did not show any results. This may be due to low concentrations of the protein in the sample. Since vascular permeability and angiogenesis are critical to the process of implantation and are influenced by VEGF and COX2, disturbance of the pattern of these two proteins by hyperstimulation may contribute to the low implantation rate in IVF programes. immunohistochemistry and Western blot analysis. While in control pregnant rats COX2 and VEGF immunolocalization occurred in the luminal epithelial cells and stroma on consecutive days, strong immunolocalization of COX2 and VEGF occurred in the luminal epithelial cells but was inhibited in the stroma of the hyperstimulated rats. This appears to have resulted in the suppression of stromal decidualization and vascular permeability. Western blot analysis did not show any results. This may be due to low concentrations of the protein in the sample. Since vascular permeability and angiogenesis are critical to the process of implantation and are influenced by VEGF and COX2, disturbance of the pattern of these two proteins by hyperstimulation may contribute to the low implantation rate in IVF programes.