Transcription is an essential step in the expression of genetic information. This process depends on protein complex of multisubunit RNA polymerases that are exceptionally conserved among all cellular organisms. These enzymes together with eukaryotic RNA-dependent RNA polymerases involved in gene silencing form a monophyletic protein family whose members contain two double-ψ β-barrel structural motifs in their active center. This family also includes a group of mainly in silico predicted non-canonical DNA-dependent RNA polymerases which differ from multisubunit RNA polymerases in reduced composition. Putative non-canonical RNA polymerase consisting of two subunits is also encoded by cytoplasmic linear plasmids of the yeast Kluyveromyces lactis and highly likely transcribes genes of these plasmids. Characterization of a unique transcription machinery of Kluyveromyces lactis plasmids with major emphasis on non-canonical RNA polymerase has become the aim of this work. Bioinformatic analysis in silico was used to examine the evidence leading to an assumption of existence of specific RNA polymerase. Subsequent genetic and biochemical methods were used for: 1) production of putative RNA polymerase subunits in several expression systems; 2) testing interaction between several components of transcription...

Le polissage mécano-chimique (CMP) en raison de spécifications sévères, telles que l‘aplanissement de la surface à ± 5 nm, est devenu un enjeu crucial pour le développement des nœuds technologiques 14 nm et au-delà. Les méthodes actuelles de caractérisation de la topographie, limitées en termes de taille de surface analysée, évaluent l'efficacité des procédés sur des structures nommées boites de mesure. Ces structures mesurent 100 µm x 50 µm et sont situées entre les circuits intégrés. Elles sont donc non représentatives de la topographie de la puce et, de ce fait, des procédés de métrologie topographique de la puce sont requis. Dans un premier temps, nous montrons que la microscopie interférométrique est capable de caractériser la nano-topographie sur des distances centimétriques avec une résolution latérale micrométrique. La caractérisation par microscopie interférométrique de la nano-topographie induite par les procédés de CMP montre que les méthodes actuelles fournissent des valeurs topographiques non représentatives de la puce. Une méthodologie associée à ce nouveau type de caractérisation est proposée et discutée. Dans un deuxième temps, nous montrons que la diffusion de la lumière permet un contrôle rapide (trois minutes par plaques) et non destructif de variations nanométriques de la topographie de grilles de quelques dizaines de nanomètres de large sur toute la plaque. / Chemical Mechanical Polishing (CMP), because of narrower specifications, as surface planarization at ± 5 nm, is becoming a critical process for the development of the 14 nm technology node and beyond. Habitual topographic characterization techniques, limited in acquisition area, appraise processes efficiency through structures called test boxes. Those structures have a size equal to 100 µm by 50 µm and they are located, in the scribe lines, between the chips. Consequently, they are not representative of the die level topography and die level topographic metrology processes are required. In a first time, we show that interferometric microscopy is able to characterize nano-topography over centimetric distances with micrometric lateral resolution. Interferometric microscopy characterization of CMP processes induced nano-topography demonstrates that usual methods provide non representative die level topography values. A new characterization kind related methodology is proposed and discussed. In a second time, we show that diffused light measurement allows fast (three minutes/wafer) and non-destructive control of gate nano-topography variations for pattern widths of some tenths of nanometer.

Les bâtiments affectent fortement l’environnement à travers les consommations d’énergies et de ressources naturelles. Afin de limiter ces impacts, l’intégration de matériaux bio-sourcés dans la construction, tels que béton de chanvre, apparaît comme une solution pertinente. Les composites à base de chanvre présentent en outre un comportement hygrothermique spécifique conduisant à limiter les besoins énergétiques du bâtiment tout en assurant un bon niveau de confort ressenti. Ce type de matériau non porteur est utilisé en remplissage pourdifférentes applications (Mur, Dalle, Toit) et en enduit isolant. Cette thèse vient en appui du projet ANR « BetonChanvre » visant à optimiser la formulation de tels mélanges en liaison avec les process de fabrication des partenaires industriels et à caractériser les matériaux élaborés. Différents types de chanvre (fibré ou non, traité hydrofuge) et différents liants (chaux, sulfate de calcium) sont utilisés. Les formulations proposées dérivent de formulations de référence produites par les partenaires industriels. Les caractéristiques physiques des différents composites étudiés (masse volumique apparente, masse volumique réelle, porosités ouverte et totale) sont mesurées. Les propriétés hydriques sont quantifiées en régime permanent via la mesure des isothermes de sorption (adsorption/désorption) et de la perméabilité à la vapeur. Les isothermes de sorption sontmesurées selon la méthode discontinue par paliers successifs d’humidité relative croissante puis décroissante. La perméabilité à la vapeur est mesurée selon la méthode de la coupelle. Différents couples d’hygrométrie sont testés pour évaluer l’évolution de la perméabilité en fonction de la teneur en eau. La diffusivité hydrique est calculée à partir de la modélisation des isothermes de sorption et de la perméabilité à la vapeur. Enfinla caractérisation des performances mécaniques repose sur l’identification de la résistance à la compression, des modules de déformation (apparent et élastique) et de la contrainte résiduelle pour une déformation à 15%. L’impact du phénomène de vieillissement/carbonatation sur les caractéristiques hydriques et mécaniques est évalué sur des échantillons carbonatés en incubateur CO2. L’interprétation des résultats permet d’identifier différents principes de formulation en lien avec les performances hydriques et mécaniques finales ciblées pour le composite. Il en ressort que c’est l’association du liant avec le chanvre qui permet d’assurer des performances optimales. Toutefois, les optimum vis à vis des réponses hydrique et mécanique ne sont pas concordants. / Buildings strongly affect environment through energy and raw consumption. In order to reduce these impacts, the use of biobased building materials, like hempconcrete appears as a relevant solution. Hemp based composites lead to specific hygrothermal behavior limiting energy needs of buildings and insuring a good felt comfort level. These non load bearing materials are used as filling material for various applications (Wall, Floor, Roof) and as insulating rendering. This phD Thesis supports the ANR project « BetonChanvre » and concerns the optimization of the formulation in link with manufacturing process of the industrial partners and the characterization ofthese materials. Several kinds of hemp shiv (with and without fibers, with water repellant treatment) and of binders (lime, calcium sulfate) are used. The proposed formulation derives from reference formulations given by industrial partners. The physical characteristics of the studied materials (apparent density, bulk density, total and open porosity) are measured. The hydric properties are quantified under steady-state through sorption isotherms (adsorption/desorption) and water vapor permeability. The sorption curves are measured following the discontinuous method at successive stages of increasing, and then decreasing, relative humidity. The water vapour permeability is measured with the cup method. Several sets of relative humidities are considered in order to study the variation of permeability versus humidity. The hydric diffusivity is calculated from the fitting of the sorption curve and of the water vapor permeability. Finally, the characterization of mechanical performances is given from the compression strength, from the strain modulus (apparent and elastic) and from the residualstrength for 15% of strain. The impact of ageing and carbonation on hydric and mechanical characteristics isestimated on specimens carbonated with CO2 incubator. The data treatment allows identifying several formulations rules for such kind of bio-based composite, in link with the expected hydric and mechanical performances. Results highlight that only the mix of shiv with mineral binder allows to reach the optimalperformances. Despite, the formulations for mechanical or hydric optimum don’t met.N°

This thesis investigates D.H. Lawrence’s idea of the “great background” in the context of Thomas Hardy’s Jude the Obscure and how it reappears in a transformed way in Lawrence’s novels Sons and Lovers, The Rainbow, and Women in Love. Through examining the perverse effects of modernism on these novels’ characters, this thesis argues that the “great background” is something that gradually moves inward––from the old, traditional “State” to an internal, inscrutable yet attainable reality.

La chitine est l’un des biopolymères les plus abondants dans la biomasse. Son principal dérivé industriel est le chitosane. Ces deux polysaccharides présentent un intérêt croissant en raison de leurs nombreuses propriétés physico-chimiques et biologiques remarquables. Leur utilisation en tant que matériaux est potentiellement intéressante dans de nombreux domaines tels que la pharmacie, la médecine, l’industrie alimentaire et l'agriculture. Malgré de nombreuses avancées dans les méthodes chimiques de production de la chitine et du chitosane, l'utilisation de solutions concentrées d'acides et de bases alcalines présente le désavantage de générer de grandes quantités d’effluents toxiques. Récemment, des méthodes d'extraction de la chitine par biotechnologie ont été proposées comme une alternative aux méthodes chimiques. Dans ce contexte, l'objectif principal de ce travail a été de développer un procédé biotechnologique d’extraction de la chitine à partir de carapaces de crustacés à l’aide de bactéries lactiques et d’enzymes. A cette fin, les facteurs influençant les réactions mises en jeu au cours de l’extraction, telles que la déminéralisation, la déprotéinisation et la N-désacétylation ont été étudiés en considérant les caractéristiques physico-chimiques des chitines et chitosanes ainsi obtenus. Ces caractéristiques sont principalement les masses molaires moyennes et le degré de N-acétylation. Ce travail s’est également intéressé à la valorisation des sous-produits d’extraction (protéines, pigments…) et aux applications potentielles des différents chitosanes préparés, notamment comme agents fongistatiques. / The chitin is one of the most abundant biopolymers in biomass. Its main industrial derivative is the chitosan. These two polysaccharides present an increasing interest thanks to their various interesting physicochemical and biological properties. Their potential applications concern diverse fields as the pharmacy, medicine, food industry and agriculture. Despite numerous advances in methods for the chemical production of chitin and chitosan, the use of concentrated solutions of acids and alkaline bases presents the disadvantage to generate large amounts of toxic wastes. Recently, biotechnological methods of chitin extractions have been proposed as an alternative to chemical methods. In this context, the main objective of this work was to develop a biotechnological process for the extraction of chitin from crustacean shells using lactic acid bacteria and enzymes. For this purpose, factors influencing reactions involved in the extraction, i.e. the demineralization, deproteinization and N-deacetylation, were studied considering the physicochemical characteristics (molecular weight and degree of N-acetylation) of chitin and chitosan produced. The recovery of extraction side products such as proteins and pigments has also been considered in this project, as well as the evaluation of various chitosans prepared by this process as fungistatic agents.

Les emballages actifs permettent d’étendre la durée de conservation des aliments, réduisent l'utilisation d'additifs et de conservateurs dans les préparations alimentaires, préservent mieux les saveurs et la qualité des aliments. La libération contrôlée des antioxydants à partir d'emballages alimentaires étend la stabilité des produits (oxydation des lipides réduite) par enrichissement continu en antioxydants alimentaires en surface de l’aliment. L'objectif général du présent travail était d'étudier l'applicabilité de l'acide poly lactique (PLA, polymère biodégradable fabriqué industriellement) comme l'emballage actif. Pour cela, nous avons choisi plusieurs antioxydants synthétiques ou naturels, comme l'alpha-tocophérol, le palmitate d'ascorbyle, le BHA, le BHT, le gallate de propyle et le TBHQ pour produire les emballages antioxydants. En premier lieu, le mode de d’inclusion de ces antioxydants dans la matrice de PLA et leurs effets sur diverses propriétés structurale, thermique, mécanique et barrière du PLA ont été étudiés. L'étude la libération des antioxydants a été réalisée à partir de films de PLA-antioxydants en contact avec trois simulateurs d'aliments (95%, 50%, et 10% d'éthanol) à deux températures (20°C et 40°C). Les résultats ont montré que le PLA a la capacité de contenir et de libérer des antioxydants dans certains produits alimentaires. Enfin, un modèle mathématique basé sur des relations quantitatives structure/propriété (QSPR) a été développé pour prédire la diffusion antioxydants dans les systèmes aliments simulés /emballage actif / Active packaging generates longer shelf-life foods, lower usage of additives and preservatives in food formulations, higher protection of flavors and higher food qualities. Antioxidant controlled release from packaging provides longer food stability (reduced lipid oxidation) by continuously liberating antioxidants at food surface. The overall objective of the present work was to study the suitability of Poly Lactic Acid (PLA, biodegradable polymer industrially produced) as active packaging. We chose various synthetic or natural antioxidants including alpha-tocopherol, Ascorbyl palmitate, BHA, BHT, Propyl gallate and TBHQ to produce the antioxidant packaging. Firstly, the mode of incorporation of these antioxidants in PLA matrix and also their potential effects on diverse structural, thermal, mechanical and barrier properties of PLA were investigated. The release study of antioxidants was accomplished from PLA-antioxidants films into three food simulants, i.e. 95%, 50%, and 10% ethanol at two temperatures (20°C and 40°C). The results showed that PLA has the capability for being as a suitable carrier for antioxidant-active packaging for some food products. Finally, a mathematical model based on quantitative structure property relationships (QSPR) was developed to predict antioxidant diffusion in food simulant/ active packaging system

Master of Science / Department of Geology / Abdelmoneam Raef / This research presents a workflow integrating several post-stack seismic attributes to assist in understanding the development history of Weirman Field, Ness County, KS. This study contributes to shaping future drilling plans by establishing a workflow combining analysis of seismic attributes and well cuttings to locate a channel fill zone of better reservoir quality, and to highlight reservoir boundaries due to compartmentalization. In this study, I have successfully outlined a fluvial channel, which is expected to be significantly different in terms of petrophysical properties. The Pennsylvanian aged Cherokee sandstones that potentially comprise channel fill lithofacies, in this study, have been linked to oil production throughout the state of Kansas. It is important to understand channel sandstones when evaluating drilling prospects, because of their potential as an oil reservoir and unpredictable shapes and locations. Since their introduction in the 1970s, seismic attributes have become an essential part of lithological and petrophysical characterization of hydrocarbon reservoirs. Seismic attributes can correlate to and help reveal certain subsurface characteristics and specific geobodies that cannot be distinguished otherwise. Extracting and analyzing acoustic impedance, root-mean-square amplitude and amplitude attenuation, guided by a time window focused on the top of the Mississippian formation, resulted in an understanding of the key seismic channel-facies framework and helped to explain some of the disappointing drilling results at Weirman Field. To form a better understanding of these seismic attributes, this study combined certain attributes and overlayed them in partially transparent states in order to summarize and better visualize the resulting data. A preliminary study of spectral decomposition, which was introduced in the late 1990s, was preformed, and a more in-depth study of this multi-resolution attribute is recommended for future study of this particular field. This study also recommends integrating the revealed compartmentalization boundary and the seismic channel-facies framework in future drilling plans of Weirman Field.

Master of Science / Department of Geology / Abdelmoneam Raef / In this study, laboratory measurements of ultrasonic frequency P- and S-wave velocities were collected and analyzed from two sets of cores. The first set is from a near surface study in southeastern Kansas, and the second set was from the deep subsurface and obtained from a newly drilled well (Wellington KGS 1-32) in Sumner County, KS. Ultrasonic velocities acquired from the second set of cores were then compared with in situ sonic and dipole sonic frequencies of P- and S-waves from well logs. Well log data, core data, and ultrasonic velocity measurements were integrated for Gassmann fluid replacement modeling. The understanding of the velocity and elastic moduli variations at ultrasonic frequencies, along with the comparison of well log velocities can potentially provide improved understanding to establish a beneficial calibration relationship. It could also allow for estimation of shear wave velocities for wells lacking dipole sonic log data. The ability to utilize cost-effective ultrasonic measurements of velocities and elastic moduli in the laboratory, for fluid replacement modeling (Gassmann) in CO[subscript]2-sequestration, as well as, enhanced oil recovery (EOR) projects, would be a significant advance. Potential alternative use of ultrasonic velocities for determining the effects of fluid replacement using Gassmann modeling, when log data is lacking, is an ongoing effort. In this study, the fluid replacement modeling is executed based on sonic and dipole sonic P- and S-wave velocities and compared with results from theoretical modeling. The significance of this work lies in the potential of establishing a calibration relationship for the representative lithofacies of the carbon geosequestration target zone of the Wellington KGS 1-32 well in Sumner County, and enabling the use of ultrasonic measurements of body wave velocities and elastic moduli in Gassmann fluid replacement modeling. This work, when integrated with continuing effort in mapping lithofacies of the Arbuckle and Mississippian groups, would potentially be of great importance to fluid flow simulation efforts and time-lapse seismic monitoring. This study will utilize Gassmann modeling and a range of measurements and data, which include: well logs and ultrasonic laboratory P- and S-wave measurements and core analysis data.

Doctor of Philosophy / Department of Chemical Engineering / James H. Edgar / The semiconductor boron phosphide (BP) has many outstanding features making it attractive for developing various electronic devices, including neutron detectors. In order to improve the efficiency of these devices, BP must have high crystal quality along with the best possible electrical properties. This research is focused on growing high quality crystalline BP films on a variety of superior substrates like AIN, 4H-SiC, 3C-SiC and ZrB₂ by chemical vapor deposition. In particular, the influence of various parameters such as temperature, reactant flow rates, and substrate type and its crystalline orientation on the properties of BP films were studied in detail. Twin-free BP films were produced by depositing on off-axis 4H-SiC(0001) substrate tilted 4° toward [1-100] and crystal symmetry matched zincblende 3C-SiC. BP crystalline quality improved at higher deposition temperature (1200°C) when deposited on AlN, 4H-SiC, whereas increased strain in 3C-SiC and increased boron segregation in ZrB₂ at higher temperatures limited the best deposition temperature to below 1200°C. In addition, higher flow ratios of PH₃ to B₂H₆ resulted in smoother films and improved quality of BP on all substrates. The FWHM of the Raman peak (6.1 cm⁻¹), XRD BP(111) peak FWHM (0.18°) and peak ratios of BP(111)/(200) = 5157 and BP(111)/(220) = 7226 measured on AlN/sapphire were the best values reported in the literature for BP epitaxial films. The undoped films on AlN/sapphire were n-type with a highest electron mobility of 37.8 cm²/V·s and a lowest carrier concentration of 3.15x1018 cm⁻ᶟ. Raman imaging had lower values of FWHM (4.8 cm⁻¹) and a standard deviation (0.56 cm⁻¹) for BP films on AlN/sapphire compared to 4H-SiC, 3C-SiC substrates. X-ray diffraction and Raman spectroscopy revealed residual tensile strain in BP on 4H-SiC, 3C-SiC, ZrB₂/4H-SiC, bulk AlN substrates while compressive strain was evident on AlN/sapphire and bulk ZrB₂ substrates. Among the substrates studied, AlN/sapphire proved to be the best choice for BP epitaxy, even though it did not eliminate rotational twinning in BP. The substrates investigated in this work were found to be viable for BP epitaxy and show promising potential for further enhancement of BP properties.

Lithium-ion batteries are today finding use in automobiles aiming at reducing fuel consumption and emissions within transportation. The requirements on batteries used in vehicles are high regarding performance and lifetime, and a better understanding of the interior processes that dictate energy and power capabilities is a key to strategic development. This thesis concerns aging in lithium-ion cells using electrochemical tools to characterize electrode and electrolyte properties that affect performance and performance loss in the cells.   A central difficulty regarding battery aging is to manage the coupled effects of temperature and cycling conditions on the various degradation processes that determine the lifetime of a cell. In this thesis, post-mortem analyses on harvested electrode samples from small pouch cells and larger cylindrical cells aged under different conditions form the basis of aging evaluation. The characterization is focused on electrochemical impedance spectroscopy (EIS) measurements and physics-based EIS modeling supported by several material characterization techniques to investigate degradation in terms of properties that directly affect performance. The results suggest that increased temperature alter electrode degradation and limitations relate in several cases to electrolyte transport. Variations in electrode properties sampled from different locations in the cylindrical cells show that temperature and current distributions from cycling cause uneven material utilization and aging, in several dimensions. The correlation between cell performance and localized utilization/degradation is an important aspect in meeting the challenges of battery aging in vehicle applications.   The use of in-situ nuclear magnetic resonance (NMR) imaging to directly capture the development of concentration gradients in a battery electrolyte during operation is successfully demonstrated. The salt diffusion coefficient and transport number for a sample electrolyte are obtained from Li+ concentration profiles using a physics-based mass-transport model. The method allows visualization of performance limitations and can be a useful tool in the study of electrochemical systems. / <p>QC 20140512</p>