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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.
61

Synthèse diastéréosélective et énantiosélective de dérivés cyclopropaniques 1,2,3-substitués à l’aide de carbénoïdes gem-dizinciques

Zimmer, Lucie 12 1900 (has links)
Les dérivés cyclopropaniques 1,2,3-substitutés sont des composés intéressants dans de nombreux domaines de la chimie. Au cours de cet ouvrage, nous nous sommes intéressés à la synthèse, tout d’abord diastéréosélective puis énantiosélective de ces composés. Nous nous sommes en particulier intéressés à l’utilisation de la zinciocyclopropanation pour l’obtention de ces dérivés cyclopropaniques 1,2,3-substitutés. Cette méthode consiste en l’utilisation d’un carbénoïde gem-dizincique pour effectuer une réaction de type Simmons-Smith. Cette stratégie a l’avantage d’être diastéréosélective favorisant la formation du zinciocyclopropane dont l’atome de zinc est dans une configuration cis avec le groupement directeur qu’est l’oxygène allylique basique. Lors de cette réaction, l’existence d’une réaction compétitive avec un réactif monozincique diminuait l’utilité de la zinciocyclopropanation. L’issue de la réaction s’est avérée dépendre fortement de la nature du carbénoïde utilisé, de la température réactionnelle et de la présence de ZnI2 dans le milieu. L’étude par GCMS de nombreuses conditions pour la formation des différents carbénoïdes a permis d’identifier les paramètres clés conduisant à la zinciocyclopropanation. Ces découvertes ont notamment permis d’étendre la réaction de zinciocyclopropanation aux alcools allyliques portant un seul groupement directeur (ie. non dérivé du 1,4-buténediol). Dans ces conditions, la réaction s’est avérée extrêmement diastéréosélective favorisant la formation du zinciocyclopropane dont l’atome de zinc est dans une configuration cis avec le groupement directeur. Afin de fonctionnaliser les zinciocyclopropanes ainsi obtenus, plusieurs réactions de fonctionnalisation in situ ont été développées. Chacune de ces méthodes a montré une conservation totale de la diastéréosélectivité obtenue lors de la réaction de zinciocyclopropanation. La versatilité de la zinciocyclopropanation a donc été démontrée. Avec une méthode diastéréosélective efficace pour la formation de zinciocyclopropanes à partir d’alcools allyliques ne portant qu’un seul groupement directeur, il est devenu possible d’envisager le développement énantiosélectif de la réaction. L’utilisation d’un dioxaborolane énantiopur a permis la zinciocyclopropanation avec de très bons excès énantiomères de divers alcools allyliques chiraux. La présence sur la même molécule d’un lien C–Zn nucléophile est d’un atome de bore électrophile a conduit à un échange bore-zinc in situ, formant un cyclopropylborinate énantioenrichi. La formation de ce composé bicyclique a permis d’obtenir une diastéréosélectivité parfaite. De nombreux alcools allyliques ont pu ainsi être convertis en cyclopropylborinates. Une réaction de Suzuki subséquente a permis la formation de dérivés cyclopropaniques 1,2,3-trisubstitués avec de très bons excès énantiomères et une excellente diastéréosélectivité. Les cyclopropylborinates obtenus à l’issue de la zinciocyclopropanation énantiosélective se sont avérés être des unités très versatiles puisque de nombreuses méthodes ont pu être développés pour leur fonctionnalisation. / 1,2,3-Substituted cyclopropanes are useful compounds present in several chemical domains. This thesis considers both the diastereo- and enantioselective synthesis of these compounds, particularly focusing on zincocyclopropanation methodologies. This method relies on a gem-diorganozinc carbenoid undergoing a Simmons-Smith type cyclopropanation. This method is advantageous due to its diastereoselectivity, forming the cyclopropylzinc adduct, where the zinc atom is cis relative to the directing group involved in the cyclopropanation. In this reaction, the existence of a competitive pathway involving a monoorganozinc reagent dramatically decreased the efficiency of the zincocyclopropanation. Reactivity studies, and screening of numerous conditions for the formation of the carbenoids highlighted the crucial parameters favouring the zincocyclopropanation reaction. This work demonstrated that the outcome of the reaction strongly depends on the nature of the carbenoid used, the temperature, and the presence of ZnI2 in the reaction mixture. Due to these findings, zincocyclopropanation was extended to allylic alcohols bearing one directing group only (i.e. not derived from 1,4-butenediol). As predicted, under these optimized conditions the zincocyclopropanation was highly cis-diastereoselective. To functionalize these cyclopropylzinc reagents many in situ functionalization reactions were developed. All these methods demonstrated total retention of the diastereoselectivity, and as such, the versatility of zincocyclopropanation for the synthesis of 1,2,3-susbtituted cyclopropanes is demonstrated. With a diastereoselective method in hand for the synthesis of 1,2,3-substituted cyclopropanes, we explored the development of an enantioselective version for this reaction. The use of a dioxaborolane-based ligand allowed the zincocyclopropanation of various allylic alcohols with high enantioselectivity. The presence of a nucleophilic C-Zn bond and an electrophilic boron center within the same molecule led to an in situ zinc-boron exchange and the formation of a cyclopropylborinate. This intramolecular zinc to boron exchange is responsible of the perfect diastereoselectivity of the reaction. These cyclopropylborinates were submitted to a Suzuki cross-coupling reaction leading to various 1,2,3-substituted cyclopropane with high enantioselectivities and excellent diastereoselectivities. These cyclopropylborinates are versatile intermediates as other functionalization reactions have been developed for these compounds.
62

Design, synthesis and biological evaluation of new platelet aggregation inhibitors and novel methodologies for the preparation of CF₂R containing molecules / Synthèse et évaluation biologique de nouveaux inhibiteurs de l'agrégation plaquettaire et nouvelles méthodologies pour la préparation de molécules contenant des motifs CF₂R

Khalaf, Ali 21 February 2013 (has links)
Dans la première partie nous décrivons la synthèse et l'évaluation biologique de nouveaux inhibiteurs de l'agrégation plaquettaire, composés dont la structure a été établie en partant du 12-HETE et du 13-HODE. Dans la seconde partie nous développons de nouvelles méthodologies pour la préparation de molécules contenant des motifs CF₂R. Tout d'abord une stratégie très flexible a été mise au point pour la préparation de composés gem-difluorobisaryliques et de leurs analogues hétéroaromatiques. Elle est basée sur l'emploi d'intermédiaires gem-difluoropropargyliques faciles d'accès. Par une séquence de Diels-alder-aromatisation on obtient les molécules cibles de la première série. Pour la seconde, des réactions de cycloaddition dipolaire 1,3 ont été utilisées. A partir de ces intermédiaires, des chimiothèques ciblées de molécules fluorées ont été préparées. Nous nous sommes intéressés ensuite à la synthèse de composés fluorés fonctionnalisés et chiraux à travers des réactions d'organocatalyse asymétrique. A partir d'énals gem-difluorés des réactions de Diels-Alder et des additions 1,4 asymétriques ont été réalisées avec succès. / The first part of the thesis deals with the synthesis and biological evaluation of new platelets aggregation inhibitors, based on 12-HETE, 13-HODE and their analogues. In the second part we are interested in novel methodologies for the preparation of CF₂-containing molecules : First, a flexible strategy for the synthesis of gem-difluoro-bisarylic derivatives and heteroaromatic analogues was designed based on the easy synthesis and the reactivity of gem-difluoro propargylic intermediates, which by Diels-Alder cycloaddition and 1,3-dipolar cycloadditions afforded respectively the bisarylic and mixed arylic heteroarylic scaffolds. In addition, two small libraries were constructed around a bisarylic scaffold as representative examples. Second, we were interested in the synthesis of optically active functionalized molecules containing a gem-difluoro group, using asymmetric organocatalysis protocols. After preparation of the gem-difluoro enals, from their difluoropropargylic precursors, asymmetric organocalytic Diels-Alder cycloaddition and 1,4-conjugated additions were successfully performed.
63

Synthèse diastéréosélective et énantiosélective de dérivés cyclopropaniques 1,2,3-substitués à l’aide de carbénoïdes gem-dizinciques

Zimmer, Lucie 12 1900 (has links)
Les dérivés cyclopropaniques 1,2,3-substitutés sont des composés intéressants dans de nombreux domaines de la chimie. Au cours de cet ouvrage, nous nous sommes intéressés à la synthèse, tout d’abord diastéréosélective puis énantiosélective de ces composés. Nous nous sommes en particulier intéressés à l’utilisation de la zinciocyclopropanation pour l’obtention de ces dérivés cyclopropaniques 1,2,3-substitutés. Cette méthode consiste en l’utilisation d’un carbénoïde gem-dizincique pour effectuer une réaction de type Simmons-Smith. Cette stratégie a l’avantage d’être diastéréosélective favorisant la formation du zinciocyclopropane dont l’atome de zinc est dans une configuration cis avec le groupement directeur qu’est l’oxygène allylique basique. Lors de cette réaction, l’existence d’une réaction compétitive avec un réactif monozincique diminuait l’utilité de la zinciocyclopropanation. L’issue de la réaction s’est avérée dépendre fortement de la nature du carbénoïde utilisé, de la température réactionnelle et de la présence de ZnI2 dans le milieu. L’étude par GCMS de nombreuses conditions pour la formation des différents carbénoïdes a permis d’identifier les paramètres clés conduisant à la zinciocyclopropanation. Ces découvertes ont notamment permis d’étendre la réaction de zinciocyclopropanation aux alcools allyliques portant un seul groupement directeur (ie. non dérivé du 1,4-buténediol). Dans ces conditions, la réaction s’est avérée extrêmement diastéréosélective favorisant la formation du zinciocyclopropane dont l’atome de zinc est dans une configuration cis avec le groupement directeur. Afin de fonctionnaliser les zinciocyclopropanes ainsi obtenus, plusieurs réactions de fonctionnalisation in situ ont été développées. Chacune de ces méthodes a montré une conservation totale de la diastéréosélectivité obtenue lors de la réaction de zinciocyclopropanation. La versatilité de la zinciocyclopropanation a donc été démontrée. Avec une méthode diastéréosélective efficace pour la formation de zinciocyclopropanes à partir d’alcools allyliques ne portant qu’un seul groupement directeur, il est devenu possible d’envisager le développement énantiosélectif de la réaction. L’utilisation d’un dioxaborolane énantiopur a permis la zinciocyclopropanation avec de très bons excès énantiomères de divers alcools allyliques chiraux. La présence sur la même molécule d’un lien C–Zn nucléophile est d’un atome de bore électrophile a conduit à un échange bore-zinc in situ, formant un cyclopropylborinate énantioenrichi. La formation de ce composé bicyclique a permis d’obtenir une diastéréosélectivité parfaite. De nombreux alcools allyliques ont pu ainsi être convertis en cyclopropylborinates. Une réaction de Suzuki subséquente a permis la formation de dérivés cyclopropaniques 1,2,3-trisubstitués avec de très bons excès énantiomères et une excellente diastéréosélectivité. Les cyclopropylborinates obtenus à l’issue de la zinciocyclopropanation énantiosélective se sont avérés être des unités très versatiles puisque de nombreuses méthodes ont pu être développés pour leur fonctionnalisation. / 1,2,3-Substituted cyclopropanes are useful compounds present in several chemical domains. This thesis considers both the diastereo- and enantioselective synthesis of these compounds, particularly focusing on zincocyclopropanation methodologies. This method relies on a gem-diorganozinc carbenoid undergoing a Simmons-Smith type cyclopropanation. This method is advantageous due to its diastereoselectivity, forming the cyclopropylzinc adduct, where the zinc atom is cis relative to the directing group involved in the cyclopropanation. In this reaction, the existence of a competitive pathway involving a monoorganozinc reagent dramatically decreased the efficiency of the zincocyclopropanation. Reactivity studies, and screening of numerous conditions for the formation of the carbenoids highlighted the crucial parameters favouring the zincocyclopropanation reaction. This work demonstrated that the outcome of the reaction strongly depends on the nature of the carbenoid used, the temperature, and the presence of ZnI2 in the reaction mixture. Due to these findings, zincocyclopropanation was extended to allylic alcohols bearing one directing group only (i.e. not derived from 1,4-butenediol). As predicted, under these optimized conditions the zincocyclopropanation was highly cis-diastereoselective. To functionalize these cyclopropylzinc reagents many in situ functionalization reactions were developed. All these methods demonstrated total retention of the diastereoselectivity, and as such, the versatility of zincocyclopropanation for the synthesis of 1,2,3-susbtituted cyclopropanes is demonstrated. With a diastereoselective method in hand for the synthesis of 1,2,3-substituted cyclopropanes, we explored the development of an enantioselective version for this reaction. The use of a dioxaborolane-based ligand allowed the zincocyclopropanation of various allylic alcohols with high enantioselectivity. The presence of a nucleophilic C-Zn bond and an electrophilic boron center within the same molecule led to an in situ zinc-boron exchange and the formation of a cyclopropylborinate. This intramolecular zinc to boron exchange is responsible of the perfect diastereoselectivity of the reaction. These cyclopropylborinates were submitted to a Suzuki cross-coupling reaction leading to various 1,2,3-substituted cyclopropane with high enantioselectivities and excellent diastereoselectivities. These cyclopropylborinates are versatile intermediates as other functionalization reactions have been developed for these compounds.
64

Jämförelse av natrium-resultat mellan patientnära instrument (GEM Premier 5000) och central laboratoriet instrument (Advia Chemistry XPT) på Universitetssjukhus Örebro. Finns det signifikant skillnad? / Comparison of sodium results between point of care analyzer (GEM Premier 5000) and central laboratory analyzer (Advia Chemistry XPT) at Örebro University Hospital. Is there a significant level difference?

Bonilla Guerrero, Jader Alfredo January 2021 (has links)
Bakgrund: Natrium (Na+) är en viktig elektrolyt i kroppen, och analyseras bland annat för att kunna bedöma patientens tillstånd och för att avgöra om akut behandling är nödvändigt. Analysen av Na+ på intensivvårdsavdelningen (IVA) i Örebro sker med hjälp av GEM Premier 5000, vilket är ett patientnära instrument som använder direkt metod för analys av helblod. Vid patientprovsjämförelse skickas provet vidare till centrallaboratoriet där plasman analyseras genom indirekt metod på Advia Chemistry XPT. Avvikelse mellan metoderna får inte överstiga 3%, annars måste orsaken utredas.  Syfte: Syftet med arbetet är att undersöka om det finns en systematisk skillnad på natrium-resultat mellan patientnära instrument, Gem Premier 5000 och centrallaboratoriets instrument, Advia Chemistry XPT hos olika patientgrupper. Metod: Mätning utfördes på blodprover tagna i litium-heparin rör på 60 deltagare, varav 30 var friska blodgivare (grupp 1) och resterande 30 bestod av inneliggande patienter (IVA) samt njurdialys-patienter, (grupp 2). Proverna analyserades för natrium i helblod på GEM Premier 5000 och strax därefter analyserades natrium, albumin, totalt protein, C-reaktivt protein (CRP), glukos och triglycerider i plasma på Advia Chemistry XPT. Resultat: Advia Chemistry XPT gav en högre medelkoncentration av Na+ (139 mmol/L) än GEM Premier 5000 (138 mmol/L) sett till samtliga deltagare. Procentuella skillnaden för natrium mellan metoderna översteg 3% för 3 deltagare i grupp 1 respektive hos hälften av deltagarna i grupp 2.   Slutsats: Na+ resultat på Advia Chemistry XPT var högre än på GEM Premier 5000 för alla deltagare. Skillnaden var större hos patienter med hög grad av sjuklighet. Detta antyder att nuvarande acceptabla avvikelse på 3% bör höjas till 5%, för att antal avvikande värden ska reduceras till nästan samma för båda grupper. Detta måste övervägas och implementeras i verksamheten. / Background: Sodium (Na +) is an important electrolyte in the body, and is analyzed, among other things, to be able to assess the patient's condition in the intensive care unit (IVA) and to determine if emergency treatment is necessary. The analysis of Na + on IVA is done with the help of GEM Premier 5000, which is a patient-centered instrument and uses a direct method for analysis of whole blood. For patient sample comparison, the sample is sent to the central laboratory where the plasma is analyzed by indirect method on Advia Chemistry XPT. Deviation between the methods must not exceed 3%, otherwise the cause must be investigated. Aim: The aim of the study is to investigate whether there is a systematic difference in Sodium results between patient-related instruments, Gem Premier 5000 and the central laboratory's instrument, Advia Chemistry XPT in different patient groups. Method: Measurement was performed on blood samples taken in Lithium Heparin tubes of 60 participants, of which 30 were healthy blood donors (group 1) and the remaining 30 consisted of inpatients (IVA) and kidney dialysis patients, (group 2). The samples were analyzed for sodium on GEM Premier 5000 and shortly thereafter for sodium, albumin, total protein, C-reactive protein (CRP), glucose and triglycerides on Advia Chemistry XPT. Results: Advia Chemistry XPT gave a higher concentration of Na + (139 mmol / L) than GEM Premier 5000 (138 mmol / L) for all participants. The percentage difference of Na between the methods differed for 3 participants in group 1 while it differed for half of the participants in group 2. Conclusion: Na + results on Advia Chemistry XPT were higher than on GEM Premier 5000 for all participants. The difference was greater in patients with a high degree of morbidity. This suggests that the current acceptable deviation of 3% should be increased to 5%, in order to reduce the number of deviating values ​​to almost the same for both groups. This must be taken into account and implemented in the business.
65

Text-Driven Fashion Image Manipulation with GANs : A case study in full-body human image manipulation in fashion / Textdriven manipulation av modebilder med GANs : En fallstudie om helkroppsbildsmanipulation av människor inom mode

Dadfar, Reza January 2023 (has links)
Language-based fashion image editing has promising applications in design, sustainability, and art. However, it is considered a challenging problem in computer vision and graphics. The diversity of human poses and the complexity of clothing shapes and textures make the editing problem difficult. Inspired by recent progress in editing face images through manipulating latent representations, such as StyleCLIP and HairCLIP, we apply those methods in editing the images of full-body humans in fashion datasets and evaluate their effectiveness. First, we assess different methodologies to find a latent representation of an image via Generative Adversarial Network (GAN) inversion; then, we apply three image manipulation schemes. Thus, a pre-trained e4e encoder is initially utilized for the inversion process, while the results are compared to a more accurate method, Pivotal Tuning Inversion (PTI). Next, we employ an optimization scheme that uses the Contrastive Language Image Pre-training (CLIP) model to guide the latent representation of an image in the direction of attributes described in the input text. We address the problem of the accuracy and speed of the process by incorporating a mapper network. Finally, we propose an optimized mapper called Text-Driven Garment Editing Mapper (TD-GEM) to achieve high-quality image editing in a disentangled way. Our empirical results show that the proposed method can edit fashion items for changing color and sleeve length. / Språkbaserad bildredigering inom mode har lovande tillämpningar inom design, hållbarhet och konst. Det betraktas dock som ett utmanande problem inom datorseende och grafik. Mångfalden och variationen av mänskliga poser och komplexiteten i klädform och texturer gör redigeringsproblemet svårt. Inspirerade av den senaste utvecklingen inom redigering av ansiktsbilder genom manipulation av latenta representationer, såsom StyleCLIP och HairCLIP, tillämpar vi dessa metoder för att redigera bilderna av fullständiga mänskliga kroppar i mode-dataset och utvärderar deras effektivitet. Först jämför vi olika metoder för att hitta en latent representation av en bild via så kallade Generative Adversarial Network (GAN) inversion; sedan tillämpar vi tre bildmanipulationsscheman. En förtränad (eng: pre-trained) e4e-encoder model används först för inversionsprocessen, medan resultaten jämförs med en mer exakt metod, Pivotal Tuning Inversion (PTI). Därefter använder vi en optimeringmetod som använder Contrastive Language Image Pre-training (CLIP) -modell för att vägleda den latenta representationen av en bild i riktning mot attribut som beskrivs i inmatningstexten. Vi tar upp problemet med noggrannhet och hastigheten i processen genom att integrera en mapper-nätverk. Slutligen föreslår vi en optimerad mapper som kallas TD-GEM för att uppnå högkvalitativ bildredigering på ett lösgjort sätt. Våra empiriska resultat visar att den föreslagna metoden kan redigera modeobjekt för att ändra färg och ärmens längd.
66

Gasoline‐Ethanol‐Methanol (GEM) Ternary Fuel Blend as an Alternative Passenger Car Fuel in Sweden

Tsirakos, Sebastiaan Nikolas January 2017 (has links)
This paper discusses the potential of gasoline, ethanol and methanol ternary blend as an alternative passenger car fuel in Sweden. Sweden has set various targets aimed to reduce its GHG emissions and to increase the share of renewables in the transportation sector. Nevertheless, the majority of the energy consumed in the road transportation sector still comes from fossil fuels. In order to replace the energy supply of fossil fuels by more renewable fuels, the potential of alternative renewable fuels needs to be explored. Therefore, the potential of a domestically produced ternary blend of Gasoline‐Ethanol‐ Methanol (GEM) fuel blend is analysed in this report. In order to test whether it has the potential to become a successful alternative fuel, an analysis is performed on the: methanol and ethanol production potential from domestic second‐generation feedstocks, the selection of the most suitable production pathways of the biofuels, the potential for a Swedish GEM fuel distribution infrastructure, the economic competitiveness of GEM fuel, and lastly on the environmental impact of the shift from cars running on neat gasoline to GEM fuel. In order to perform the analysis, two scenarios are developed for projecting the share of the GEM cars(cars running on GEM fuel blends) in the Swedish passenger car fleet, considering a time horizon from 2017 to 2030. In Scenario 1, a high share of passenger cars running on GEM fuel is obtained with 22 percent by 2030. In Scenario 2, a low share of cars running on GEM fuel is obtained with 17 percent by 2030. In both scenarios, the passenger cars running on GEM fuel take over the share of cars running on gasoline. The scenarios serve to project the energy demand for GEM fuels. By 2030, the projected energy demand for GEM fuels is 9.7 and 7.5 TWh for Scenario 1 and Scenario 2, respectively. From the biofuel potential studies, it can be concluded that the production potential of the alcohol fuels, derived from currently untapped domestic secondary resources, exceeds the projected energy demand of 9.7 and 7.5 TWh in 2030. According to this thesis, the production potential of 2nd generation ethanol and methanol are 36 and 61.1 TWh, respectively, by 2030. Moreover, the study shows that the majority of the existing fuel distribution network of E85 and gasoline, which is forecasted to have a significant overcapacity in the same time‐span as the scenarios, can be utilized in a GEM fuel distribution network. As a consequence, no major investments are required to develop a Swedish GEM fuel distribution network. Regarding the selection of the biofuel production pathways, this study indicates the most suitable way of producing methanol is by black‐liquor gasification. Regarding second‐generation ethanol, this thesis indicates that the fermentation forestry residues is the most beneficial production pathway. The biofuel production pathways are selected based on the energy yield ratios, the biofuel production cost and biomass feedstock cost. Moreover, this study demonstrates that under the current Swedish policies, GEM fuels blends are economic competitive with gasoline and E85. In order to test the economic competitiveness, a pay‐off curve was developed based on the pump price of gasoline and fuel economy of GEM fuel blends. This study shows the pump prices of GEM fuel blends pay‐off in comparison to gasoline. This analysis indicates that the pump prices of GEM fuel blends lays between 0.87 and 0.92 euro per liter. Regarding the environmental impact, this study indicates that the amount of GHG emissions avoided varies between 10.1 and 13.3 million metric tons CO2eq in Scenario 1. In Scenario 2, the amount of GHG emissions that can be avoided varies between 8.6 and 11.3 million metric tons CO2eq. Moreover, this study indicates that high methanol containing GEM fuel blend are more favourable in terms of biomass utilization, and high ethanol containing GEM fuel blends are more favourable in terms of economy and GHG savings.
67

Influence of meteorological network density on hydrological modeling using input from the Canadian Precipitation Analysis (CaPA)

Abbasnezhadi, Kian 31 March 2017 (has links)
The Canadian Precipitation Analysis (CaPA) system has been developed by Environment and Climate Change Canada (ECCC) to optimally combine different sources of information to estimate precipitation accumulation across Canada. The system combines observations from different networks of weather stations and radar measurements with the background information generated by ECCC's Regional Deterministic Prediction System (RDPS), derived from the Global Environmental Multiscale (GEM) model. The main scope of this study is to assess the importance of weather stations when combined with the background information for hydrological modeling. A new approach to meteorological network design, considered to be a stochastic hydro-geostatistical scheme, is proposed and investigated which is particularly useful for augmenting data-sparse networks. The approach stands out from similar approaches of its kind in that it is comprised of a data assimilation component included based on the paradigm of an Observing System Simulation Experiment (OSSE), a technique used to simulate data assimilation systems in order to evaluate the sensitivity of the analysis to new observation network. The proposed OSSE-based algorithm develops gridded stochastic precipitation and temperature models to generate synthetic time-series assumed to represent the 'reference' atmosphere over the basin. The precipitation realizations are used to simulate synthetic observations, associated with hypothetical station networks of various densities, and synthetic background data, which in turn are assimilated in CaPA to realize various pseudo-analyses. The reference atmosphere and the pseudo-analyses are then compared through hydrological modeling in WATFLOOD. By comparing the flow rates, the relative performance of each pseudo-analysis associated with a specific network density is assessed. The simulations show that as the network density increases, the accuracy of the hydrological signature of the CaPA precipitation products improves hyperbolically to a certain limit beyond which adding more stations to the network does not result in further accuracy. This study identifies an observation network density that can satisfy the hydrological criteria as well as the threshold at which assimilated products outperforms numerical weather prediction outputs. It also underlines the importance of augmenting observation networks in small river basins to better resolve mesoscale weather patterns and thus improve the predictive accuracy of streamflow simulation. / May 2017
68

Um discurso sobre a escolarização da língua materna: língua, linguagem e lingua(gem) / A discourse on the schooling of the native language: language, language and language

Favaretto, Simone Aparecida Conceição 17 April 2013 (has links)
Este estudo teve o objetivo de problematizar a maneira como o ensino de língua materna pode funcionar como forma de modelar as subjetividades contemporâneas, nas interações vivenciadas pela criança-aluno que ocorrem na escola, da mesma forma que esse ensino evidencia a modelação das redes locais em relação ao sistema nacional. Em um diálogo cauteloso entre Michel Foucault, a Psicanálise e a Linguística, a teia discursiva que se estrutura a partir de tema tão complexo foi analisada, assim como sua forma de captura dos sujeitos no ambiente escolar e no próprio discurso educacional em vigor. Da análise do discurso foram utilizados elementos para compreender e fazer viver os saberes, postos no currículo de língua portuguesa de uma rede municipal do sistema educacional brasileiro, os quais, tratados como discurso de seus atores sociais sobre o manejo no ensino da língua materna, responderam às seguintes questões: Qual a relevância da comunicação, da linguagem, da língua e dos sujeitos no ensino de língua materna? Como se entende a formação do sujeito de linguagem? Quais são as práticas discursivas desejadas na articulação sujeitos-atores e língua, nas propostas de ensino da língua materna? Qual a importância das diferenças individuais nas políticas de ensino de língua materna? A delimitação dos referenciais teóricos que sustentam o ensino de língua materna como objeto de conhecimento e como estratégia de governamentalidade, no ambiente escolar, a perspectiva do currículo como documento de identidade e a apresentação da rede em discurso sobre o ensino pro-posto desencadearam o entrecruzamento das finalidades, objetivos, conteúdos e orientações didáticas, com os sentidos de língua, linguagem e infância materializados, permitindo pensar que a sujeição às diretrizes nacionais apagou o percurso histórico e a singularidade da rede local, ao mesmo tempo que o controle do discurso prescindiu da subjetividade como agente de expressão. Deste estudo decorreu a constatação de que a língua e a linguagem compõem o cenário de tensões entre os dispositivos de poder e o funcionamento dos sujeitos, assim como a forma pensada de ensinar escolariza a língua e aprisiona a ela e a seus agentes, o que faz pensar que a diferenciação entre língua e linguagem não é algo dispensável de reflexão nos dias de hoje. / This study aimed to discuss how the teaching of native language can function as a way of modeling the contemporary subjectivities, the interactions experienced by the child-student in the school likewise that teaching emphasizes the modeling education networks of cities in compared to the national system. In a cautious dialogue between Michel Foucault, psychoanalysis and linguistics, the discursive structure from subject as complex was analyzed as well as their way of capturing the subject in the school environment and the own educational discourse in force. Of discourse analysis were used to understand the elements and the knowledge, put in the curriculum of portuguese language teaching in the a municipal educational system, which, treated as social actors talk about their management in native language teaching, answered the following questions: What is the relevance of communication, speech, language and subjects in native language teaching? What is the formation of the subject of language? What are the discursive practices desired joint subject-actors and language in the proposed teaching of native language? What is the importance of individual differences in the policies of native language teaching? The demarcation of the theoretical frameworks that underpin the teaching of native language as an object of knowledge and as a strategy of The demarcation of the theoretical frameworks that underpin the teaching of native language as an object of knowledge and as a strategy of governmentality, in the school environment, the prospect of the curriculum as an identity document and presentation of network discourse about teaching proposed triggered the intersection of purposes, goals, content and instructional guidance with the different meanings of language and childhood materialized, thinking that subjection to national guidelines erased the historical background and the uniqueness of the local school system, while control the discourse of subjectivity dispenses as agent expression. This study took the realization that the language set the scene of tensions between the power devices and operation of the subject, as well as the form designed to teach the language schooling and imprisons her and her agents, what makes you think that differentiation between the different meanings of the word language is not something dispensable for reflection today.
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Caractérisation et modélisation du comportement mécanique d'éléments d'étanchéité par presse garniture / Characterization of the mechanical behaviour and modelling of sealing elements by stuffing-box

Viéville, Émilie 02 February 2018 (has links)
L'impact des émissions fugitives sur l'environnement est un enjeu capital pour les industries. Ainsi, de nombreuses réglementations et normes sont établies afin de prévenir des risques et limiter leurs impacts. L'une des sources majeures de ces émissions provient de la robinetterie industrielle. Dans ce domaine, l'un des systèmes les plus communs est le presse-garniture. Dans le secteur de l'Energie, l'étanchéité peut être garantie sur les éléments mobiles par un empilement de bagues en Graphite Expansé Matricé (GEM); matériau relativement souple, plébiscité pour ses caractéristiques et ayant une structure macroscopique particulière. Ces travaux de thèse s'intéressent à la compréhension du comportement mécanique complexe des solutions d'étanchéité de type GEM. L'objectif est de déterminer le comportement mécanique de ces garnitures afin de prédire leur étanchéité. Dans le but de caractériser ce comportement, diverses campagnes d'essais sont menées sur des joints en situation. Ainsi, sur la base d'un montage existant et d'un dispositif développé spécifiquement pour cette étude, la caractérisation de ce type de joints est effectuée via des essais de compression charge-décharge et cyclique. La base de données qui en résulte permet le développement d'un modèle numérique apte à décrire le comportement complexe de ces systèmes presse-garnitures. Ce modèle phénoménologique de type Hyperélasto-Hystérésis (HH) correspond à une loi additive en contrainte avec une contribution hyperélastique et une contribution hystérétique. La comparaison des réponses expérimentales et numériques du joint, dans le cadre de l'étude d'un seul joint mais également pour des empilements, est discutée. / The impact of fugitive emissions leakage rate on the environment is an essential issue for industries. Therefore, many regulations and standards are created to prevent risks and to limit their impacts. One of these major sources of fugitive emissions comes from industrial valves. In the Valve Industrie, the tightness of stem are often ensured by stuffing box seal. In the energy sector, the tightness could be ensure with compression packing which is manufactured in exfoliated graphite; which is a relatively flexible material, endorsed for its characteristics and having a particular macroscopic structure. The aim of this study is to improve the knowledge of the complex mechanical behaviour of compression packing in exfoliated graphite. The aim is to determinate the mechanical behaviour of these packings in order to predict their tightness. To characterize this behaviour, various test campaigns are conducted on seals in situation. Thus, based on an existing apparatus and a device developed specifically for this study, the characterization of this kind of packing is performed through loading-unloading and cyclic compression tests. A numerical model which is able to describe a complexe mechanical behaviour of compression packing, is performed thanks to resulting database. This Hyperelasto-Hysteresis phenomenological model corresponds to an additive decomposition in stress with an hyperelastic contribution and an hysteretic contribution. The comparison of the experimental and numerical responses of the seal, as part of the study a single seal but also of a packing, is discussed.
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Overlay Window Management: User interaction with multiple security domains

Feske, Norman, Helmuth, Christian 14 November 2012 (has links) (PDF)
Graphical user interfaces for high-assurance systems must fulfill a range of security requirements such as protected and reliable presentation, prevention of unauthorized cross-domain talk, and prevention of user-input eavesdropping. Additionally, it is desirable to support legacy applications running in confined compartments. Standard isolation methods such as virtual-machine monitors provide one frame buffer per security domain, where each frame buffer is managed by one legacy window system. This raises the question of how to safely integrate multiple (legacy) window systems and protect the displayed data while preserving the usability of modern user interfaces. Our paper describes the OverlayWindow System, a general mechanism for multiplexing windows of multiple distinct window systems into the host frame buffer. Thus, each legacy window appears to the user as one corresponding host window that can be moved and resized. To achieve this, only slight modifications of the legacy window system are required whereby, the source code does not have to be available. Our implementation of an Overlay Window System successfully multiplexes Linux, GEM and native L4 applications.

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