Les diradicaux sont des espèces réputées extrêmement instables. A titre d'exemple, le<br />cyclobutanediyle qui est l'archétype de ce genre d'espèce en série carbonée n'a en effet pu<br />être isolé que dans des matrices à basse température.<br />La première partie de cet exposé sera consacrée aux diradicaux formés des éléments<br />lourds des groupes principaux.<br />Nous montrerons dans une introduction bibliographique comment l'utilisation de ces<br />hétéroéléments a permis l'isolation du premier diradical localisé singulet stable basé sur un<br />squelette formé uniquement des hétéroéléments bore et phosphore.<br />Dans un deuxième chapitre, nous nous intéresserons aux isomères de ce diradical, en<br />particulier ses isomères de valence. Après un bref retour sur le concept, nous étudierons les<br />facteurs qui permettent de stabiliser les différents isomères déjà connus. Nous montrerons<br />ensuite comment il a été possible d'isoler de nouveaux isomères.<br />Dans un troisième chapitre, nous nous arrêterons sur deux isomères de valence<br />particuliers et étudierons l'isomérie d'élongation (bond-stretch isomerism). Dans notre cas,<br />deux isomères qui ne diffèrent que par la longueur d'une liaison sont en équilibre. Grâce à<br />des études de RMN à température variable, nous mettrons en évidence l'influence des<br />facteurs électroniques dans cet équilibre.<br />Ce travail nous a amenés à nous interroger sur la possibilité de préparer un diradical<br />purement organique formé uniquement d'éléments de la seconde ligne : carbone et azote.<br />Cette réflexion nous a conduits à mettre au point une nouvelle méthode de synthèse de sels<br />d'iminium et d'imidazolinium que nous présenterons dans une deuxième partie.

Morbidity and mortality attributable to asthma arise mainly from contraction of airway smooth muscle (ASM) and resulting bronchospasm. Bronchospasm that is induced in the laboratory is easily reversed by a spontaneous deep inspiration (DI) whereas bronchospasm that occurs spontaneously in asthma is not. In response to a spontaneous DI, contracted ASM fluidizes rapidly and then resolidifies slowly, but molecular mechanisms accounting for these salutary bronchodilatory responses -and their dramatic breakdown in asthma- are unknown. Using a multi-scale approach, I show here that both the baseline contractile force and the fluidization response of ASM are independent of the cytoskeletal protein zyxin, whereas the resolidification response is zyxin-dependent. At the levels of the stress fiber, the isolated cell, and the integrated airway, zyxin acts to stabilize the contractile apparatus and promote the resolidification response. More than just the motor of contraction, ASM is thus viewed in the broader context of a self-healing active material wherein resolidification and its molecular determinants contribute to the biology of bronchospasm.

Although asthma is primarily thought to be an inflammatory disease of the airways, it has recently been hypothesized that the altered mechanical environment of an asthmatic airway may contribute to the development of the disease through changes in cellular phenotype. In regards to this hypothesis, the effects of stretch on airway smooth muscle (ASM) have previously been investigated using 2D cell culture. However, over the last few years there has been an increasing appreciation to the importance of the role of the 3D extracellular matrix in the regulation of cellular response. For this reason, the work presented in this thesis covers the development of a device capable of high-throughput investigations into the effects of acute or chronic, uniaxial, oscillatory mechanical strain on an array of miniature, 3D, multi-cell, tissue-engineered constructs.

Valvular interstitial cells (VICs) are responsible for the maintenance of heart valve leaflet structure, however their responses to mechanical loading are not fully understood. Further characterization of VIC responses with regards to phenotype (quiescent or activated via ?-smooth muscle actin [?-SMA]) and communication (through gap junction proteins connexins 43 and 26) were studied. Tissue strips from porcine aortic, pulmonary, and mitral valves were cyclically stretched in the circumferential direction at normal and above normal membrane tensions for 48 hours at 1 Hz, 37°C, and 5% CO2. Unloaded tissues were statically incubated concurrently with loaded tissues, and fresh tissue controls were collected immediately. VIC phenotype was identified by ?- SMA via immunohistochemical staining and cell enumeration, as well as by gene expression via RT-PCR. Gap junction protein Cx43 was also evaluated via immunohistochemical staining and cell enumeration and by gene expression via RT-PCR, whereas Cx26 was evaluated using immunohistochemical staining and cell enumeration only. Within the range tested, it was found that mechanical loading did not affect ?-SMA or gap junction protein levels, nor were any differences in responses noted between valve types. However, the ?-SMA gene expression level was significantly lower in the mitral valve compared to the aortic and pulmonary valves. This may indicate a difference in the genetic response pathways among the valves, but not in the functional outcomes. This difference may be explained by embryological origins, since the mitral valve, unlike the aortic and pulmonary valves, contains only VICs and no neural crest cells.

As school accountability intensifies, school districts strive not only to prepare their students to meet the No Child Left Behind (NCLB) mandates, but also to prepare students for college and careers after high school. Understanding the necessary reading rigor to ensure academic success is key for educators. Although Texas opted not to adopt the Common Core Curriculum Standards and the accompanying Stretch Lexile measures for reading that require higher reading levels at each grade, Texas educators must still prepare students for academic success. This study determined how the use of more rigorous Lexile standards found in other states and associated with the Common Core Curriculum Standards would affect passing scores on Texas reading assessments in grades 6-8. The population for this study included three middle schools during the 2010 school year within one large suburban school district. State reading assessment data collected from these three schools included students' scores from grades 6, 7, and 8. A Chi-square Test for Independence determined that there was statistical significance for some groups of students in the accountability system: all students, Hispanic students, and economically disadvantaged students. Each of these groups was found to pass at a significantly lower rate when using the Stretch Lexile standard. Results were also examined in terms of political, economical, educational, and social policy implications. The policy implications discussed in this study are far-reaching for Texas educators and students, especially economically disadvantaged and Hispanic students. The higher standards can potentially trigger the school improvement process for campuses and districts failing to make NCLB's required adequate yearly progress. Additional expenses related to supplemental educational services, school choice, and professional development drain district Title I budgets due to mandatory set-aside amounts, disallowing funds for other student-centered programs. Implications for practitioners include clearly establishing intervention systems, adhering to a multi-tiered intervention system, and providing a screening tool for teachers so that progress monitoring can be accomplished for students as they move toward more rigorous reading expectations that will result in college and career preparedness.

Studies suggest that deficits in central regulation of stretch reflex thresholds (SRT) underlie both spasticity and other disorders of motor control. We investigated intra- and inter-evaluator reliability to quantify spasticity based on tonic SRT (TSRT) and the relationship between TSRT and Modified Ashworth Scale (MAS, clinical assessment of resistance to stretch). Spasticity was evaluated in 20 subjects with chronic stroke-related spasticity in two different days, by three evaluators. Twenty different velocity-dependent dynamic SRT (angle where biceps brachii EMG signal increased for a given velocity of stretch) were recorded. TSRT (excitability of motoneurons at 0&deg;/sec) was then computed. Spasticity was also estimated with MAS. Reliability was moderately good for subjects with moderately high spasticity (intra--evaluator: 0.46 to 0.68, inter--evaluator: 0.53 to 0.68). There was no correlation between TSRT and MAS since they measure different phenomena. TSRT is a promising new measure of spasticity. Further improvements for its quantification are suggested.

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Spectral graph theory is the interplay between linear algebra and combinatorial graph theory. Laplace’s equation and its discrete form, the Laplacian matrix, appear ubiquitously in mathematical physics. Due to the recent discovery of very fast solvers for these equations, they are also becoming increasingly useful in combinatorial optimization, computer vision, computer graphics, and machine learning. In this thesis, we develop highly efficient and parallelizable algorithms for solving linear systems involving graph Laplacian matrices. These solvers can also be extended to symmetric diagonally dominant matrices and M-matrices, both of which are closely related to graph Laplacians. Our algorithms build upon two decades of progress on combinatorial preconditioning, which connects numerical and combinatorial algorithms through spectral graph theory. They in turn rely on tools from numerical analysis, metric embeddings, and random matrix theory. We give two solver algorithms that take diametrically opposite approaches. The first is motivated by combinatorial algorithms, and aims to gradually break the problem into several smaller ones. It represents major simplifications over previous solver constructions, and has theoretical running time comparable to sorting. The second is motivated by numerical analysis, and aims to rapidly improve the algebraic connectivity of the graph. It is the first highly efficient solver for Laplacian linear systems that parallelizes almost completely. Our results improve the performances of applications of fast linear system solvers ranging from scientific computing to algorithmic graph theory. We also show that these solvers can be used to address broad classes of image processing tasks, and give some preliminary experimental results.

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