The academic achievement gap in the State of California has been a persistent problem. In California the achievement gap is defined as the disparity between the academic performance of white students and other ethnic groups as well as that between English learners and native English speakers, socioeconomically disadvantaged and non-disadvantaged students, and students with disabilities as compared with students without disabilities (CDE, P-16, 2008, p. 11). Jack O'Connel, State Superintendent of Public Instruction, has identified closing the achievement gap as one of the primary goals for the State of California. Research has consistently shown that children of color and children of poverty have not experienced the academic success of their white peers. Utilizing the meta-analysis of research data from Mid-continent Research for Educational Learning (McREL), this study is a quantitative review of the 21 Leadership Responsibilities and Best Practices identified by school leaders from Ceres Unified School District, more specifically, from leaders in nine high-achieving schools within the district. The nine identified schools and leaders have experienced academic success with children of color and children of poverty based on their Academic Performance Index Similar Schools Rankings. In the study, two levels of surveys were conducted. The first survey reviewed the leadership responsibilities identified by McREL and asked the study participants to rank the leadership responsibilities based on the responsibilities that they perceive to have the most significant impact on student academic achievement. Employing the results of the first survey, a second survey utilized the top five leadership responsibilities identified by the study participants. Under the umbrella of the top five responsibilities, five best practices were listed and again ranked by the participants based on their perceptions of the leadership practices that have the greatest effect on increasing student achievement. The results of this survey identified the best practices perceived by leaders of high-achieving, high poverty schools. Additionally, a questionnaire was completed by the participants to provide additional demographic data. The study results support the findings that best pedagogical practices are complimented by effective leadership. Effective leaders and leadership practices do have a positive effect on student academic achievement.

Les réactions de macrocyclisation constituent un défi pour les chimistes de synthèse, car les sélectivités pour les réactions intramoléculaires par rapport à celles intermoléculaires sont difficiles à maximiser. Celles-ci sont donc effectuées dans des milieux dilués et sont souvent lentes. La chimie en flux continu a été utilisée pour améliorer les réactions présentées dans cette thèse, car elle permet un meilleur transfert de masse qui se traduit par un mélange et un chauffage plus efficace, donc des temps de réaction plus courts. À la suite d’introductions sur les macrocycles (Chapitre 1) et sur la métathèse d’alcènes (Chapitre 2), nos efforts pour améliorer l’étape de macrocyclisation par métathèse d’alcènes d’un musc découvert par l’industrie des fragrances sont décrits au chapitre 3. Alors que les conditions rapportées ne permettaient pas de réaliser cette réaction de façon reproductible sur une échelle de plus de 100 mg, il a été possible de l’effectuer sur une échelle d’un gramme grâce à l’emploi du catalyseur approprié. La réaction a été effectuée dans un montage traditionnel (ballon à fond rond) à température ambiante pour fournir 57% du macrocycle désiré après 5 jours. En comparaison, le montage en flux continu n’a nécessité que 5 minutes de temps de résidence à 150 °C pour fournir 32% de rendement. Le second projet présenté dans cette thèse porte sur la synthèse totale de la néomarchantine A (Chapitre 5) et est précédé d’une introduction sur les composés bisbibenzyliques (Chapitre 4). Cette synthèse a permis de démontrer l’avantage d’incorporer plusieurs étapes clés en flux continu. Différentes conditions ont été investiguées pour réaliser les deux étapes de couplage C-O en début de synthèse. Les meilleurs résultats ont été obtenus avec le couplage de Chan-Evans-Lam dans un cas (34%) et la substitution nucléophile (SNAr) dans l’autre (71%), ce qui a permis de s’éloigner des conditions classiques de couplage d’Ullmann. La première macrocyclisation par métathèse d’alcènes pour la synthèse d’un composé bisbibenzylique est également rapportée. Les conditions en flux continu ont permis de réaliser la réaction en seulement 10 minutes de temps de résidence avec un rendement de 49%, ce qui est similaire au rendement obtenu dans un montage traditionnel, mais qui nécessite 17 heures de temps de réaction. Précédé d’une introduction sur la photochimie (Chapitre 6), le chapitre 7 décrit la conception et l’évaluation d’un réacteur en flux continu adapté à la macrocyclisation photochimique. Celui-ci est inspiré des réacteurs à agitation continue (CSTR), mais est aminci pour permettre une irradiation plus uniforme. Son efficacité a été démontrée par l’application de la réaction d’oxydation aérobique de thiols en disulfures. En plaçant plusieurs réacteurs en série, un rendement d’environ 47% a été obtenu peu importe l’échelle de la réaction, allant de 100 mg à 1 g. En comparaison, le montage traditionnel, le réacteur standard en flux continu (PFR) ainsi que le réacteur CSTR n’ont pas été en mesure de fournir plus de 20% du macrocycle désiré. L’étendue de la réaction a été démontrée en synthétisant différents macrocycles d’intérêt biologique ou structurel avec des rendements entre 33 % et 50 %. / Macrocyclization reactions pose a challenge for synthetic chemists because the selectivity for the intramolecular reaction over intermolecular is difficult to achieve. They are usually done in diluted medium and are often slow. Continuous flow chemistry has been used to improve the reactions developed in the present thesis by allowing better mass and energy transfer which results in more efficient mixing and heating, and thus shorter reaction times. Following introductions on macrocycles (Chapter 1) and olefin metathesis (Chapter 2), our efforts to improve the olefin metathesis macrocyclization step of a musk discovered by the fragrance industry are described in Chapter 3. While the reported conditions did not allow the reaction to be performed reproducibly on a scale greater than 100 mg, the use of the appropriate catalyst allowed us to perform the reaction on a gram scale. The reaction was carried out in batch at room temperature to provide 57% of the desired macrocycle after 5 days. In comparison, the continuous flow setup required only 5 minutes of residence time at 150 °C to provide 32% yield. The second project focuses on the total synthesis of neomarchantine A (Chapter 5) and is preceded by an introduction on bisbibenzyl compounds (Chapter 4). The goal of the synthesis was to show the advantage of integrating several key steps in continuous flow. Different conditions were investigated to carry out the two C-O bond forming steps early in the synthesis. The best results were obtained with Chan-Evans-Lam coupling in one case (34%) and a SNAr reaction in the other (71%), which allowed to deviate from the classical conditions of Ullmann coupling. The first macrocyclization by ring-closing metathesis for the synthesis of a bisbibenzyl is also reported. The continuous flow conditions produced a 49% yield of a key macrocycle, which is similar to the batch results but only required 10 minutes of residence time in flow instead of 17 hours of reaction time in batch. Preceded by an introduction on photochemistry (Chapter 6), Chapter 7 describes the design and evaluation of a continuous flow reactor suitable for photochemical macrocyclization. It is inspired by CSTR reactors but is “flattened” to allow a uniform irradiation. Its effectiveness has been demonstrated by the application of aerobic oxidation of thiols to disulfides. By placing reactors in series, a yield of 47% was obtained regardless of the scale, ranging from 100 mg to 1 g. In comparison, the batch setup as well as the CSTR and PFR reactors were not able to provide more than 20% of the desired macrocycle. The scope of the reaction was demonstrated by synthesizing different macrocycles of biological or structural interest in yields of 33-50%.

[pt] O modelo de Dois-Fluidos 1D vem sendo usado de forma abrangente em simulações industriais para prever escoamentos bifásicos em dutos. Avanços recentes na metodologia de Regime Capturing permitem a detecção das transições entre padrões de escoamento através do crescimento de instabilidades interfaciais. Contudo, devido aos procedimentos de média necessários para a redução da dimensionalidade do problema, perdas de informação tornam o modelo mal posto, i.e., perturbações de comprimentos de onda curtos são amplificados a taxas ilimitadas e soluções não físicas são obtidas. Relações de fechamento possuem um papel chave nesse problema, uma vez que estas são necessárias para fechar o sistema 1D e reintroduzem os mecanismos físicos perdidos que podem estabilizar o escoamento e tornar o modelo bem-posto. O presente trabalho propõe um modelo para o parâmetro de fluxo de quantidade de movimento da fase líquida (ou fator de forma), baseado na distribuição da velocidade do filme, que depende das grandezas locais do escoamento. A Teoria de Estabilidade Linear (LST) pode ser usada para avaliar a influência dos parâmetros de fechamento no crescimento de perturbações e na hiperbolicidade do modelo. A abordagem viscosa da análise de estabilidade diferencial de Kelvin-Helmholtz e a análise discreta de von Neumann são realizadas para avaliar relações de fechamento comumente utilizadas na literatura, bem como as formulações propostas para o parâmetro de fluxo. Simulações numéricas são realizadas, e relações de dispersão numéricas são extraídas dos resultados para verificar as previsões com os dados da LST. Uma avaliação numérica rigorosa dos novos modelos do parâmetro de fluxo com um grande banco de dados experimental é realizada. Os resultados mostraram que as correlações propostas superam os valores padrão constantes de fator de forma para avaliações de gradiente de pressão e espessura do filme de líquido. Os modelos também mostraram melhor consistência ao longo do extenso banco de dados. / [en] The 1D Two-Fluid model has been widely used in industrial simulations to predict two-phase flows in pipelines. Recent advances of the Regime Capturing methodology allow for the detection of flow pattern transitions from the onset and development of interfacial instabilities. However, due to the averaging processes required to reduce the dimensionality of the problem, the loss of information renders the model ill-posed, i.e., short wavelengths disturbances are amplified at an unbounded rate and unphysical solutions are obtained. Closure relations play a key role in this problem, since they are required to close the 1D system. Further, the reintroduction of the missing physics may stabilize the flow and render the model well-posed. The present work proposes a model for the liquid momentum flux parameter based on the liquid film velocity profile that is dependent on the local flow quantities. Linear Stability Theory (LST) can be used to assess the influence of closure parameters in the growth of disturbances and to evaluate the hyperbolicity of the model. A viscous approach of the differential Kelvin-Helmholtz and a discrete von Neumann stability analyses are performed to evaluate commonly employed closure models and the proposed formulations for the liquid momentum flux parameter. Numerical simulations are performed, and numerical dispersion relations are extracted from the results to verify the predictions against LST data. A rigorous numerical evaluation of the novel momentum flux parameter models against a large experimental database taken from the literature is carried out. Results show that the proposed models outperform the standard constant 𝐶𝐿 values for both pressure drop and liquid film thickness. The models also showed better overall consistency throughout the extensive experimental database.

Leaflet replacement in aortic valve repair (AVr) is associated with increased long-term repair failure. Hemodynamic performance and mechanical stress levels were investigated after porcine AVr with 5 types of clinically relevant replacement materials to ascertain which material(s) would be best suited for repair. Porcine aortic roots with intact aortic valves were placed in a left-heart simulator mounted with a high-speed camera for baseline valve assessment. Then, the non-coronary leaflet was excised and replaced with autologous porcine pericardium (APP), glutaraldehyde-fixed bovine pericardial patch (BPP; Synovis™), extracellular matrix scaffold (CorMatrix™), or collagen-impregnated Dacron (HEMASHIELD™). Hemodynamic parameters were measured over a range of cardiac outputs (2.5–6.5L/min) post-repair. Material properties of the above materials along with St. Jude Medical™ Pericardial Patch with EnCapTM Technology (SJM) were determined using pressurization experiments. Finite element models of the aortic valve and root complex were then constructed to verify the hemodynamic characteristics and determine leaflet stress levels. This study demonstrates that APP and SJM have the closest profiles to normal aortic valves; therefore, use of either replacement material may be best suited. Increased stresses found in BPP, HEMASHIELD™, and CorMatrix™ groups may be associated with late repair failure.

Leaflet replacement in aortic valve repair (AVr) is associated with increased long-term repair failure. Hemodynamic performance and mechanical stress levels were investigated after porcine AVr with 5 types of clinically relevant replacement materials to ascertain which material(s) would be best suited for repair. Porcine aortic roots with intact aortic valves were placed in a left-heart simulator mounted with a high-speed camera for baseline valve assessment. Then, the non-coronary leaflet was excised and replaced with autologous porcine pericardium (APP), glutaraldehyde-fixed bovine pericardial patch (BPP; Synovis™), extracellular matrix scaffold (CorMatrix™), or collagen-impregnated Dacron (HEMASHIELD™). Hemodynamic parameters were measured over a range of cardiac outputs (2.5–6.5L/min) post-repair. Material properties of the above materials along with St. Jude Medical™ Pericardial Patch with EnCapTM Technology (SJM) were determined using pressurization experiments. Finite element models of the aortic valve and root complex were then constructed to verify the hemodynamic characteristics and determine leaflet stress levels. This study demonstrates that APP and SJM have the closest profiles to normal aortic valves; therefore, use of either replacement material may be best suited. Increased stresses found in BPP, HEMASHIELD™, and CorMatrix™ groups may be associated with late repair failure.

La synthèse énantiosélective de la (+)-ambruticine S, un produit naturel antifongique a été effectuée au sein de notre groupe. Trois approches ont été développées pour la synthèse du fragment lactone (cycle A). Ces trois voies d’accès au cycle A ont pour intermédiaire commun le methyl α-D-glycopyranoside déjà porteur du diol requis et disponible commercialement à bon prix. Une désoxygénation de l’hydroxyle en C-4 et l’homologation d’un carbone de la chaine latérale en C-6 ont permis l’obtention du cycle lactonique A. Le deuxième projet est une collaboration entre le groupe Hanessian et ISIS Pharmaceuticals afin de développer de nouveaux oligonucléosides antisens. Les nucléosides antisens [4.3.0]-bicycliques cis et trans ont été synthétisés avec succès à partir d’un monosaccharide naturel commun, L-arabinose, porteur des stéréocentres requis. Un réaction clé d’allylation de Sakurai a permis d’obtenir les diastéréoisomères cis et trans dans des conditions de contrôle de type Felkin-Ahn et de contrôle par chélation respectivement. Les composés bicycliques finaux cibles ont été obtenus par une réaction d’aldol intramoléculaire catalyzéé par la proline, par métathèse de fermeture de cycle et par l’application de la méthode de Vorbrüggen pour la synthèse de nucléosides. / An enantioselective synthesis of the antifungal natural product (+)-ambruticin S has been accomplished in our group. For the synthesis of a ring A lactone fragment, three approaches were developed. They all started from commercially available and inexpensive methyl α-D-glycopyranoside, which already possesses the required diol unit. A deletion of the hydroxyl group at C-4 and a one-carbon homologation of the C-6 side chain furnished the ring A lactone. The second project is an ongoing collaboration between the Hanessian group and ISIS pharmaceuticals to develop new antisense oligonucleosides. The cis- and trans-[4.3.0]bicyclic antisense nucleosides were successfully synthesized from a common natural monosaccharide, L-arabinose, which bears the required stereocenters. A key Sakurai allylation led to the cis- and trans diastereomers under Felkin-Ahn and chelation-controlled conditions respectively. The final bicyclic targets were achieved by a practical proline-catalyzed intramolecular aldol reaction and ring-closing metathesis (RCM) strategy, and application of the Vorbrüggen method for nucleoside synthesis.

Introdução: A pressão crítica de fechamento da faringe (PCrit) é a pressão nasal em que há colapso da faringe. Conceitualmente a Pcrit reflete a contribuição anatômica na gênese da apnéia obstrutiva do sono (AOS). No entanto, a relação entre a PCrit e a anatomia das vias aéreas superiores (VAS) tem sido pouco estudada. A PCrit determinada durante o sono requer pesquisadores experientes durante a noite. A indução do sono com midazolam é usada na prática clínica para a realização de procedimentos ambulatoriais e poderia ser uma alternativa mais conveniente para se determinar a Pcrit. Porém, o midazolam pode provocar sedação além de simples indução do sono, reduzir a atividade muscular das VAS e aumentar a colapsabilidade quando comparado com o sono normal. Objetivos: 1. validar a determinação da PCrit durante o dia após a indução do sono com midazolam; 2. comparar a arquitetura do sono induzido com baixa dose de midazolam com o sono natural; 3. correlacionar a PCrit com a anatomia das VAS. Métodos: Homens com graus variados de sintomas sugestivos de AOS foram submetidos a polissonografia completa noturna, determinação da PCrit durante o sono natural e após a indução do sono com midazolam bem como tomografia computadorizada de cabeça e pescoço para avaliação das VAS. Resultados: Foram estudados 15 sujeitos com idade (média±DP) de 54 ± 10 anos, índice de massa corporal de 29,9 ± 3,9 kg/m2 e índice de apnéiahipopnéia (IAH) de 38 ± 22 (variação: 8-66 eventos/h). A indução do sono foi obtida em todos os sujeitos, utilizando doses mínimas de midazolam (mediana [intervalo interquartil]) (2,4 [2,0-4,4] mg). A PCrit durante o sono natural e induzido foram semelhantes (-0,82 ± 3,44 e -0,97 ± 3,21 cmH2O, P = 0,663) e se associaram (coeficiente de correlação intraclasse=0,92 (IC 95% 0,78-0,97 P<0,001). A distribuição das fases do sono durante sono natural e induzido foi similar, com excessão da fase 1 (10,5 ± 5,1% vs. 20,6 ± 8,1, respectivamente; P=0,001). A Pcrit determinada durante o sono natural e induzido se correlacionaram com o IAH (r=0,592, P=0,020 e r=0,576, P=0,025, respectivamente). Além disso tanto a Pcrit determinada por sono natural e induzido se correlacionaram com diversas variáveis tomográficas de VAS, incluindo a posição do osso hióide, ângulo da base do crânio e as áreas seccionais da velofaringe e hipofaringe (r variando de 0,577 a 0,686, P<0,05). A regressão linear múltipla revelou que o IAH foi independentemente associado com a Pcrit durante sono induzido, circunferência da cintura e idade (r2 = 0,785, P = 0,001). Conclusão: A PCrit determinada durante o dia com indução do sono é semelhante à determinada durante o sono natural e é um método alternativo promissor para determinar a PCrit. O sono induzido por doses baixas de midazolan promove um sono similar ao sono natural. A Pcrit determinada tanto durante o sono natural e induzido correlaciona-se com várias características anatômicas das VAS / Introduction: The pharyngeal critical closing pressure (Pcrit) is the nasal pressure at which the airway collapses. Pcrit is thought to reflect the anatomical contribution to the genesis of obstructive sleep apnea (OSA). However, the relationship between Pcrit and upper airway anatomy has been poorly investigated. Pcrit determined during sleep requires experienced investigators at night. Sleep induction with midazolam is frequently used in clinical practice during ambulatory procedure and could be a more convenient alternative to assess Pcrit. On the other hand, midazolam could induce sedation rather than sleep, decrease upper airway muscle activity and increase collapsibility compared with natural sleep. Objectives: 1. validate Pcrit determination during the day after sleep induction with midazolam; 2. compare the sleep architecture of induced sleep after low doses of midazolam with natural sleep; 3.correlate Pcrit with upper airway anatomy. Methods: Men with different severity of OSA symptoms underwent baseline full polysomnography, Pcrit determination during natural sleep and after sleep induction with midazolam and head and neck computed tomography. RESULTS: Fifteen men aged (mean±SD) 54±10ys, body mass index=29.9 ± 3.9 Kg/m2 and apnea hypopnea index=38±22, range: 8-66 events/h were studied. Sleep induction was obtained with minimum doses of midazolam (median[interquartile range] (2.4 [2.0-4.4] mg). Sleep phase distribution during natural and induced sleep was similar, except for stage 1 (10.5 ± 5.1% vs. 20.6 ± 8.1, respectively; P=0.001). Natural and induced sleep Pcrit were similar (-0.82 ± 3.44 and -0.97 ± 3.21 cmH2O, P=0.663) and closely associated (intraclass correlation coefficient=0.92 (95%CI 0.78-0.97, P<0.001). Natural and sleep induced Pcrit correlated with AHI (r=0.592, P=0.020; r=0.576, P=0.025, respectively). Pcrit determined both during natural and induced sleep were significantly associated with several tomographic variables, including hyoid position, cranial base angle and cross sectional areas of the velopharynx and hypopharynx (r range: 0.577 to 0.686, P<0.05). Multiple linear regression revealed that AHI was independently associated with induced sleep Pcrit, waist circumference and age (r2=0.785, P=0.001). Conclusion: Pcrit determined during the day with sleep induction is similar to natural sleep and is a promising alternative method to determine Pcrit. Sleep induction with small doses of midazolam promoted sleep similar to natural sleep. Pcrit determined both during natural and induced sleep correlates with several anatomical characteristics of the upper airway

This study consisted of two sheep grazed dryland pasture experiments. Experiment l compared sheep production from 3-year-old cocksfoot based pastures grown in combination with white, Caucasian, subterranean or balansa clover with a ryegrass-white clover pasture and a pure lucerne forage. Sheep liveweight gain per head from each pasture treatment and the pure lucerne stand was recorded in the 2006/07 and 2007/08 seasons. The cocksfoot-subterranean clover pasture provided equal (381 kg LW/ha in 2006) or higher (476 kg LW/ha in 2007) animal production in spring and gave the highest total animal production (646 kg LW/ha) averaged across years of the five grass based pastures. However, total annual liveweight production from lucerne was higher than any grass based pasture mainly due to superior animal production during summer when lucerne provided 42-85% higher animal production than any of the grass based pastures. In Experiment 2, the effect of stocking rate (8.3 (low) and 13.9 (high) ewes + twin lambs/ha) and time of closing in spring on lamb liveweight gain, pasture production and subterranean clover seedling populations was monitored over 2 years for a dryland cocksfoot-subterranean clover and ryegrass-subterranean clover pasture in Canterbury. In both years, twin lambs grew faster (g/head/d) in spring at low (327; 385) than high (253; 285) stocking rate but total liveweight gain/ha (kg/ha/d) was greater at high (7.26; 7.91) than low (5.43; 6.38) stocking rate. Ewes also gained 0.5 and 1.5 kg/head at the low stocking rate in 2006 and 2007 respectively but lost 0.2 kg/head in 2006 and gained 0.3 kg/head at high stocking rate in 2007. Mean subterranean clover seedling populations (per m²) measured in autumn after grazing treatments in the first spring were similar at both low (2850) and high (2500) stocking rate but declined with later closing dates in spring (3850, 2950, 2100 and 1700 at 2, 4, 6, 8 weeks after first visible flower). Seedling populations measured in autumn after grazing treatments in the second spring were also unaffected by stocking rate (low 1290, high 1190) but declined with later closing dates in spring (1470, 1320 and 940 at 3, 5 and 8 weeks after first flowering, respectively). The effect of stocking rate and closing dates in spring on pasture and clover production in the following autumn was similar to the effects on seedling numbers in both years. However, clover production in the following spring was unaffected by stocking rate or closing date in the previous year at the relatively high seedling populations generated by the treatments. This was presumably due to runner growth compensating for lower plant populations in pastures that were closed later in spring. Subterranean clover runner growth in spring may not compensate in a similar manner if seedling numbers in autumn fall below 500/m². Mean annual dry matter production from cocksfoot and ryegrass pastures grown with and without annual clovers pasture production ranged from 6.4 to 12.4 t DM/ha/y but stocking rate (8.3 vs. 13.9 ewes/ha) during spring did not affect annual pasture production. Pastures overdrilled with annual clovers yielded 23-45% more dry matter production than pastures grown without annual clovers. The study confirms the important role of subterranean clover in improving pasture production and liveweight gains of sheep in dryland cocksfoot and ryegrass pastures. Lowering stocking rate from 13.9 to 8.3 ewes/ha was a less effective method of increasing seed production of subterranean clover in dryland pastures although it did lead to increased liveweight gain per head.

La synthèse énantiosélective de la (+)-ambruticine S, un produit naturel antifongique a été effectuée au sein de notre groupe. Trois approches ont été développées pour la synthèse du fragment lactone (cycle A). Ces trois voies d’accès au cycle A ont pour intermédiaire commun le methyl α-D-glycopyranoside déjà porteur du diol requis et disponible commercialement à bon prix. Une désoxygénation de l’hydroxyle en C-4 et l’homologation d’un carbone de la chaine latérale en C-6 ont permis l’obtention du cycle lactonique A. Le deuxième projet est une collaboration entre le groupe Hanessian et ISIS Pharmaceuticals afin de développer de nouveaux oligonucléosides antisens. Les nucléosides antisens [4.3.0]-bicycliques cis et trans ont été synthétisés avec succès à partir d’un monosaccharide naturel commun, L-arabinose, porteur des stéréocentres requis. Un réaction clé d’allylation de Sakurai a permis d’obtenir les diastéréoisomères cis et trans dans des conditions de contrôle de type Felkin-Ahn et de contrôle par chélation respectivement. Les composés bicycliques finaux cibles ont été obtenus par une réaction d’aldol intramoléculaire catalyzéé par la proline, par métathèse de fermeture de cycle et par l’application de la méthode de Vorbrüggen pour la synthèse de nucléosides. / An enantioselective synthesis of the antifungal natural product (+)-ambruticin S has been accomplished in our group. For the synthesis of a ring A lactone fragment, three approaches were developed. They all started from commercially available and inexpensive methyl α-D-glycopyranoside, which already possesses the required diol unit. A deletion of the hydroxyl group at C-4 and a one-carbon homologation of the C-6 side chain furnished the ring A lactone. The second project is an ongoing collaboration between the Hanessian group and ISIS pharmaceuticals to develop new antisense oligonucleosides. The cis- and trans-[4.3.0]bicyclic antisense nucleosides were successfully synthesized from a common natural monosaccharide, L-arabinose, which bears the required stereocenters. A key Sakurai allylation led to the cis- and trans diastereomers under Felkin-Ahn and chelation-controlled conditions respectively. The final bicyclic targets were achieved by a practical proline-catalyzed intramolecular aldol reaction and ring-closing metathesis (RCM) strategy, and application of the Vorbrüggen method for nucleoside synthesis.

The aim of this thesis is the evaluation of the risk items of financial statements in the selected joint-stock company, their comparison with the real and genuine picture according to the International Financial Reporting Standards (IFRS). The first part is theoretical and it deals with the characteristics of the balancing of books, its types, financial statements, also the annual report, release of the balancing of books and the external audit. The source of information for me was proffesional literature. The second and practical part focuses on the selected company. I decided for the joint-stock construction company OHL ŽS, a.s. I gathered the information about the company from the annual report of the company, from the internet and also from personal meetings and dialogues. Next, I dealt with the activities connected with the balancing of books. I focused on the procedure of stocktaking, bringing closing operations to book and the course of the balancing of books. After that I concentrated on the individual statements of the balancing of books the balance, the profit and loss statement, the supplement to the balancing of books, overview of cash flow and summary of the changes of the owned capital. At the end I evaluated the risk items of the statements and their information capabilities. The accounting entity provided data for the accounting year 2012, that is the reason for the balancing of books by 31. 12. 2012.